JP5029870B2 - Exposure method and apparatus, immersion member, exposure apparatus maintenance method, and device manufacturing method - Google Patents

Description

  The present invention relates to an exposure technique and a device manufacturing technique for exposing a substrate with exposure light through an optical member and a liquid. Furthermore, the present invention relates to an immersion member that can be used in the exposure technique to form an immersion space filled with a liquid.

  Electronic devices (microdevices) such as semiconductor devices and liquid crystal display devices are so-called photolithography in which a pattern formed on a mask such as a reticle is transferred onto a substrate such as a wafer coated with a photoresist (photosensitive material). It is manufactured by the method of. In this photolithography process, in order to transfer the pattern on the mask onto the substrate through the projection optical system, a step-and-repeat type projection exposure apparatus (so-called stepper) and a step-and-scan type projection exposure An exposure apparatus such as an apparatus (so-called scanning stepper) is used.

  In this type of exposure apparatus, in order to meet the demand for higher resolution (resolution) year by year with the miniaturization of patterns due to high integration of semiconductor devices and the like, the exposure light has a shorter wavelength and a projection optical system. The numerical aperture (NA) has been increased (larger NA). However, shortening the exposure light wavelength and increasing the NA increase the resolution of the projection optical system, but reduce the depth of focus. Therefore, the depth of focus becomes too narrow as it is, and the focus margin during the exposure operation increases. There is a risk of shortage.

  Therefore, an exposure apparatus using an immersion method has been developed as a method of substantially shortening the exposure wavelength and increasing the depth of focus as compared with the air. In this immersion method, a liquid such as water or an organic solvent is supplied from a liquid supply mechanism to a local space between the lower surface of the projection optical system and the substrate surface to form an immersion area. Exposure is performed through a liquid. This makes it possible to improve the resolution by utilizing the fact that the wavelength of the exposure light in the liquid is 1 / n times that in air (where n is the refractive index of the liquid and about 1.4 in the case of water), The depth of focus can be enlarged about n times.

Further, conventionally, in order to maintain the liquid immersion area in a local area, a liquid repellent coating is applied to the substrate surface to make it difficult for the liquid to spread on the substrate surface other than the lower surface of the projection optical system (for example, Patent Document 1) or an air curtain was formed by blowing gas around the immersion area (see, for example, Patent Document 2).
International Publication No. 2005/122221 Pamphlet JP 2005-109488 A

  When exposure processing is performed using the immersion method as described above, the immersion region may be formed with a liquid having a refractive index as high as possible in order to further improve the resolution. However, some liquids with a high refractive index do not have an appropriate liquid repellent coating that can be formed on a photoresist, because the contact angle in the natural state is very small and they are easily adapted to various objects. is there. When such a liquid is used in the immersion method, it is difficult to limit the immersion area to a local area only by the liquid repellent action on the substrate surface.

Further, when such a liquid is used, there is a possibility that the liquid leaks to the surroundings even if the liquid immersion area is limited by the air curtain.
In view of such circumstances, the present invention can perform exposure by the immersion method while suppressing the spread of the liquid even when using a liquid that is easily compatible with other objects or a liquid that does not have an appropriate liquid repellent coating. An object of the present invention is to provide an exposure technique and a device manufacturing technique that can be used.

The first exposure method according to the present invention is an exposure method in which the substrate (P) is exposed with exposure light through the optical member (2) and the liquid (LQ), and is arranged so as to surround the optical path of the exposure light, The liquid is supplied to the inside of the liquid immersion member (70) in which an acute inclined surface (72A) is formed on at least a part of the outer surface on the one end side that is annular and the substrate is opposed to the substrate. A first step of forming an immersion space between the optical member and the substrate; and at least a portion of the liquid leaking out of the immersion member through a gap between the immersion member and the substrate. And a second step of holding at the inclined surface.
Further, in the present invention and the following second and third exposure method inventions, the liquid immersion member having the inclined surface or the second surface has an end surface or the first surface disposed to face the substrate. The outer surface or the second surface is provided on the optical member side with respect to the end surface or the first surface, and the inclined surface or the second surface is from the optical path of the exposure light with respect to the end surface or the first surface. It is formed at an acute angle so as to be closer to the substrate as it is further away.

  A second exposure method according to the present invention is an exposure method in which a substrate (P) is exposed with exposure light via an optical member (2) and a liquid (LQ), and between the optical member and the substrate. The liquid leaks from the immersion space to the outside of the liquid immersion member through a gap between the substrate and one end of the liquid immersion member (70) that forms the liquid immersion space including the optical path of the exposure light. At least a part of the liquid is held by an acutely inclined surface (72A) provided on at least a part of the outer surface on one end side of the liquid immersion member.

  A third exposure method according to the present invention is an exposure method in which a substrate (P) is exposed with exposure light through an optical member (2) and a liquid (LQ), and between the optical member and the substrate. The liquid immersion member passes from the liquid immersion space through the gap between the first surface (70A) of the liquid immersion member (70) that forms the liquid immersion space including the optical path of the exposure light and the substrate. The liquid leaking outside is held by the second surface (72A) of the liquid immersion member that forms an acute angle with the first surface.

  According to these exposure methods of the present invention, when the substrate is exposed by the liquid immersion method, at least a part of the liquid leaking outside the liquid immersion member is guided to the inclined portion (because it spreads wet). The amount of liquid leaking outside the immersion member is reduced. Therefore, even when a liquid that is easily compatible with other objects or a liquid that does not have an appropriate liquid repellent coating that can be applied to a substrate is used, the spread of the liquid can be suppressed.

The first exposure apparatus according to the present invention is arranged to surround the optical path of the exposure light in the exposure apparatus that exposes the substrate (P) with the exposure light through the optical member (2) and the liquid (LQ). And a liquid immersion member (70) in which an acute inclined surface (72A) is formed on at least a part of the outer surface on one end side where the substrate is disposed opposite to the ring, and the inside of the liquid immersion member And a liquid supply part (10) for supplying the liquid to form an immersion space between the optical member and the substrate.
Further, in the present invention and the following second and third exposure apparatus inventions, the liquid immersion member having the inclined surface or the second surface has an end surface or the first surface disposed to face the substrate. The outer surface or the second surface is provided on the optical member side with respect to the end surface or the first surface, and the inclined surface or the second surface is from the optical path of the exposure light with respect to the end surface or the first surface. The inclined surface or the second surface holds at least a part of the liquid leaking to the outside of the liquid immersion member.

  A second exposure apparatus according to the present invention is an exposure apparatus that exposes a substrate (P) with exposure light via an optical member (2) and a liquid (LQ), and between the optical member and the substrate. An acute inclined surface (72A) is formed on at least a part of the outer surface on one end side, which is disposed to form a liquid immersion space including the optical path of the exposure light and is opposed to the substrate. The liquid immersion member (70) and the liquid supply part (10) for supplying the liquid to the liquid immersion space are provided.

  A third exposure apparatus according to the present invention is an exposure apparatus that exposes a substrate (P) with exposure light via an optical member (2) and a liquid (LQ), and between the optical member and the substrate. A first surface (70A) disposed to form an immersion space for the liquid including the optical path of the exposure light and disposed so as to face the substrate, and a second surface (an acute angle with the first surface) 72A) and a liquid supply part (10) for supplying the liquid to the immersion space formed by the liquid immersion member.

According to these exposure apparatuses of the present invention, when one end of the liquid immersion member is opposed to the substrate and the liquid is supplied to the liquid immersion space, at least a part of the liquid leaking to the outside of the liquid immersion member Is guided to the inclined surface (second surface) (spreads wet), and therefore the exposure method of the present invention can be used.
In addition, the first, second, and third liquid immersion members according to the present invention fill the space between the optical member (2) and the substrate (P) with the liquid (LQ) to form a liquid immersion space. The liquid immersion member is attached to an exposure apparatus that exposes the substrate with exposure light through the member and the liquid.

The first liquid immersion member according to the present invention can be disposed so as to surround the optical path of the exposure light, and has a ring-shaped main body portion (70) in which a space for forming the liquid immersion space is formed. ), A liquid flow path (14A) is formed inside the main body, and an acute inclined surface (at least part of the outer surface on one end side where the substrate of the main body is opposed is disposed ( 72A) is formed.
Further, in the present invention and the following second and third liquid immersion member inventions, the main body having the inclined surface or the second surface faces the substrate in a state where the main body is mounted on the exposure apparatus. The outer surface or the second surface is provided on the optical member side with respect to the end surface or the first surface, and the inclined surface or the second surface is the end surface or the first surface. The first surface is formed at an acute angle so as to be closer to the substrate as it is farther from the optical path of the exposure light, and the inclined surface or the second surface has at least a part of the liquid leaking outside the liquid immersion member. Used to hold.

The second liquid immersion member according to the present invention includes a main body portion (70) disposed to form the immersion space between the optical member and the substrate, and the main body portion includes the main body portion (70). A liquid flow path (14A) is formed, and an acute inclined surface (72A) is formed on at least a part of the outer surface on one end side where the substrate of the main body portion is arranged to face.
The third liquid immersion member according to the present invention includes a main body portion (70) arranged to form the liquid immersion space between the optical member and the substrate, and the main body portion includes the main body portion (70). A liquid flow path (14A) is formed, and the main body has a first surface (70A) on which the substrate is disposed facing and a second surface (72A) forming an acute angle with the first surface. It is.

The exposure method of the present invention can be used by using the liquid immersion member of the present invention, and the liquid immersion member can be used as the liquid immersion member of the exposure apparatus of the present invention.
A device manufacturing method according to the present invention uses the exposure method or exposure apparatus of the present invention. According to the present invention, it is possible to perform exposure by a liquid immersion method using a liquid having a high refractive index that is easily adapted to other objects or does not have an appropriate liquid repellent coating. Therefore, in the exposure process, the resolution can be further improved and the depth of focus can be increased, so that a device having a fine pattern can be manufactured with high accuracy and high yield.

  In the exposure apparatus maintenance method according to the present invention, the space between the optical member (2) and the substrate (P) is filled with a liquid (LQ) to form an immersion space, and the optical member and the liquid are interposed therebetween. An exposure apparatus maintenance method for exposing a substrate with exposure light, comprising 1) a step of cleaning the liquid immersion member (70) of the present invention mounted on the exposure apparatus, and 2) a book mounted on the exposure apparatus. Removing the liquid immersion member (70) of the invention, re-mounting the liquid immersion member after cleaning the liquid immersion member, and 3) the liquid immersion member (70) of the present invention mounted on the exposure apparatus ) And at least one of the steps of attaching another liquid immersion member to the exposure apparatus by exchanging with the liquid immersion member.

According to the present invention, even if a foreign object is attached to the liquid immersion member mounted on the exposure apparatus, the liquid immersion method is performed by cleaning the foreign material or replacing it with another clean liquid immersion member. The exposure by can be continued and performed satisfactorily.
In addition, although the reference numerals in parentheses attached to the predetermined elements of the present invention correspond to members in the drawings showing an embodiment of the present invention, each reference numeral of the present invention is provided for easy understanding of the present invention. The elements are merely illustrative, and the present invention is not limited to the configuration of the embodiment.

Hereinafter, an example of a preferred embodiment of the present invention will be described with reference to FIGS.
FIG. 1 shows a scanning exposure type exposure apparatus (projection exposure apparatus) EX comprising a scanning stepper of this example. In FIG. 1, the exposure apparatus EX includes a mask stage MST for supporting a mask M and a substrate P. A substrate stage PST to be supported, an illumination optical system IL for illuminating the mask M supported by the mask stage MST with the exposure light EL, and a projection for projecting a pattern image of the mask M illuminated with the exposure light EL onto the substrate P The optical system PL and a control device CONT including a computer that controls the overall operation of the exposure apparatus EX are provided.

  The exposure apparatus EX of this example is an immersion exposure apparatus to which an immersion method is applied in order to improve the resolution by substantially shortening the exposure wavelength and substantially increase the depth of focus. A liquid supply mechanism 10 for supplying the liquid LQ and a liquid recovery mechanism 20 for recovering the liquid LQ on the substrate P are provided. The exposure apparatus EX, while transferring at least the pattern image of the mask M onto the substrate P, is applied to a part on the substrate P including the projection area AR1 of the projection optical system PL by the liquid LQ supplied from the liquid supply mechanism 10. An immersion area AR2 that is larger than the projection area AR1 and smaller than the substrate P is locally formed. Specifically, the exposure apparatus EX includes an optical path of the exposure light EL between the optical element 2 at the image plane side end portion of the projection optical system PL and the surface of the substrate P arranged on the image plane side. A local immersion method that fills the liquid LQ in the immersion space is adopted, and the mask is formed by irradiating the exposure light EL that has passed through the mask M onto the substrate P via the liquid LQ in the immersion space and the projection optical system PL. The M pattern is projected and exposed onto the substrate P.

