JP2009152497A - Liquid immersion system, exposure apparatus, exposure method, and device manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid immersion system capable of filling an optical path with a liquid having a desired characteristic. <P>SOLUTION: This liquid immersion system is used for liquid immersion exposure exposing a substrate with exposure light. The liquid immersion system is provided with: a liquid adjustment unit; a first passage supplied with a liquid from the liquid adjustment unit; a second passage branched from the first passage for guiding at least a part of the liquid supplied to the first passage to an optical path of the exposure light; and a third passage branched from the first passage for returning at least a part of the liquid without flowing in the second passage out of the liquid supplied to the first passage to the liquid adjustment unit as a first liquid. The liquid adjustment unit can supply a liquid produced by adding a second liquid having an optical characteristic different from that of the first liquid in at least a part of the first liquid to the first passage. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an immersion system used for immersion exposure, an exposure apparatus that exposes a substrate through a liquid, an exposure method, and a device manufacturing method.

In an exposure apparatus used in a photolithography process, for example, an immersion exposure apparatus is disclosed in which an optical path of exposure light is filled with a liquid and a substrate is exposed with the exposure light through the liquid as disclosed in the following patent document. ing.
US Patent Application Publication No. 2005/0179877 European Patent Application No. 1806773

  In the immersion exposure apparatus, for example, when the characteristics of the liquid change, the pattern image formed via the liquid deteriorates, and as a result, an exposure failure or a defective device may occur.

  An object of an aspect of the present invention is to provide an immersion system that can fill an optical path with a liquid having desired characteristics (physical properties). Another object of the present invention is to provide an exposure apparatus and an exposure method that can suppress the occurrence of exposure failure. Another object of the present invention is to provide a device manufacturing method that can suppress the occurrence of defective devices.

  According to the first aspect of the present invention, there is provided an immersion system used for immersion exposure in which a substrate is exposed with exposure light, and a liquid adjustment device and a first flow path to which liquid from the liquid adjustment device is supplied A second flow path that branches from the first flow path and guides at least part of the liquid supplied to the first flow path to the optical path of the exposure light, and a first flow path that is branched from the first flow path. And a third flow path for returning at least a part of the liquid that has not flowed into the second flow path to the liquid adjustment apparatus as the first liquid. An immersion system is provided in which a liquid generated by adding a second liquid having optical properties different from that of the first liquid to at least a part of the liquid can be supplied to the first flow path.

  According to the second aspect of the present invention, the liquid immersion system according to the first aspect is provided, and the liquid supplied from the liquid adjusting device of the liquid immersion system via the first flow path and the second flow path is used. An exposure apparatus that exposes a substrate with exposure light is provided.

  According to a third aspect of the present invention, there is provided a device manufacturing method including exposing a substrate using the exposure apparatus according to the second aspect and developing the exposed substrate.

  According to a fourth aspect of the present invention, there is provided an exposure method for exposing a substrate with exposure light, wherein the liquid supplied from the liquid adjustment device is supplied to the first flow path, and the liquid supplied to the first flow path. Is supplied to the optical path of the exposure light through the second flow path, the substrate is exposed with the exposure light through the liquid supplied to the optical path of the exposure light, and is supplied to the first flow path. Returning at least a portion of the liquid that has not flowed into the second flow path to the liquid adjusting device via the third flow path as the first liquid; Adding a second liquid having optical characteristics different from that of the first liquid, and supplying