As an example, the substrate P is obtained by applying a photoresist (photosensitive material) to the surface of a circular (or rectangular) flat substrate made of a silicon wafer (or glass substrate, ceramic substrate or the like), If necessary, a back coat is formed on the bottom surface of the photoresist, and a protective top coat is formed on the surface.
In addition, a nozzle member 70 described later is disposed in the vicinity of the optical element 2 at the end of the projection optical system PL. The nozzle member 70 is an annular member provided so as to surround the optical element 2 above the substrate P (substrate stage PST) disposed to face the projection optical system PL. In this example, the nozzle member 70 constitutes a part of each of the liquid supply mechanism 10 and the liquid recovery mechanism 20. The nozzle member 70 is provided with a supply port 13 for supplying the liquid LQ to the surface of the substrate P supported by the substrate stage PST. Further, the nozzle member 70 is provided with a rectangular filter member (porous member) 30 made of a lyophilic porous material such as metal or ceramics for removing foreign matters, and the liquid LQ is passed through the filter member 30. A frame-shaped recovery port 23 is provided for recovery. Further, the exposure apparatus EX includes an exhaust mechanism 90 having a suction port 98 provided on the image plane side of the projection optical system PL, specifically, the nozzle member 70.

  In the following description, the case where the bottom surface (lower surface) of the nozzle member 70 and the substrate P are opposed to each other will be described as an example. However, other objects other than the substrate P (for example, the upper surface of the substrate stage PST) The same applies to the case where) faces the bottom surface of the nozzle member 70. In the following, the Z-axis is taken in parallel with the optical axis AX of the projection optical system PL, and the scanning direction (synchronous movement direction, in FIG. The X axis is taken along the direction parallel to the scanning direction, and the Y axis is taken along the non-scanning direction (direction perpendicular to the plane of FIG. 1) perpendicular to the scanning direction. In addition, the directions parallel to the X axis, Y axis, and Z axis are X direction, Y direction, and Z direction, respectively, and the rotation (tilt) directions around the X axis, Y axis, and Z axis are respectively θX direction, The directions are the θY direction and the θZ direction. In this example, the surface of the substrate P and the object plane and the imaging plane of the projection optical system PL are substantially parallel to the XY plane, and the XY plane is substantially a horizontal plane.

First, the illumination optical system IL includes an optical integrator that uniformizes the illuminance of a light beam emitted from an exposure light source (not shown), a condenser lens that collects the exposure light EL from the optical integrator, a relay lens system, and exposure light. It has a variable field stop for setting the illumination area on the mask M by EL in a slit shape. A predetermined illumination area on the mask M is illuminated with the exposure light EL having a uniform illuminance distribution by the illumination optical system IL. In this example, ArF excimer laser light (wavelength 193 nm) is used as the exposure light EL. In addition to this, as the exposure light EL, far ultraviolet light (DUV light) such as an ultraviolet bright line (g-line, h-line, i-line) or KrF excimer laser light (wavelength 248 nm) emitted from a mercury lamp, or Vacuum ultraviolet light (VUV light) such as F ₂ laser light (wavelength 157 nm) is used.

  In this example, decalin (Decalin: Decahydronaphthalene), which is a liquid having a higher refractive index than pure water (water), is used for the liquid LQ supplied to the liquid immersion area AR2 (immersion space). The refractive index for the exposure light EL is said to be about 1.44 for water and about 1.60 for decalin. Decalin can transmit not only ArF excimer laser light but also ultraviolet rays emitted from mercury lamps and far ultraviolet light (DUV light) such as KrF excimer laser light. By using decalin, the resolution of the projection optical system PL can be improved by about 10% and the depth of focus can be increased by about 10% compared to the case of using water, and as a result, a finer pattern can be obtained with high accuracy and It can be formed on a substrate with a high yield.

  However, a liquid with a high refractive index such as decalin generally has a small contact angle with an object compared to water and easily spreads out. Therefore, at present, appropriate liquid repellency that can be formed on a photoresist applied to a substrate. There is no coat. Therefore, the liquid LQ supplied to the liquid immersion area AR2 tends to spread outward on the substrate P as compared with water. In this example, in order to suppress the spread, inclined surfaces 72A, 72B, etc. (see FIG. 5) having acute angles (more preferably lyophilic) with respect to the bottom surface are provided on the outer surface of the nozzle member 70 as described later. Provided.

The present invention is particularly effective when a liquid that has a refractive index of 1.5 or more with respect to the exposure light EL and easily spreads as the liquid LQ, such as decalin.
Next, in FIG. 1, the mask stage MST can move on a mask base (not shown) while holding the mask M, and for example, the mask M is fixed by vacuum suction (or electrostatic suction). The mask stage MST can be moved two-dimensionally in the plane perpendicular to the optical axis AX of the projection optical system PL, that is, the XY plane, and can be slightly rotated in the θZ direction by a mask stage driving device MSTD including a linear motor or the like. The mask stage MST is movable at a scanning speed specified in the X direction, and has a movement stroke in the X direction that can allow at least the entire surface of the mask M to cross the optical axis AX of the projection optical system PL. is doing.

  On the mask stage MST, there is provided a movable mirror 31 (which may also be used as a reflecting surface at the end face of the stage. The same applies to the substrate stage PST). A total of 32 is provided. The position of the mask stage MST (mask M) in the two-dimensional direction and the rotation angle in the θZ direction (or the rotation angle in the θX and θY directions) are measured in real time by the laser interferometer 32, and the measurement result is sent to the control unit CONT. Is output. The control device CONT controls the position of the mask M supported by the mask stage MST by driving the mask stage drive device MSTD based on the measurement result of the laser interferometer 32.

  The projection optical system PL projects the pattern of the mask M onto the substrate P at a predetermined projection magnification β, and includes a plurality of optical elements (lenses in this example) 2 provided at the front end portion on the substrate P side. These optical elements are supported by a lens barrel PK. The projection optical system PL is a reduction system having a projection magnification β of, for example, 1/4 or 1/5. The projection optical system PL is disposed in an opening provided in the column 35 and is fixed by a flange portion PF. The projection optical system PL may be a unity magnification system or an enlargement system, and includes a refractive system that does not include a reflective optical element, a reflective system that does not include a refractive optical element, or a refractive optical element and a reflective optical element. Any of catadioptric systems may be used. Further, the projection image generated in the projection area AR1 of the projection optical system PL may be either an inverted image or an erect image. Further, the projection area AR1 is an on-axis area including the optical axis AX within the field of the projection optical system PL. For example, the projection area AR1 is a so-called inline-type catadioptric projection optical system disclosed in International Publication No. 2004/107011. Similarly, an off-axis region that does not include the optical axis AX may be used. In this example, the projection optical system PL is placed on the column 35. However, as disclosed in, for example, International Publication No. 2006/038952 pamphlet, above the position in FIG. 1 (+ Z side). The projection optical system PL may be suspended and supported with respect to the column 35 disposed in the position.

The optical element 2 at the tip of the projection optical system PL of this example is exposed from the lens barrel PK, and the liquid LQ in the liquid immersion area AR2 comes into contact therewith. The optical element 2 is made of meteorite. Since the meteorite surface has a high affinity with the liquid LQ, the liquid LQ can be brought into close contact with almost the entire contact surface (end surface) 2A of the optical element 2 with the liquid. The optical element 2 may be quartz having high affinity with the liquid LQ. Further, the contact surface 2A of the optical element 2 is subjected to a lyophilic process such as adhesion of magnesium fluoride (MgF ₂ ), aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO ₂ ), etc. You may make it raise the affinity of. Alternatively, as a lyophilic treatment, for example, a larger lyophilic property can be imparted to the contact surface 2A of the optical element 2 by forming a thin film with a substance having a molecular structure having a large polarity such as alcohol.

  The substrate stage PST can move while holding the substrate P, and includes an XY stage 53 and a Z tilt stage (substrate table) 52 mounted on the XY stage 53. The XY stage 53 is supported in a non-contact manner on the stage base SB via a gas bearing (air bearing) (not shown). The XY stage 53 (substrate stage PST) can be moved two-dimensionally in a plane perpendicular to the optical axis AX of the projection optical system PL, that is, in the XY plane, and minutely in the θZ direction by a substrate stage driving device PSTD including a linear motor and the like. It can be rotated. A Z tilt stage 52 is mounted on the XY stage 53. The Z tilt stage 52 is movably provided in the Z direction, the θX direction, and the θY direction. The substrate stage driving device PSTD is controlled by the control device CONT. The substrate P is held on the Z tilt stage 52 by, for example, vacuum suction or the like via the substrate holder PH.

  A recess 50 is provided on the Z tilt stage 52, and a substrate holder PH for holding the substrate P is disposed in the recess 50. The upper surface 51 of the Z tilt stage 52 other than the recess 50 is a flat surface that is substantially the same height (level) as the surface of the substrate P held by the substrate holder PH. Since the upper surface 51 that is substantially flush with the surface of the substrate P is provided around the substrate P, the liquid LQ is held on the image surface side of the projection optical system PL even when the edge region E of the substrate P is subjected to immersion exposure. The liquid immersion area AR2 can be formed satisfactorily. Further, since there is a gap of about 0.1 to 2 mm between the edge portion of the substrate P and the flat surface (upper surface) 51 provided around the substrate P, the liquid LQ flowing into the gap is recovered. Therefore, an inflow port of a pipe for discharging the liquid LQ to an external collection device (not shown) may be provided on the bottom surface side of the substrate holder PH in the Z tilt stage 52. There may be a step between the surface of the substrate P and the upper surface 51 of the Z tilt stage 52.

  Since the surface of the substrate P is coated with a photoresist, the type of liquid repellent coat that can be applied thereon is limited, but the upper surface 51 of the Z tilt stage 52 is formed of an arbitrary liquid repellent material. Or any liquid repellent coat can be applied thereon. Therefore, by making the upper surface 51 lyophobic with respect to the liquid LQ (contact angle with the liquid LQ is, for example, 90 to 130 °), the liquid LQ toward the outside (upper surface 51 side) of the substrate P during the immersion exposure. Can be suppressed. Further, the liquid LQ in the liquid immersion area AR2 can be smoothly collected, and the inconvenience that the liquid LQ remains on the upper surface 51 can be prevented. In order to make the upper surface 51 liquid repellent with respect to the liquid LQ in this way, the upper surface 51 may be formed of a material having liquid repellent properties such as polytetrafluoroethylene (Teflon (registered trademark)). Alternatively, a liquid repellent material such as a fluorine-based resin material such as polytetrafluoroethylene, an acrylic resin material, or a silicon-based resin material that is insoluble in the liquid LQ with respect to a part or the entire area of the upper surface 51. A functional material may be applied.

  In addition, a movable mirror 33 is provided on the substrate stage PST (Z tilt stage 52), and a laser interferometer 34, which is partly disposed so as to face the movable mirror 33, is provided. In this example, the upper surface of the movable mirror 33 is also substantially flush with the upper surface of the upper surface 51 of the Z tilt stage 52. The position and rotation angle of the substrate stage PST (substrate P) in the XY plane are measured in real time by the laser interferometer 34, and the measurement result is output to the control device CONT. The controller CONT positions the substrate P supported by the substrate stage PST by driving the substrate stage driving device PSTD including a linear motor and the like based on the measurement result of the laser interferometer 34. The laser interferometer 34 may be capable of measuring the position of the substrate stage PST in the Z direction and rotation information in the θX and θY directions, as disclosed in, for example, International Publication No. 1999/28790.

  Further, the exposure apparatus EX detects the position of the surface of the substrate P supported by the substrate stage PST (substrate holder PH), which will be described later (hereinafter referred to as “AF sensor”) 80 (see FIG. 2). It has. The detection result of the AF sensor is output to the control device CONT. The control device CONT detects position information in the Z direction on the surface of the substrate P and tilt information in the θX and θY directions based on the detection result of the AF sensor, and controls the Z tilt stage 52 based on the detection results. The Z tilt stage 52 controls the focus position and tilt angle of the substrate P to adjust the surface of the substrate P to the image plane of the projection optical system PL, and the XY stage 53 positions the substrate P in the X direction and the Y direction. . Needless to say, the Z tilt stage and the XY stage may be provided integrally.

Next, the liquid supply mechanism 10, the liquid recovery mechanism 20, and the nozzle unit 66 (nozzle member 70) will be described with reference to FIGS. 2 is a schematic perspective view showing the nozzle member 70, and FIG. 3 is a perspective view of the nozzle member 70 viewed from the bottom surface 70A side.
In FIG. 1, the nozzle member 70 is an annular member that is disposed so that the substrate P (substrate stage PST) is opposed to one end (bottom surface) side thereof and surrounds the optical element 2 at the end of the projection optical system PL. It is. The nozzle member 70 has a hole portion 70H in which the optical element 2 can be disposed at the center thereof. The nozzle member 70 is formed of a lyophilic material that is easily compatible with the liquid LQ, for example, a metal such as aluminum, titanium, stainless steel, or duralumin, or an alloy containing these. Alternatively, the nozzle member 70 may be made of a lyophilic and light transmissive material such as glass (quartz).

  One end of a substantially L-shaped connecting member 68A, 68B, 68C (see FIG. 2) is fixed at three positions on the upper surface of the nozzle member 70, and below the column 35 supporting the projection optical system PL, the projection optical system. Support plates 36A and 36B are fixed to a column (not shown) (vibrated from column 35) so as to sandwich PL in the X direction. Then, substantially L-shaped support members 38A and 38B (38B not shown) are fixed at two positions in the Y direction on the bottom surface of one support plate 36A, and the substantially L-shape is formed on the bottom surface of the other support plate 36B. The support member 38C is fixed. Furthermore, for example, voice coil motor type fixed to the support members 38A to 38C (EI core type motor combining an E-shaped core and an I-shaped core, etc.) 39A to 39C (39B is not shown) ) Are connected to the other ends of the connecting members 68A to 68C. For example, the control device CONT drives the drive units 39A to 39C based on the measurement value of the AF sensor 80 (see FIG. 2). The drive units 39A to 39C independently drive the connecting members 68A to 68C within a predetermined stroke in the Z direction. Accordingly, the position of the nozzle member 70 in the Z direction and the angles in the θX and θY directions can be controlled. The nozzle unit 66 is configured to include the nozzle member 70 and the connecting members 68A to 68C, and includes the support members 38A to 38C and the drive units 39A to 39C to adjust the position and leveling of the nozzle unit 66 (nozzle member 70) in the Z direction. A nozzle moving mechanism 37 to be controlled is configured.

  In this example, the nozzle unit is provided via the nozzle moving mechanism 37 so that the gap between the bottom surface of the nozzle member 70 and the surface of the substrate P is maintained within a predetermined range during exposure by the scanning exposure method and the liquid immersion method. 66 positions and angles are controlled. In addition, when the flatness of the substrate P is good, or when the leakage amount of the liquid LQ to the outside of the nozzle member 70 is small (details will be described later), the nozzle unit 66 is not provided without providing the nozzle moving mechanism 37. It may be simply fixed to the measurement system support plate 36. The nozzle unit 66 may be fixed to the column 35 or the like via the moving mechanism 37 and / or the vibration isolating mechanism or directly. In this example, the nozzle unit 66 is provided in a column that is vibrationally separated from the column 35, for example, a column that is fixed to the installation surface of the exposure apparatus via a vibration isolation mechanism independently of the column 35. 1 is configured such that the projection optical system PL is suspended and supported from the column 35, for example, the nozzle unit 66 is mounted on a frame that is suspended and supported from the column 35 independently of the projection optical system PL. It may be provided.

  In FIG. 2, the liquid supply mechanism 10 is for supplying the liquid LQ to the image plane side of the projection optical system PL, and includes a liquid supply unit 11 capable of delivering the liquid LQ, and one end of the liquid supply unit 11. Supply pipes 12A and 12B (represented by the supply pipe 12 in FIG. 1), the other ends of which are connected to one ends of supply flow paths 14A and 14B formed inside the nozzle member 70, A liquid LQ formed on the nozzle member 70, connected to the other ends of the supply channels 14A and 14B, and substantially parallel to the surface of the substrate P disposed on the image plane side of the projection optical system PL, that is, substantially parallel to the XY plane. Supply ports 13A and 13B (see FIG. 3). The supply ports 13A and 13B are represented by the supply port 13 in FIG. The liquid supply unit 11 includes a tank that stores the liquid LQ, a temperature control device that adjusts the temperature of the liquid LQ to be supplied, a filter device that removes foreign matter in the liquid LQ, and a pressure pump. When the liquid immersion area AR2 is formed on the substrate P, the liquid supply mechanism 10 receives the optical element 2 on the image plane side of the projection optical system PL and the image plane side from the supply ports 13A and 13B formed in the nozzle member 70. The liquid LQ is supplied between the substrate P and the substrate P. Note that the liquid supply mechanism 10 of the exposure apparatus EX does not have to include all of the tank, the temperature control apparatus, the filter apparatus, the pressure pump, and the like, and at least a part of them is a factory where the exposure apparatus EX is installed. You may substitute the equipment.

  The liquid recovery mechanism 20 is for recovering the liquid LQ on the image plane side of the projection optical system PL, and has a liquid recovery part 21 capable of recovering the liquid LQ and one end thereof connected to the liquid recovery part 21. A recovery pipe 22 having the other end connected to one end of a recovery channel 24 (see FIG. 3) formed inside the nozzle member 70, and a bottom surface of the nozzle member 70. The recovery port 23 (refer FIG. 1) connected to the edge part is provided. The liquid recovery unit 21 includes, for example, a vacuum system (suction device) such as a vacuum pump, a gas-liquid separator that separates the recovered liquid LQ and gas, a tank that stores the recovered liquid LQ, and the like. As a vacuum system, a vacuum system such as a vacuum pump, a gas-liquid separator, and a tank are not provided in the exposure apparatus EX, and at least one of them may be replaced with equipment in a factory where the exposure apparatus EX is disposed. . The liquid recovery mechanism 20 is supplied from the liquid supply mechanism 10 via the recovery port 23 formed in the nozzle member 70 so that the liquid immersion area AR2 is formed in a predetermined space on the image plane side of the projection optical system PL. A predetermined amount of the liquid LQ is collected.

  A gap is provided between the inner side surface of the hole 70H of the nozzle member 70 and the side surface 2T of the optical element 2 of the projection optical system PL in order to vibrationally separate the optical element 2 and the nozzle member 70. . In addition, the liquid supply mechanism 10 and the liquid recovery mechanism 20 including the nozzle member 70 and the projection optical system PL are supported by separate support mechanisms, and are separated vibrationally. Thereby, vibration generated in the liquid supply mechanism 10 including the nozzle member 70 and the liquid recovery mechanism 20 is prevented from being transmitted to the projection optical system PL side. In addition, a seal member (packing) such as a V-ring or an O-ring formed of a material with less metal ion elution is disposed in the gap between the hole 70H of the nozzle member 70 and the side surface 2T of the optical element 2. In addition to preventing the liquid LQ forming the liquid immersion area AR2 from leaking from the gap, it prevents the gas (bubbles) from entering the liquid LQ forming the liquid immersion area AR2 from the gap. is doing. Further, since the seal member has flexibility, the nozzle member 70 is allowed to move relative to the optical element 2 in the Z direction within a predetermined stroke.

  As shown in FIG. 3, a concave portion 77 having a longitudinal direction in the Y direction is formed on the bottom surface 70A of the nozzle member 70 on which the substrate P is opposed, and a deeper concave portion 78 is formed on the inside thereof. The hole 70 </ b> H passes through the center of the recess 78. The recess 78 includes an inner surface 79X that faces the Y axis in parallel, an inner surface 79Y that faces the X axis, and an inclined surface (tapered surface) 79T that connects the inner surface 79X and the inner surface 79Y. It has a side surface 79.

  The two circular supply ports 13A and 13B are arranged in the Y direction on the inner side surface 79X (surface on the scanning direction (X direction) side with respect to the projection area AR1) substantially parallel to the YZ plane forming the recess 78. It is provided side by side.

  Inside the nozzle member 70, two supply passages 14A and 14B communicating with the supply ports 13A and 13B are formed. The supply passages 14A and 14B are connected to the supply pipes 12A and 12B, and the supply pipes 12A and 12B are connected to each other. In the middle, flow controllers 16A and 16B called mass flow controllers that are delivered from the liquid supply unit 11 and control the amount of liquid supplied per unit time to the supply ports 13A and 13B are provided. Control of the liquid supply amount by the flow rate controllers 16A and 16B is performed under the command of the control device CONT. In this example, the interval between the supply ports 13A and 13B in the Y direction is longer than at least the length of the projection area AR1 in the Y direction. The liquid supply mechanism 10 can simultaneously supply the liquid LQ above the substrate P from each of the supply ports 13A and 13B.

  Further, the recess 77 has a boundary portion set by a step 73 (see FIG. 5) on the bottom surface 70A of the nozzle member 70, and the interval between the bottom surface 70A and the substrate P is a flat surface substantially parallel to the XY plane. This is set to be narrower than the distance between the substrate P and the substrate P. The recovery port 23 is formed in an annular shape on the inner surface of the recess 77 so as to surround the supply ports 13A and 13B and the projection area AR1 and outside the recess 78. An annular filter member 30 is disposed so as to cover the entire surface of the recovery port 23. The liquid LQ for forming the liquid immersion area AR2 is supplied between the projection area AR1 of the projection optical system PL and the recovery port 23 via the supply ports 13A and 13B.

  The projection area AR1 of the projection optical system PL is set in a rectangular shape whose longitudinal direction is the Y direction (non-scanning direction), and the liquid immersion area AR2 filled with the liquid LQ substantially includes the projection area AR1. In the region surrounded by the annular collection port 23 and during exposure of the substrate P, it is locally formed on a part of the substrate P. The liquid immersion area AR2 only needs to cover at least the projection area AR1, and the entire area surrounded by the recovery port 23 does not necessarily have to be the liquid immersion area.

The inner surface of the recess 78 (a flat surface substantially parallel to the XY plane) is formed at a position higher than the liquid contact surface 2A of the optical element 2 and the inner surface of the recess 77 (so as to be far from the substrate P). ing. The liquid contact surface 2 </ b> A of the optical element 2 is exposed to the substrate P side from the inner surface of the recess 78.
Further, a step is also formed between the liquid contact surface 2 A of the optical element 2 and the inner surface of the recess 77. Therefore, the distance between the surface of the substrate P and the liquid contact surface 2 </ b> A of the optical element 2 is longer than the distance between the surface of the substrate P and the inner surface of the recess 77.

  When the liquid immersion area AR2 is formed, the liquid LQ in the liquid immersion area AR2 comes into contact with the concave portion 78 and the concave portion 77. Therefore, the concave portion 78 and the concave portion 77 are lyophilic like the liquid contact surface 2 </ b> A of the optical element 2. That is, the lyophilic process is performed on at least the recess 78 and the recess 77 in the bottom surface of the nozzle member 70. If the nozzle member 70 is formed of a lyophilic material, the recesses 78 and 77 do not need to be lyophilic.

  As shown in FIG. 2, the exposure apparatus EX of this example includes a so-called oblique incidence type AF sensor 80 that detects surface position information of the surface of the substrate P held by the substrate stage PST. The AF sensor 80 includes a light projecting unit 81 that projects the detection light La on the substrate P from an oblique direction via the liquid LQ in the liquid immersion area AR2, and a light receiving unit that receives the reflected light of the detection light La reflected by the substrate P. 82. As the configuration of the AF sensor 80, for example, the one disclosed in JP-A-8-37149 can be used. The AF sensor 80 may be configured to detect surface position information of the substrate P without passing through the liquid LQ in the liquid immersion area AR2.

  In the nozzle member 70, concave portions 75 and 76 toward the center (projection optical system PL side) are formed on the side surfaces 72G and 72H on the −Y direction side and the + Y direction side, respectively. One recess 75 is provided with a first optical member 83 that can transmit the detection light La emitted from the light projecting portion 81 of the AF sensor 80, and the other recess 76 receives the detection light La reflected on the substrate P. A transmissive second optical member 84 is provided.

  As shown in FIG. 3, the second optical member 84 disposed in the recess 76 in FIG. 2 is exposed at a part of the + Y-direction inner surface 79Y of the recess 78 formed on the bottom surface of the nozzle member 70. An opening 79K for exposing the first optical member 83 disposed in the recess 75 is formed in a part of the inner surface 79Y in the −Y direction of the recess 78. ing. In the example illustrated in FIG. 2, the light projecting unit 81 and the light receiving unit 82 are provided at positions separated from the projection region AR1 on each of the ± Y direction sides across the projection region AR1. As described above, the control apparatus CONT in FIG. 1 determines the position information in the Z direction on the surface of the substrate P and the θX and θY directions based on the focus positions at a plurality of points on the substrate P detected by the AF sensor 80. Inclination information can be obtained. In this example, the detection light La of the AF sensor 80 is irradiated substantially parallel to the YZ plane, but may be irradiated substantially parallel to the XZ plane.

  As described above, the optical members 83 and 84 in FIG. 2 constitute a part of the optical system of the AF sensor 80 and a part of the nozzle member 70. In other words, in this example, part of the nozzle member 70 also serves as part of the AF sensor 80. Then, by providing the recess 78 on the bottom surface of the nozzle member 70, the AF sensor 80 can smoothly irradiate the desired region on the substrate P with the detection light La at a predetermined incident angle.

  In this example, the AF sensor 80 detects the relative position in the Z direction of the substrate P with respect to a reference plane, for example, the imaging plane of the projection optical system PL, at a plurality of measurement points, and the imaging plane and the bottom surface of the nozzle member 70. Since the positional relationship with 70A is known (however, it is updated in accordance with the movement of the imaging surface and / or the nozzle member 70), the bottom surface 70A of the nozzle member 70 and the substrate P are determined from the measurement result of the AF sensor 80. The distance g from the surface can be determined. Then, the contact between the bottom surface 70A of the nozzle member 70 and the substrate P can be avoided by moving the nozzle member 70 so that the obtained interval g is maintained at a set value that satisfies the following formula (1). It is possible. In this example, the gap sensor for measuring the gap g is also used as the AF sensor 80, but the gap sensor (described later) may be provided separately from the AF sensor 80. If the distance between the imaging plane of the projection optical system PL on which the surface of the substrate P is disposed and the bottom surface 70A of the nozzle member 70 is large enough to avoid the contact, the measuring device for the distance g (and the above-mentioned) The nozzle moving mechanism 37) may not be provided.

  In FIG. 2, the exposure apparatus EX includes an exhaust mechanism 90 that exhausts the gas on the image plane side of the projection optical system PL. The exhaust mechanism 90 includes an exhaust unit 91 including a vacuum system (a suction device) such as a vacuum pump, a gas-liquid separator that separates the recovered liquid LQ and gas, a tank that stores the recovered liquid LQ, and the like. I have. As a vacuum system, a vacuum system such as a vacuum pump, a gas-liquid separator, and a tank are not provided in the exposure apparatus EX, and at least one of them may be replaced with equipment in a factory where the exposure apparatus EX is disposed. .

One end of two recovery pipes 95A and 95B (represented by the recovery pipe 95 in FIG. 1) is connected to the exhaust part 91, and the other end of the recovery pipes 95A and 95B is the interior of the nozzle member 70. Are connected to one end of the recovery channels 96A, 96B. One end portions of the recovery channels 96 </ b> A and 96 </ b> B are formed in the recesses 75 and 76 of the nozzle member 70.
As shown in FIG. 3, in the recess 78 of the nozzle member 70, two suction ports 98A and 98B (represented by the suction port 98 in FIG. 1) are provided in the vicinity of the optical element 2 of the projection optical system PL. The suction ports 98A and 98B are connected to the other end portions of the recovery channels 96A and 96B formed in the nozzle member 70, respectively. As a result, each of the suction ports 98A and 98B is connected to the exhaust part 91 via the recovery passages 96A and 96B and the recovery pipes 95A and 95B of FIG. By driving the exhaust unit 91, the gas on the image plane side of the projection optical system PL can be discharged (suctioned and negative pressure) via the suction ports 98 </ b> A and 98 </ b> B disposed in the vicinity of the optical element 2. it can. Further, since the exhaust unit 91 includes a vacuum system and a gas-liquid separator, the liquid LQ on the image plane side of the projection optical system PL can also be recovered through the suction ports 98A and 98B.

The suction ports 98A and 98B are provided in the vicinity of the projection area AR1 of the projection optical system PL in the recess 78, and are provided on both sides of the projection area AR1 with respect to the non-scanning direction (Y direction). A plurality of suction ports 98A and 98B (two in FIG. 3) are provided corresponding to the supply ports 13A and 13B.
In this example, the nozzle member 70 (nozzle unit 66) constitutes a part of each of the liquid supply mechanism 10, the liquid recovery mechanism 20, and the exhaust mechanism 90. The supply ports 13A and 13B constituting the liquid supply mechanism 10 eject the liquid LQ substantially in parallel with the surface of the substrate P disposed on the image plane side of the projection optical system PL, so that the image plane side of the projection optical system PL. To supply liquid LQ. The recovery port 23 constituting the liquid recovery mechanism 20 is provided so as to surround the projection area AR1, the supply ports 13A and 13B, and the suction ports 98A and 98B.

  The operations of the liquid supply unit 11 and the flow rate controllers 16A and 16B are controlled by the control device CONT. When supplying the liquid LQ onto the substrate P, the control device CONT sends out the liquid LQ from the liquid supply unit 11, and projects from the supply ports 13A and 13B via the supply pipes 12A and 12B and the supply flow paths 14A and 14B. The liquid LQ is supplied to the image plane side of the optical system PL. The supply ports 13A and 13B may be provided so as to face the substrate P or obliquely, and the liquid LQ may be ejected substantially perpendicularly or obliquely to the surface of the substrate P.

The liquid recovery operation of the liquid recovery unit 21 is controlled by the control device CONT. The control device CONT can control the liquid recovery amount per unit time by the liquid recovery unit 21. The liquid LQ on the substrate P recovered from the recovery port 23 is recovered by the liquid recovery part 21 via the recovery flow path 24 and the recovery pipe 22 of the nozzle member 70 of FIG.
In this example, the recovery port 23 is formed in an annular shape, and each of the recovery channel 24, the recovery pipe 22, and the liquid recovery unit 21 connected to the recovery port 23 is provided one by one. The recovery port 23 may be divided into a plurality of portions, and the recovery pipes 22 may be provided according to the number of the recovery ports 23 divided into a plurality of portions. Even when the collection port 23 is divided into a plurality of portions, the plurality of collection ports 23 may be disposed so as to surround the projection area AR1, the supply ports 13A and 13B, and the suction ports 98A and 98B. preferable.

4 is a bottom view showing the positional relationship between the supply ports 13A, 13B and the suction ports 98A, 98B formed in the nozzle member 70 of FIG. 3. In FIG. 4, in this example, the suction ports 98A and the supply ports are shown. The port 13A, the suction port 98B, and the supply port 13B are provided so as to be aligned along a straight line substantially parallel to the X axis.
Each of the supply ports 13A and 13B is provided on the inner side surface 79X facing substantially the + X direction side, and the substrate P on which the liquid LQ delivered from the liquid supply unit 11 is disposed on the image plane side of the projection optical system PL. Spouts almost parallel to the surface. And one supply port 13A spouts the liquid LQ toward the inner surface 79Y which faces the + Y direction side arrange | positioned in the vicinity of the supply port 13A among the inner surfaces surrounding the recessed part 78. As shown in FIG. The other supply port 13B ejects the liquid LQ toward the inner side surface 79Y facing the −Y direction side symmetrically with the supply unit 13A. That is, each of the supply ports 13A and 13B blows out the liquid LQ substantially parallel to the XY plane and in an inclined direction with respect to the X direction. Further, each of the supply ports 13A and 13B ejects the liquid LQ along a taper surface 79Ta provided closest to the plurality of taper surfaces 79T, and the ejected liquid LQ is disposed in the vicinity thereof. It is applied to the inner surface 79Y.

  The liquid LQ ejected from the supply ports 13A and 13B toward the inner surface 79 forms a vortex VF in the liquid LQ, and the suction ports are positioned so that the vicinity of the center of the vortex VF is located at the suction ports 98A and 98B, respectively. 98A and 98B are arranged. Therefore, by sucking the gas from the suction ports 98A and 98B into the exhaust part 91 of FIG. 2, a part of the vortex VF is sucked into the exhaust part 91, and the vortex VF is stably maintained. As a result, the liquid LQ is always stably supplied to the liquid immersion area AR2.

  5 is a cross-sectional view taken along the line AA in FIG. 4. In FIG. 5, the supply flow path 14A formed in the nozzle member 70 has one end connected to the supply pipe 12A and the other end. Is connected to the liquid supply port 13A. The supply pipe 12B, the supply flow path 14B, and the supply port 13B in FIG. 2 have the same configuration. One end of the recovery channel 24 in the nozzle member 70 is connected to the recovery pipe 22, and the other end is connected to a part of the recovery port 23. The recovery channel 24 is also connected to a plurality of branch channels 24s communicating with other locations of the recovery port 23, and the liquid LQ on the substrate P moves the filter member 30 together with the surrounding gas (air) to + Z. After passing in the direction, it is sucked and collected from the entire surface of the collection port 23 to the liquid collection unit 21 through the collection channel 24 and the collection tube 22 almost uniformly. In order to form the supply channels 14A and 14B and the recovery channel 24 (branch channel 24s) having complicated paths in the nozzle member 70, the nozzle member 70 is manufactured by stacking, for example, a plurality of members in the Z direction. May be.

  In FIG. 5, a recess 77 substantially parallel to the surface (XY plane) of the substrate P is formed at the center (projection optical system PL side) of the bottom surface 70 </ b> A of the nozzle member 70 constituting the nozzle unit 66 with the annular step 73 as a boundary. A concave portion 78 is formed at the center of the concave portion 77 with the annular inner side surface 79 as a boundary portion, and a hole portion 70H for passing the optical element 2 at the tip of the projection optical system PL is formed at the central portion of the concave portion 78. Yes. Further, the liquid LQ in FIG. 1 is supplied to the liquid immersion space inside the concave portion 77 and the concave portion 78 inside the step 73 to form the liquid immersion region AR2 in FIG. An annular collection port 23 is formed in the outer peripheral portion of the recess 77 near the step 73, and supply ports 13A and 13B (see FIG. 3) are formed on the inner side surface 79 inside the collection port 23. Therefore, in this example, since the liquid LQ for forming the liquid immersion space is supplied and collected inside the step 73 provided on the bottom surface 70A of the nozzle member 70, the configuration is simplified. .

It is also possible to provide an annular recess on the bottom surface 70A so as to surround the step 73, and to provide the recovery port 23 for the liquid LQ in this recess. Although this structure is complicated, the recovery rate of the liquid LQ can be improved.
Further, as described above, the recesses 77 and 78 for forming the liquid immersion area AR2 of the nozzle member 70 are subjected to a lyophilic process, but the outer peripheral edge is formed on the bottom surface 70A of the nozzle member 70 on the outer side. A liquid repellency treatment that repels the liquid LQ is applied to the entire area excluding the portion. Accordingly, the bottom surface 70A has a liquid repellency having a lower affinity for the liquid LQ than the concave portions 77 and 78 on the inside and the liquid contact surface 2A of the optical element 2. As the liquid repellent treatment for the bottom surface 70A, for example, a non-soluble liquid repellent material is applied to the liquid LQ such as a fluorine resin material such as polytetrafluoroethylene, an acrylic resin material, or a silicon resin material. Or the process of depositing the thin film (single layer or multiple layers) which consists of the said liquid repellent material is mentioned.

  However, the liquid LQ of this example has a high refractive index, and in FIG. 5, there is no appropriate liquid repellent coat that can be applied on the photoresist PR applied to the base material SU of the substrate P. The liquid LQ supplied to the recess 77 may pass through a gap (flow path) between the bottom surface 70 </ b> A and the surface of the substrate P and leak to the outside of the nozzle member 70. Accordingly, in order to suppress the spread of the leaked liquid LQ, the side surface in the scanning direction (X direction) of the nozzle member 70 adjacent to the bottom surface 70A intersects the bottom surface 70A at an acute angle θ that is smaller than 90 °. Inclined surfaces 72A and 72B are formed.

  The inclined surfaces 72A and 72B are preferably lyophilic with respect to the liquid LQ (the contact angle is 90 ° or less). In this example, the lyophilicity with respect to the liquid LQ of the inclined surfaces 72A and 72B is set higher than the lyophilicity with respect to the liquid LQ on the surface of the substrate P. Highly lyophilic means that the adhesion force to the liquid (intermolecular force when atoms are regarded as monoatomic molecules) is large and the contact angle of the liquid is small. In other words, the surface tension is apparently reduced on a highly lyophilic object. Therefore, if the same amount of the liquid LQ is dropped onto the surface A and the surface B while both the inclined surface 72A (referred to as surface A) and the surface of the substrate P (referred to as surface B) are held horizontally, the surface A The spreading radius of the upper liquid LQ is larger than the spreading radius of the liquid LQ on the surface B. That is, the adhesion force that tries to spread the liquid LQ on the surface A is larger than the adhesion force that tries to spread the liquid LQ on the surface B.

Specifically, the nozzle member 70 itself is a lyophilic material with respect to the liquid LQ as described above, for example, a metal such as aluminum, titanium, stainless steel, or duralumin, an alloy containing these, glass (quartz), or the like. In the case of being formed from the above material, the lyophilicity of the inclined surfaces 72A and 72B with respect to the liquid LQ remains as it is and is higher than the lyophilicity of the surface of the substrate P. On the other hand, when the nozzle member 70 is made of a material that is not so lyophilic, for example, MgF ₂ , Al ₂ O ₃ , SiO _2, etc. are adhered to the inclined surfaces 72A and 72B in advance. The lyophilic treatment is performed so that the lyophilic property is higher than the lyophilic property of the surface of the substrate P.

  In order to widen the difference between the lyophilicity of the inclined surfaces 72A and 72B and the lyophilicity of the surface of the substrate P, a liquid repellent coating effective for the liquid LQ, for example, may be formed on the surface of the substrate P. Good. Thereby, if the lyophilicity with respect to the liquid LQ on the surface of the substrate P is slightly reduced, the lyophilicity of the inclined surfaces 72A and 72B can be relatively increased. Thus, by making the lyophilicity of the inclined surfaces 72A and 72B larger than the lyophilic property of the surface of the substrate P, out of the liquid LQ leaking to the outside of the nozzle member 70, it flows onto the inclined surfaces 72A and 72B. As a result, the ratio of the liquid retained (wetting and spreading) can be increased. Since the liquid tends to be integrated by surface tension, the amount of the liquid LQ leaking outside the nozzle member 70 is thereby reduced.

  Further, when the substrate P is exposed by the immersion method, in order to reduce the amount of the liquid LQ leaking outside from the gap between the bottom surface 70A of the nozzle member 70 and the surface of the substrate P, the bottom surface 70A and the substrate P can be reduced. It is preferable to make the distance g from the surface as small as possible. However, during exposure, the substrate P moves (relatively moves) in the X direction parallel to the image plane of the projection optical system PL, and fine irregularities are formed on the surface of the substrate P by the previous steps. If the gap g is too small, the bottom surface 70A may come into contact with the surface of the substrate P due to the movement of the substrate P in the X direction. Therefore, it is preferable that the gap g be within a predetermined range as follows as an example.

10 μm ≦ g ≦ 200 μm (1)
If the gap g is smaller than the lower limit of the expression (1), the bottom surface 70A may come into contact with the surface of the substrate P when the substrate P moves in the X direction during scanning exposure. Further, when the gap g is larger than the upper limit of the formula (1), the amount of the liquid LQ leaking outside from between the bottom surface 70A and the surface of the substrate P may be too large. For example, when the recovery speed of the liquid LQ by the liquid recovery mechanism 20 is increased, the interval g may be larger than the upper limit of the expression (1). In addition, when the interval g can be detected and adjusted as described above, the interval g may be smaller than the lower limit of Expression (1).

Further, in this example, even if the substrate P moves in the X direction during scanning exposure, the interval g is maintained at the bottom surface 70A of the nozzle member 70 in the vicinity of the value specified in advance in the expression (1). In addition, based on the measurement value of the AF sensor 80 in FIG. 2, the control device CONT drives the connecting members 68A to 68C fixed to the nozzle member 70 via the nozzle moving mechanism 37 in the Z direction in a servo manner.
In order to more accurately control the distance between the bottom surface 70A of the nozzle member 70 and the surface of the substrate P, as shown in FIG. 5, for example, electrostatic capacity type gap sensors 74A, 74B, 74C (74C is not shown) may be provided. Since the dielectric constant of the liquid LQ is higher than the dielectric constant of the gas, the measured values of the gap sensors 74A, 74B and the like are corrected by the known dielectric constant of the liquid LQ. In this case, the control device CONT drives the nozzle moving mechanism 37 in a servo manner based on the measurement values of the gap sensors 74A, 74B, etc., so that the distance g between the bottom surface 70A of the nozzle member 70 and the surface of the substrate P is more accurate. Can be controlled to the target value. Instead of the gap sensors 74A, 74B, etc., for example, an optical sensor using light in a wavelength range that does not expose the photoresist PR of the substrate P may be used. Further, a sensor (not shown) that measures position information (including tilt information) of the nozzle member 70 in the Z direction, the position of the substrate stage PST (Z tilt stage 52) in the Z direction, and the rotation amount in the θX and θY directions ( The interval g may be obtained from both measurement results of the laser interferometer 34 capable of measuring the rolling amount and the pitching amount).

A preferable range of the predetermined angle θ formed by the inclined surfaces 72A and 72B with respect to the bottom surface 70A is as follows as an example. In the example of FIG. 5, the angle θ is set to approximately 35 °.
15 ° ≦ θ ≦ 45 ° (2)
If the angle θ is smaller than the lower limit of the expression (2), the outer periphery of the bottom surface 70A of the nozzle member 70 may be too large. Further, when the angle θ is larger than the upper limit of the expression (2), the liquid LQ leaking outside the nozzle member 70 hardly wets and spreads on the inclined surfaces 72A and 72B, so that the effect of suppressing the spread of the liquid LQ is obtained. Get smaller. The inclined surfaces 72A and 72B are not flat surfaces, but may be substantially concave, convex, wavy surfaces, or rough surfaces (for example, surfaces such as frosted glass). The angle is an acute angle with respect to the bottom surface 70A (the surface of the substrate P), and preferably satisfies the formula (2).

Here, with reference to FIGS. 7A to 7C, the relationship between the lyophilicity of the inclined surfaces 72A and 72B with respect to the liquid LQ and the angle θ will be described.
When the liquid LQ leaks outside the nozzle member 70 through the gap between the bottom surface of the nozzle member 70 and the surface of the substrate P, as shown in FIG. The adhesion force F2 to the surface and the adhesion force F1 to the surface of the substrate P act, but the liquid LQ is almost integrated by the surface tension. Further, since the inclined surface 72A is inclined with respect to the surface of the substrate P at an angle θ, when the adhesion force F2 is decomposed into a force F2X parallel to the surface of the substrate P (horizontal direction) and a force F2Z in the vertical direction, The forces F2X and F2Z using θ are as follows.

F2X = F2 · cos θ, F2Z = F2 · sin θ (3)
In this case, even if a part of the liquid LQ spreads on the inclined surface 72A, the spread of the liquid LQ on the substrate P is reduced. Furthermore, when the horizontal adhesion force F2X with respect to the inclined surface 72A becomes equal to or greater than the adhesion force F1 with respect to the substrate P, the liquid LQ tends to stay on the inclined surface 72A side as a whole. Therefore, it is preferable that the following relationship is established. Since the angle θ is an acute angle, the sign of cos θ is positive. Further, since the inclined surface 72A is not liquid repellent, the sign of F2 is positive.

F2 · cos θ ≧ F1 (4)
If the surface of the substrate P is liquid repellent, the sign of the adhesive force F1 is negative, and the formula (4) always holds. In this example, since the sign of the force F1 is positive, the maximum value of the angle θ in the range where the formula (4) is satisfied is arccos (F1 / F2). This means that the angle θ can be increased as the difference between the lyophilicity (adhesive force F2) of the inclined surface 72A with respect to the liquid LQ and the lyophilic property (adhesive force F1) of the surface of the substrate P increases.

  In the state where the angle θ is the maximum value, the bottom area of the nozzle member 70 can be reduced while the liquid LQ is retained on the nozzle member 70 side. Further, since the surface tension acts so as to cancel the adhesion force in the liquid LQ, the horizontal component of the surface tension of the liquid LQ on the inclined surface 72A side and the substrate P in the state where the angle θ is the maximum value. It can also be said that the surface tension of the liquid LQ on the side is substantially equal. In this state, it can be said that the contact angle of the liquid LQ with respect to the inclined surface 72A and the contact angle of the liquid LQ with respect to the substrate P are substantially equal.

  Further, the liquid LQ wets and spreads upward along the inclined surface 72A from the state of FIG. 7A, and as shown in FIG. 7B, the load FG and the vertical adhesion force of the liquid LQ on the inclined surface 72A. When F2Z becomes equal, most of the liquid LQ is held on the inclined surface 72A as it is. However, a part of the liquid LQ spreads further upward. Further, since the liquid LQ tends to be integrated by the surface tension, when the amount of the liquid LQ leaked to the outside of the nozzle member 70 further increases, as shown in FIG. Since the amount of the liquid LQ that is held increases and the load FG increases, the position of the center of gravity of the liquid LQ on the inclined surface 72A decreases.

  Instead of the inclined surface 72A of FIG. 5, for example, an inclined surface 72A1 provided on a part of the outer surface close to the substrate P of the nozzle member 70 may be used as shown in the modified example of FIG. In FIG. 8, the angle θ of the tip portion of the inclined surface 72A1 is an acute angle, and the inclined surface 72A1 is formed on the side surface 72A3 perpendicular to the surface (XY plane) of the substrate P via the recess 72A2 for accommodating the liquid LQ. It is fixed. In addition, the inclined surface 72A1 is also preferably lyophilic, and the liquid LQ accumulated in the recess 72A2 through the inclined surface 72A1 is recovered by the liquid recovery unit 21 in FIG. 5 through the recovery pipe 64A. According to the configuration of FIG. 8, the angle θ of the inclined surface 72A1 can be reduced to an angle close to approximately 0 ° without significantly increasing the outer periphery of the bottom surface of the nozzle member 70, thereby improving the liquid LQ recovery capability. it can.

  In addition, as shown in FIG. 2, the side surfaces adjacent to the inclined surfaces 72A and 72B of the nozzle member 70 are also inclined at an acute angle (preferably an angle θ in the range of the expression (2)) with respect to the bottom surface 70A. The inclined surfaces 72C, 72D, 72E, and 72F are lyophilic with respect to the liquid LQ similar to the surfaces 72A and 72B. However, these side surfaces may be surfaces perpendicular to the bottom surface 70A without forming the inclined surfaces 72C to 72F. Further, the side surfaces 72G and 72H in the non-scanning direction (Y direction) of the nozzle member 70 are perpendicular to the bottom surface 70A, but the side surfaces 72G and 72H are acute angles with respect to the bottom surface 70A, similar to the inclined surfaces 72A and 72B. Preferably, it may be a lyophilic inclined surface inclined at.

  Next, a method of exposing the pattern image of the mask M onto the substrate P using the exposure apparatus EX of FIG. 1 having the above-described configuration will be described with reference to FIGS. 6 (A) and 6 (B) corresponding to FIG. To do. 6A and 6B, the supply pipes 12A and 12B in FIG. 2 are represented by the supply pipe 12, the supply flow paths 14A and 14B are represented by the supply flow path 14, and the collection pipes 95A and 95B are represented by the collection pipe 95. In FIG. 3, the supply ports 13 </ b> A and 13 </ b> B are represented by the supply pipe 13, and the suction ports 98 </ b> A and 98 </ b> B are represented by the suction port 98.

  In FIG. 1, after the mask M is loaded on the mask stage MST and the substrate P is loaded on the substrate stage PST, the control device CONT starts the liquid exposure mechanism when the scanning exposure processing by the liquid immersion method of the substrate P is started. 10 is driven to start supplying the liquid LQ onto the substrate P. As shown in FIG. 6A, the liquid LQ supplied from the liquid supply unit 11 of the liquid supply mechanism 10 flows through the supply pipe 12 and the supply flow path 14, and then the image of the projection optical system PL from the supply port 13. Supplied to the surface side.

  The control device CONT in FIG. 1 drives the liquid recovery unit 21 of the liquid recovery mechanism 20 and starts the exhaust mechanism when the supply of the liquid LQ is started using the liquid supply mechanism 10 to form the liquid immersion area AR2. 90 exhaust parts 91 are driven. When the exhaust unit 91 having a vacuum system is driven, the image plane of the projection optical system PL from the suction port 98 provided in the vicinity of the optical element 2 on the image plane side of the projection optical system PL of FIG. The gas in the space near the side is exhausted (exhausted), and the space is made negative. Accordingly, the liquid LQ can be smoothly supplied into the nozzle member 70, and a gas portion remains in the immersion space on the immersion area AR2 formed on the image plane side of the projection optical system PL. It is possible to prevent inconvenience that bubbles are mixed in the liquid LQ for forming AR2.

  In this example, the liquid supply mechanism 10 ejects the liquid LQ from the supply port 13 in the nozzle member 70 substantially in parallel with the surface of the substrate P, and the suction port 98 is formed by the ejected liquid LQ. This is a configuration provided near the center of the vortex. Therefore, even if a bubble (gas portion) exists in the liquid LQ, the bubble moves to the vicinity of the center of the vortex flow based on the specific gravity difference with the liquid, so the exhaust mechanism 90 is disposed near the center of the vortex flow. The air bubbles can be satisfactorily collected by suction through the suction port 98 and removed. Therefore, it is possible to prevent inconvenience that bubbles are mixed in the liquid LQ on the image plane side of the projection optical system PL.

  As described above, the control device CONT performs the supply of the liquid LQ via the supply port 13 of the liquid supply mechanism 10 and the recovery of the liquid LQ via the recovery port 23 of the liquid recovery mechanism 20 in parallel. Eventually, as shown in FIG. 6B, an immersion area AR2 smaller than the substrate P and larger than the projection area AR1 so as to include the projection area AR1 between the projection optical system PL and the substrate P. Form locally (immersion space forming step). The liquid immersion area AR2 is formed on the upper surface 51 of the substrate stage PST different from the surface of the substrate P or on the upper surface of a movable body (such as a measurement stage described later) different from the substrate stage PST. In the latter case, the liquid immersion area AR2 may be moved from the upper surface to the surface of the substrate P by moving the substrate stage PST and another movable body in the proximity or contact.

  In this state, a part of the liquid LQ in the projection area AR2 passes outside the nozzle member 70 through the gap 7 (flow path) 65 between the bottom surface 70A of the nozzle member 70 of the nozzle unit 66 and the surface of the substrate P. Leak. A part of the leaked liquid LQ is guided by the adhesive force on the lyophilic inclined surface 72A (wetting spread), and the remaining part is wet spread on the surface of the substrate P (liquid spreading suppressing step). In this case, since the liquid LQ tries to maintain an integrated state by the surface tension, the liquid LQ tends to spread upward on the inclined surface 72A and the liquid LQ is outside the surface of the substrate P. The adhesion force ST2 to be spread (this absolute value is smaller than the absolute value of ST1) is approximately equal, or the vertical component (the absolute value in the + Z direction) of the adhesion force ST1 and the load of the liquid LQ on the inclined surface 72A In a state where (the absolute value in the −Z direction) becomes substantially equal, the spread of the liquid LQ on the surface of the substrate P almost stops. During the scanning exposure, the substrate P moves in the + X direction or the −X direction, and the liquid LQ is also collected by the collection port 23, so that the liquid LQ leaked to the outside of the nozzle member 70 is again in the liquid LQ. Some return to the liquid immersion area AR2 and be recovered from the recovery port 23 to the liquid recovery mechanism 20. Therefore, even when a liquid that does not have an appropriate liquid-repellent coating for the photoresist (or is easy to become familiar with an object) like the liquid LQ is used, the liquid LQ is prevented from spreading to the outside of the nozzle member 70 and is immersed in the liquid. The exposure can be performed by the method.

  Then, after forming the immersion area AR2 as shown in FIG. 6B, the control device CONT in FIG. 1 irradiates the substrate P with the exposure light EL in a state where the projection optical system PL and the substrate P face each other. The pattern image of the mask M is exposed on the substrate P through the projection optical system PL and the liquid LQ. When exposing the substrate P, the control device CONT performs the recovery of the liquid LQ by the liquid recovery mechanism 20 in parallel with the supply of the liquid LQ by the liquid supply mechanism 10 and the substrate stage PST that supports the substrate P X The pattern image of the mask M is projected and exposed onto the substrate P via the liquid LQ between the projection optical system PL and the substrate P and the projection optical system PL while moving in the direction (scanning direction) (exposure process). At this time, the control device CONT uses the flow rate controllers 16A and 16B (see FIG. 2) of the liquid supply mechanism 10 to adjust the liquid supply amount per unit time and is substantially the same as the surface of the substrate P via the supply port 13. The liquid LQ is blown out and supplied in parallel. During the exposure of the substrate P, the control device CONT uses the AF sensor 80 to detect the position information of the surface of the substrate P via the liquid LQ, and projects within the projection area AR1 based on the detection result. For example, exposure is performed while driving the Z tilt stage 52 so that the image plane by the optical system PL matches the surface of the substrate P. When the movement of the substrate P in the X direction and the focus leveling operation are performed as described above, the control unit CONT uses the measurement value of the AF sensor 80 to perform the servo movement and the nozzle moving mechanism 37 of FIG. To maintain the distance g between the bottom surface 70A of the nozzle member 70 and the surface of the substrate P at a predetermined value (or within a range) (moving step of the nozzle member 70). Thereby, the leakage amount of the liquid LQ to the outside of the nozzle member 70 is reduced.

  Even during the exposure of the substrate P, the controller CONT continues to collect part of the liquid LQ in the liquid immersion area AR2 via the suction port 98 of the exhaust mechanism 90. Thus, even if bubbles are mixed in the liquid LQ in the liquid immersion area AR2 or a gas portion is generated during the exposure of the substrate P, the bubbles (gas portion) are passed through the suction port 98. It can be recovered and removed. In particular, since the suction port 98 is disposed nearer to the optical element 2 of the projection optical system PL than the recovery port 23, it is possible to quickly recover bubbles or the like existing in the vicinity of the optical element 2 of the projection optical system PL. .

  In the above-described embodiment, the entire bottom surface 70A of the nozzle member 70 has been described as being water-repellent, but a part thereof may be used. When the liquid repellent region is formed on a part of the bottom surface 70A, the liquid repellent region may be one place or any plurality of places. Further, the bottom surface 70A is formed by a member different from the nozzle member 70, for example, a material having liquid repellency such as polytetrafluoroethylene or acrylic resin, without performing the liquid repellency treatment on the bottom surface 70A. You can also

  In the above-described embodiment, the liquid supply amount per unit time at the time of liquid supply before exposing the substrate P (state of FIG. 6A) and the liquid supply during exposure of the substrate P (FIG. 6 ( The liquid supply amount per unit time in the state B) may be set to a different value. For example, the liquid supply amount per unit time before exposing the substrate P is set to about 2 liters / minute, and the liquid supply amount per unit time during exposure of the substrate P is set to about 0.5 liters / minute. The liquid supply amount before exposing the substrate P may be larger than the liquid supply amount during exposure of the substrate P. By increasing the liquid supply amount before exposing the substrate P, for example, the space (2) of the optical element 2 and the gas (bubbles) in the recess 77 of the nozzle member 70 are removed, and the space can be quickly removed. Can be filled with liquid LQ. Further, during the exposure of the substrate P, since the supply amount of the liquid LQ is reduced, vibrations to the projection optical system PL and the like can be suppressed. Conversely, the liquid supply amount before the substrate P is exposed may be smaller than the liquid supply amount during the exposure of the substrate P. By reducing the amount of liquid supplied before exposing the substrate P, the gas (bubbles) in the space in the liquid contact surface 2A and the recess 77 of the nozzle member 70 can be surely expelled, and the space can be filled with the liquid LQ. it can. Further, by relatively increasing the liquid supply amount during the exposure of the substrate P, the temperature change (temperature distribution fluctuation) of the liquid LQ on the image plane side of the projection optical system PL can be suppressed, and the liquid LQ is passed through the liquid LQ. The formed image and detection by the AF sensor 80 can be performed with high accuracy. As described above, the liquid supply amount before the exposure of the substrate P and the liquid supply amount during the exposure of the substrate P include the shape of the bottom surface 70A of the nozzle member 70, the contact angle with the liquid LQ, and the liquid LQ on the surface of the substrate P. What is necessary is just to set suitably in consideration of a contact angle, the vibration proof performance of the projection optical system PL and the nozzle member 70, exposure conditions, target throughput, target imaging performance, and the like.

Next, another example of the embodiment of the present invention will be described with reference to FIG. 9, parts corresponding to those in FIG. 5 are denoted by the same reference numerals, and detailed description thereof is omitted. The exposure apparatus of this example has a configuration similar to that of the exposure apparatus EX of FIG. 1 except that the nozzle unit 66A of FIG.
FIG. 9 shows a nozzle unit 66A of this example. In FIG. 9, the inclined surface 72A, 72B of the nozzle member 70 of this example has an interval (for example, about 0.5 mm) at which the liquid LQ is sucked up by capillary action. The slit members 62A and 62B having a shape in which multilayer slits are arranged at the following intervals are fixed. Note that the slit member 62A and the storage portion 63A (described later) on the inclined surface 72A side are shown in cross section. The slit members 62A and 62B are made of a lyophilic material with respect to the liquid LQ, for example, a metal such as aluminum, titanium, stainless steel, or duralumin, an alloy containing them, or glass (quartz).

  One end sides of the slit members 62A and 62B are substantially flush with the bottom surface 70A of the nozzle member 70 and face the surface of the substrate P. In addition, the storage portions 63A and 63B for accumulating the liquid LQ are fixed so that the other ends of the slit members 62A and 62B on the inclined surfaces 72A and 72B are sealed from the bottom surface side, and the interior of the storage portions 63A and 63B is fixed. And the liquid recovery part 21 are connected by recovery pipes 64A and 64B. A recovery mechanism that recovers the liquid LQ via the recovery tubes 64A and 64B is also provided in the liquid recovery unit 21. For example, a check valve is provided in the recovery pipes 64A and 64B and connected to the recovery pipe 22, and the liquid LQ from the recovery port 23 and the storage parts 63A and 63B is recovered by a common recovery part in the liquid recovery part 21. May be. Alternatively, the storage units 63A and 63B may be communicated to recover the liquid LQ in the storage unit 63B to the liquid recovery unit 21 from the common recovery pipe 64A.

  In this example, a part of the liquid LQ leaking out of the nozzle member 70 through the gap 65 between the bottom surface 70A of the nozzle member 70 and the surface of the substrate P during exposure by the liquid immersion method is inclined by capillary action. It is sucked into the storage parts 63A and 63B through the slit members 62A and 62B of the surfaces 72A and 72B. Then, since the liquid LQ in the storage parts 63A and 63B is recovered by the liquid recovery part 21 via the recovery pipes 64A and 64B, the liquid LQ leaking outside the nozzle member 70 is more spread on the substrate P. It can be reliably suppressed.

In addition, you may provide slit member 62A, 62B on the other inclined surfaces 72C-72F of the nozzle member 70 of FIG. In this case, the slit members 62A and 62B do not need to be provided on the entire surfaces of the inclined surfaces 72A to 72F. It may be provided only on the surface.
As the slit members 62A and 62B, it is also possible to use a two-dimensional lattice shape of the cross-sectional shape or a large number of minute tube aggregates composed of a large number of small through-hole aggregates.

  The exposure apparatus of the above-described embodiment is a cleaning apparatus that removes foreign matters (including residual liquid) adhering to the liquid contact surface by fluid cleaning and / or optical cleaning of the nozzle member 70 (and the optical element 2). It is preferable to provide. For example, cleaning in which a cleaning liquid ejection section (including a cleaning nozzle) and / or a light emitting section of a cleaning light beam is mounted on a movable body (such as a measurement stage) different from the substrate stage PST. An apparatus may be provided, and cleaning (exposure apparatus (nozzle member 70, etc.) maintenance) may be performed periodically with the ejection part or the light emission part facing the nozzle member 70 or the like. Further, in the exposure apparatus of the above-described embodiment, the nozzle member 70 is detachable. For example, when the nozzle member 70 is contaminated or damaged, which cannot be dealt with by the cleaning apparatus, the nozzle member 70 is exposed from the exposure apparatus. The nozzle member 70 may be removed and remounted on the exposure apparatus after the nozzle member 70 is cleaned, or another nozzle member may be mounted on the exposure apparatus by replacement with the nozzle member 70.

  In the above embodiment, a part of the AF sensor 80 (the optical members 83 and 84) constitutes a part of the nozzle member 70. However, the nozzle member 70 may not include a part of the AF sensor 80. Good. Furthermore, the AF sensor 80 in which at least some of the plurality of measurement points are set in the liquid immersion area AR2 may not be provided. In this case, the surface position information of the substrate P is measured prior to exposure, and during the exposure operation, the position information in the Z direction of the substrate stage PST and the rotation information in the θX and θY directions are measured based on the prior measurement information. The position of the substrate P in the Z direction, θX and θY directions may be controlled using a possible laser interferometer 34.

  In the above embodiment, the optical element 2 is replaceably attached to the tip of the projection optical system PL, and the optical characteristics of the projection optical system PL, such as aberration (spherical aberration, coma aberration, etc.), are provided by this optical element 2. Adjustments can be made. The optical element attached to the tip of the projection optical system PL may be an optical plate used for adjusting the optical characteristics of the projection optical system PL. Alternatively, it may be a plane parallel plate that can transmit the exposure light EL.

Further, when the pressure between the optical element at the tip of the projection optical system PL generated by the flow of the liquid LQ and the substrate P is large, the optical element is not exchangeable but the optical element is moved by the pressure. It may be fixed firmly so that there is no.
In the above embodiment, the space between the projection optical system PL and the surface of the substrate P is filled with the liquid LQ. For example, in a state where a cover glass made of a plane parallel plate is attached to the surface of the substrate P. The structure which fills the liquid LQ may be sufficient.

  In the above embodiment, the nozzle member 70 that forms the liquid LQ immersion space including the optical path of the exposure light EL between the optical element 2 of the projection optical system PL and the substrate P is not limited to the above-described configuration. For example, European Patent Publication No. 1,420,298, International Publication No. 2004/055803 Pamphlet, International Publication No. 2004/057590 Pamphlet, International Publication No. 2005/029559 Pamphlet, International Publication No. 2004/086468 Pamphlet (corresponding The aforementioned inclined surfaces (72A, 72A1) may be provided on the nozzle member disclosed in US Publication No. 2005 / 0280791A1), Japanese Patent Application Laid-Open No. 2004-289126 (corresponding US Pat. No. 6,952,253) and the like. Further, the local immersion apparatus including the nozzle member 70 and the like may form an immersion space also on the incident surface side of the optical element 2 of the projection optical system PL.

  In the above embodiment, the nozzle member 70 has an annular shape. However, as disclosed in, for example, WO 99/49504, the liquid supply nozzle and the liquid recovery nozzle are separated. In this case, as an example, an inclined surface having an acute angle with respect to the surface of the substrate is formed on the substrate side of the outer surface of the nozzle for liquid recovery, and a part of the liquid leaking to the outside through this inclined surface May be held.

The liquid LQ in the above embodiment is decalin (trans-decalin or cis-decalin). As the liquid LQ, for example, a predetermined liquid having a C—H bond or an O—H bond such as isopropanol or glycerol, or hexane. A predetermined liquid (organic solvent) such as heptane or decane can also be used. Alternatively, the liquid LQ may be a mixture of any two or more of these predetermined liquids, or a liquid obtained by adding (mixing) the predetermined liquid to pure water. Also good. Alternatively, the liquid LQ can be used even if pure water is added (mixed) with a base or acid such as H ⁺ , Cs ⁺ , K ⁺ , Cl ⁻ , SO ₄ ²⁻ , PO ₄ ^3−. . Furthermore, it can be used by adding (mixing) fine particles such as aluminum oxide to pure water. Liquids that can be used as these liquids LQ can transmit ArF excimer laser light. Further, the liquid LQ has a small light absorption coefficient, a low temperature dependency, and is stable with respect to the photosensitive material applied on the surface of the projection optical system PL (optical element 2) or the substrate P. Is preferred.

  In the above embodiment, the position information of the mask stage and the substrate stage is measured using the interferometer system. However, the present invention is not limited to this, and for example, an encoder that detects a scale (diffraction grating) provided on the upper surface of the substrate stage. A system may be used. In this case, it is preferable that a hybrid system including both the interferometer system and the encoder system is used, and the measurement result of the encoder system is calibrated using the measurement result of the interferometer system. Further, the position of the substrate stage may be controlled by switching between the interferometer system and the encoder system or using both.

  In the present invention, in addition to a step-and-scan type scanning exposure apparatus (scanning stepper) that scans and exposes a mask pattern by moving the mask and the substrate synchronously, the mask and the substrate are stationary. Step-and-repeat projection exposure apparatus (stepper) that performs batch exposure of the pattern of the mask M and sequentially moves the substrate P stepwise, or transfers a plurality of patterns partially on the substrate, and sequentially transfers the substrates. The present invention can also be applied to a moving step-and-stitch type exposure apparatus.

Further, as disclosed in, for example, JP-A-10-163099, JP-A-10-214783, JP 2000-505958, US Pat. No. 6,208,407, etc., a plurality of wafer stages are provided. The present invention can also be applied to a multistage exposure apparatus provided.
In addition, as disclosed in, for example, Japanese Patent Application Laid-Open Nos. 11-135400 and 2000-164504, the present invention includes a substrate stage for holding a substrate, a reference member on which a reference mark is formed, and various sensors. The present invention can also be applied to an exposure apparatus that includes a mounted measurement stage.

  In the above-described embodiment, a light-transmitting mask in which a predetermined light-shielding pattern (or phase pattern / dimming pattern) is formed on a light-transmitting substrate is used. As disclosed in US Pat. No. 6,778,257, an electronic mask (also called a variable molding mask) that forms a transmission pattern or a reflection pattern, or a light emission pattern based on electronic data of a pattern to be exposed. For example, a DMD (Digital Micro-mirror Device) which is a kind of non-light emitting image display element (spatial light modulator) may be used.

Further, in the above-described embodiment, the substrate is exposed by projecting a pattern image onto the substrate P using the projection optical system PL, but as disclosed in International Publication No. 2001/035168 pamphlet. The present invention can also be applied to an exposure apparatus (lithography system) that exposes a line and space on the substrate P by forming interference fringes on the substrate P. In this case, the projection optical system PL need not be used, and the diffraction grating for forming the interference fringes can be regarded as an optical member.
Further, as disclosed in, for example, Japanese translations of PCT publication No. 2004-51850 (corresponding US Pat. No. 6,611,316), two mask patterns are synthesized on a substrate via a projection optical system, and The present invention can also be applied to an exposure apparatus that double exposes one shot area on a substrate almost simultaneously by scanning exposure.

  In addition, an illumination optical system and projection optical system composed of a plurality of lenses are incorporated into the exposure apparatus body for optical adjustment, and a mask stage and wafer stage consisting of a number of mechanical parts are attached to the exposure apparatus body to provide wiring and piping. The exposure apparatus of the above-described embodiment can be manufactured by connecting and further performing general adjustment (electric adjustment, operation check, etc.). The exposure apparatus is preferably manufactured in a clean room where the temperature, cleanliness, etc. are controlled.

  Further, when a semiconductor device is manufactured using the exposure apparatus of the above-described embodiment, the semiconductor device includes a step of designing a function and performance of the device, a step of manufacturing a reticle based on this step, and a wafer from a silicon material. Forming, aligning with the exposure apparatus of the above embodiment to expose the reticle pattern onto the substrate (wafer), developing the exposed substrate, heating (curing) the developed substrate, and etching. It is manufactured through a substrate processing step, a device assembly step (including a dicing process, a bonding process, and a packaging process), an inspection step, and the like.

  Further, the present invention is not limited to application to a semiconductor device manufacturing process, for example, a manufacturing process of a display device such as a liquid crystal display element formed on a square glass plate or the like, or a plasma display, or imaging. The present invention can be widely applied to manufacturing processes of various devices such as devices (CCD, etc.), micromachines, MEMS (Microelectromechanical Systems), thin film magnetic heads using ceramic wafers as substrates, and DNA chips. Furthermore, the present invention can also be applied to a manufacturing process when manufacturing a mask (photomask, reticle, etc.) on which mask patterns of various devices are formed using a photolithography process.

  In addition, this invention is not limited to the above-mentioned embodiment, A various structure can be taken in the range which does not deviate from the summary of this invention.

  According to the device manufacturing method of the present invention, the exposure is improved by the immersion method using a liquid having a high refractive index which is easy to adjust to an object or does not have an appropriate liquid repellent coating, thereby improving the focus. Deepen the depth. Therefore, a device having a fine pattern can be manufactured with high accuracy and high yield.

1 is a partially cutaway view showing a schematic configuration of an exposure apparatus as an example of an embodiment of the present invention. It is a perspective view which shows the nozzle member 70 of FIG. It is the perspective view which looked at the nozzle member 70 of FIG. 1 from the bottom face side. It is a bottom view which shows the nozzle member 70 of FIG. It is sectional drawing which follows the AA line of FIG. It is a schematic diagram which shows the exposure operation | movement by the liquid immersion method in an example of embodiment of this invention. In an example of an embodiment of the present invention, it is a figure showing signs that liquid LQ spreads on inclined surface 72A of a nozzle member. It is a figure which shows the principal part of the modification of the inclined surface provided in a nozzle member. It is sectional drawing which shows the nozzle unit of the other example of embodiment of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 2 ... Optical element, 10 ... Liquid supply mechanism, 13 (13A, 13B) ... Supply port, 20 ... Liquid recovery mechanism, 23 ... Recovery port, 30 ... Filter member, 37 ... Nozzle movement mechanism, 66 ... Nozzle unit, 70 ... Nozzle member, 70A ... bottom surface, 72A, 72B ... inclined surface, 77 ... concave, 78 ... concave, 90 ... exhaust mechanism, 98A, 98B ... suction port, P ... substrate, AR1 ... projection area, AR2 ... immersion area, EL ... exposure light, EX ... exposure device, PL ... projection optical system, LQ ... liquid

Claims (61)

In an exposure method of exposing a substrate with exposure light via an optical member and a liquid,
Is arranged to surround the optical path of the exposure light, has an end face arranged opposite the annular a and the substrate, wherein at least a portion of the outer surface provided on the optical member side relative to the end face The liquid is supplied to the inside of the liquid immersion member formed with an acute inclined surface so as to approach the substrate as it is farther from the optical path with respect to the end surface, and a liquid immersion space is formed between the optical member and the substrate. A first step of forming;
And a second step of holding at least a part of the leaked liquid composed of the liquid leaking outside the liquid immersion member through the gap between the liquid immersion member and the substrate by the inclined surface. Exposure method. In an exposure method of exposing a substrate with exposure light via an optical member and a liquid,
A liquid immersion member that forms an immersion space for the liquid including the optical path of the exposure light between the optical member and the substrate passes through a gap between the end surface of the liquid immersion member that faces the substrate and the substrate. Te, at least a portion of the leakage liquid leaking from the immersion space outside the liquid immersion member, wherein at least a portion of the outer surface provided on the optical member side with respect to the end surface of the immersion member An exposure method comprising holding an inclined surface having an acute angle so as to be closer to the substrate as it is farther from the optical path with respect to the end surface .   The exposure method according to claim 1, wherein the inclined surface is lyophilic and suppresses expansion of the leaked liquid to the outside of the liquid immersion member.   The exposure method according to claim 1, wherein the leaked liquid on the inclined surface is held on the inclined surface by at least a surface tension thereof.   5. The leaked liquid according to claim 1, wherein a surface tension at the inclined surface and a surface tension at the surface of the substrate outside the liquid immersion member are substantially equal. Exposure method.   6. The leaking liquid according to claim 1, wherein a contact angle with the inclined surface is substantially equal to a contact angle with the substrate outside the liquid immersion member. Exposure method. The gap between the outer region of the step provided on the end face side of the liquid immersion member and the substrate facing each other is smaller than the inner region than the inner region. The exposure method according to claim 1. The exposure method according to claim 7, wherein the liquid in the immersion space is recovered through a recovery port provided in the inner region of the end surface of the immersion member.   The exposure method according to claim 1, wherein the leaked liquid is sucked up by a capillary phenomenon by the slit portion of the inclined surface.   The exposure method according to claim 9, wherein the leaked liquid is collected through the slit portion.   The exposure method according to claim 1, wherein an angle of the inclined surface is 15 ° to 45 °. In an exposure method of exposing a substrate with exposure light via an optical member and a liquid,
Through the gap between the first surface and the substrate facing the substrate of the liquid immersion member which forms a liquid immersion space of the liquid containing the optical path of the exposure light between the substrate and the optical member, Leakage liquid consisting of the liquid that leaks from the immersion space to the outside of the immersion member is provided on the optical member side with respect to the first surface, and the substrate is further away from the first surface and the optical path. An exposure method comprising: holding the second surface of the liquid immersion member having an acute angle so as to approach the second surface.   The exposure method according to claim 12, wherein the second surface is lyophilic, and expansion of the leaked liquid to the outside of the liquid immersion member is suppressed.   The exposure method according to claim 12 or 13, wherein the leaking liquid is held on the second surface at least by its surface tension.   15. The leaked liquid according to claim 12, wherein a surface tension of the second surface is substantially equal to a surface tension of the surface of the substrate outside the liquid immersion member. The exposure method as described.   The contact angle between the leaked liquid and the second surface is substantially equal to a contact angle with the substrate outside the liquid immersion member. Exposure method.   The exposure method according to any one of claims 12 to 16, wherein the first surface of the liquid immersion member has a gap between the outer region of the step and the surface of the substrate smaller than the inner region.   The exposure method according to claim 17, wherein the liquid in the immersion space is recovered through a recovery port provided in an inner region of the first surface.   The exposure method according to claim 12, wherein an angle of the second surface with respect to the first surface is 15 ° to 45 °.   The exposure method according to claim 1, wherein the liquid immersion member moves according to a change in a gap with the surface of the substrate accompanying the movement of the substrate.   During the exposure, the relative positional relationship between the substrate and a predetermined surface on which a pattern image is generated is adjusted via the optical member, and the liquid immersion member has a gap between the substrate surface and a predetermined range. The exposure method according to any one of claims 1 to 20, wherein the exposure method moves so as to be within a range.   The exposure method according to claim 20 or 21, wherein the liquid immersion member is maintained at a gap of 10 to 200 µm with the surface of the substrate.   The exposure method according to any one of claims 1 to 22, wherein the liquid has a refractive index larger than that of pure water.   The exposure method according to any one of claims 1 to 23, wherein the liquid has a refractive index of 1.5 or more. In an exposure apparatus that exposes a substrate with exposure light via an optical member and a liquid,
It is arranged so as to surround the optical path of the exposure light, and has an end surface that is annular and is arranged to face the substrate, and at least a part of the outer surface provided on the optical member side with respect to the end surface A liquid immersion member in which an acute inclined surface is formed so as to approach the substrate as the distance from the optical path with respect to the end surface ;
A liquid supply unit that supplies the liquid into the liquid immersion member and forms an immersion space between the optical member and the substrate;
The exposure apparatus according to claim 1, wherein the inclined surface holds at least a part of the liquid leaking outside the liquid immersion member . In an exposure apparatus that exposes a substrate with exposure light via an optical member and a liquid,
An end surface is disposed between the optical member and the substrate to form an immersion space for the liquid including the exposure light path, and the substrate is disposed to face the end surface. A liquid immersion member in which an inclined surface having an acute angle is formed on at least a part of an outer surface provided on the optical member side so as to approach the substrate as the distance from the optical path with respect to the end surface ;
A liquid supply part for supplying the liquid to the immersion space;
The exposure apparatus according to claim 1, wherein the inclined surface holds at least a part of the liquid leaking outside the liquid immersion member .   The inclined surface is lyophilic, and at least a part of the liquid leaking to the outside of the liquid immersion member through the gap between the liquid immersion member and the substrate is guided to the inclined surface. An exposure apparatus according to claim 25 or 26.   The angle of the inclined surface is determined by the surface tension at the inclined surface of the liquid leaking to the outside of the liquid immersion member through the gap between the liquid immersion member and the substrate, and the outside of the liquid immersion member. The exposure apparatus according to any one of claims 25 to 27, wherein the exposure apparatus is set so that the surface tension on the surface of the substrate is substantially equal.   The angle of the inclined surface is determined by the contact angle between the inclined surface of the liquid leaking outside the liquid immersion member through the gap between the liquid immersion member and the substrate, and the outside of the liquid immersion member. 28. The exposure apparatus according to claim 25, wherein the contact angle with the substrate is set to be substantially equal. A step is provided on the end surface side of the liquid immersion member that is disposed so as to face the substrate,
30. The exposure apparatus according to claim 25, wherein an outer area of the step of the liquid immersion member has a smaller gap from the surface of the substrate than an inner area. 31. The exposure according to claim 30, further comprising a first liquid recovery unit that recovers the liquid in the liquid immersion space via a recovery port provided in the inner region of the end surface of the liquid immersion member. apparatus.   32. The exposure apparatus according to claim 25, wherein a slit portion for sucking up the liquid by capillary action is formed on at least a part of the inclined surface of the liquid immersion member.   33. The exposure apparatus according to claim 32, further comprising a second liquid recovery part that recovers the liquid through the slit part.   34. The exposure apparatus according to claim 25, wherein an angle of the inclined surface is 15 [deg.] To 45 [deg.]. In an exposure apparatus that exposes a substrate with exposure light via an optical member and a liquid,
A first surface disposed to form an immersion space for the liquid including the optical path of the exposure light between the optical member and the substrate, and the substrate is disposed to face the first surface; In contrast , a liquid immersion member provided on the optical member side and having a second surface that forms an acute angle so as to approach the substrate as the distance from the first surface and the optical path increases .
A liquid supply part for supplying the liquid to the immersion space formed by the liquid immersion member,
The exposure apparatus , wherein the second surface holds at least a part of the liquid leaking outside the liquid immersion member .   36. The exposure apparatus according to claim 35, wherein the second surface is lyophilic.   The angle of the second surface is determined by the surface tension at the second surface of the liquid leaking out of the liquid immersion member through the gap between the first surface of the liquid immersion member and the substrate, and 37. The exposure apparatus according to claim 35 or 36, wherein a surface tension on the surface of the substrate outside the immersion member is set to be substantially equal.   The angle of the inclined surface includes a contact angle with the second surface of the liquid leaking out of the liquid immersion member through the gap between the first surface of the liquid immersion member and the substrate, and the liquid 37. The exposure apparatus according to claim 35 or 36, wherein the contact angle with the substrate outside the immersion member is set to be substantially equal.   The step is provided on the first surface of the liquid immersion member, and the gap between the outer region of the step and the surface of the substrate is smaller than the inner region. The exposure apparatus described.   40. The exposure apparatus according to claim 39, further comprising a liquid recovery unit that recovers the liquid in the immersion space via a recovery port provided in the inner region of the first surface of the liquid immersion member. .   The exposure apparatus according to any one of claims 35 to 40, wherein an angle of the second surface with respect to the first surface is 15 ° to 45 °.   The liquid immersion member moving part that moves the liquid immersion member in accordance with a change in a gap with the surface of the substrate accompanying the movement of the substrate is provided. Exposure equipment. A stage device that adjusts a relative positional relationship between the substrate and a predetermined surface on which a pattern image is generated via the optical member during the exposure;
A liquid immersion member moving unit that moves the liquid immersion member so that a gap between the liquid immersion member and the surface of the substrate is within a predetermined range in accordance with the position adjustment of the substrate by the stage device; 42. The exposure apparatus according to any one of claims 25 to 41, wherein:   44. The exposure apparatus according to claim 42 or 43, wherein a gap between the liquid immersion member and the surface of the substrate is maintained at 10 to 200 [mu] m.   45. The exposure apparatus according to any one of claims 25 to 44, wherein the liquid has a refractive index higher than that of pure water.   The exposure apparatus according to any one of claims 25 to 45, wherein the liquid has a refractive index of 1.5 or more. A liquid immersion member mounted on an exposure apparatus that fills a space between the optical member and the substrate to form an immersion space, and exposes the substrate with exposure light through the optical member and the liquid,
It can be arranged so as to surround the optical path of the exposure light, and includes a main body portion that is annular and has a space for forming the immersion space therein.
The liquid channel is formed inside the main body,
In order to hold at least a part of the liquid leaking out of the liquid immersion member in a state where the main body is mounted on the exposure apparatus, the end of the main body is opposed to the end surface of the main body facing the substrate. A liquid immersion member, wherein an inclined surface having an acute angle is formed on at least a part of an outer surface provided on the optical member side so as to approach the substrate as the distance from the optical path with respect to the end surface . A liquid immersion member mounted on an exposure apparatus that fills a space between the optical member and the substrate to form an immersion space, and exposes the substrate with exposure light through the optical member and the liquid,
A main body disposed to form the immersion space between the optical member and the substrate;
The liquid channel is formed inside the main body,
In order to hold at least a part of the liquid leaking out of the liquid immersion member in a state where the main body is mounted on the exposure apparatus, the end of the main body is opposed to the end surface of the main body facing the substrate. The liquid immersion is characterized in that an inclined surface having an acute angle is formed on at least a part of the outer surface provided on the optical member side so as to approach the substrate as the distance from the optical path of the exposure light increases with respect to the end surface. Element. The inclined surface is lyophilic,
49. A step is formed on the end face of the main body portion facing the substrate, and the gap between the outer region of the step and the surface of the substrate is smaller than the inner region. The liquid immersion member according to 1.   The liquid immersion member according to any one of claims 47 to 49, wherein a slit portion for sucking up the liquid by capillary action is provided on at least a part of the inclined surface of the main body portion.   51. The liquid immersion member according to any one of claims 47 to 50, wherein an angle of the inclined surface of the main body portion is 15 [deg.] To 45 [deg.]. A liquid immersion member mounted on an exposure apparatus that fills a space between the optical member and the substrate to form an immersion space, and exposes the substrate with exposure light through the optical member and the liquid,
A main body disposed to form the immersion space between the optical member and the substrate;
The liquid channel is formed inside the main body,
In a state where the main body is mounted on the exposure apparatus, the main body holds the first surface on which the substrate is opposed and at least a part of the liquid that leaks outside the liquid immersion member. In addition, the second surface is provided on the optical member side with respect to the first surface and has a second surface that forms an acute angle so as to approach the substrate as the distance from the optical path of the exposure light increases. Immersion member. The second surface is lyophilic,
53. The liquid immersion member according to claim 52, wherein a step is formed on the first surface of the main body, and the gap between the outer region of the step and the surface of the substrate is smaller than the inner region.   54. The liquid immersion member according to claim 52 or 53, wherein a slit for sucking up the liquid by capillary action is provided on at least a part of the second surface of the main body.   The liquid immersion member according to any one of claims 52 to 54, wherein an angle of the second surface of the main body portion is 15 ° to 45 °.   25. A device manufacturing method using the exposure method according to any one of claims 1 to 24. A maintenance method for an exposure apparatus that fills a space between an optical member and a substrate to form a liquid immersion space, and exposes the substrate with exposure light through the optical member and the liquid,
56. A maintenance method for an exposure apparatus, comprising a step of cleaning the liquid immersion member according to any one of claims 47 to 55 attached to the exposure apparatus.   58. The exposure apparatus maintenance method according to claim 57, wherein the liquid immersion member is taken out of the exposure apparatus, and the liquid immersion member is remounted on the exposure apparatus after cleaning.   59. The exposure apparatus maintenance method according to claim 57 or 58, wherein the liquid immersion member is taken out of the exposure apparatus, and another liquid immersion member is attached to the exposure apparatus by replacement with the liquid immersion member. . A maintenance method for an exposure apparatus that fills a space between an optical member and a substrate to form a liquid immersion space, and exposes the substrate with exposure light through the optical member and the liquid,
56. The liquid immersion member according to any one of claims 47 to 55, which is mounted on the exposure apparatus, is removed, and the liquid immersion member is cleaned and then remounted on the exposure apparatus. Exposure apparatus maintenance method. A maintenance method for an exposure apparatus that fills a space between an optical member and a substrate to form a liquid immersion space, and exposes the substrate with exposure light through the optical member and the liquid,
56. The liquid immersion member according to any one of claims 47 to 55, which is attached to the exposure apparatus, is taken out, and another liquid immersion member is attached to the exposure apparatus in exchange for the liquid immersion member. A maintenance method for the exposure apparatus.

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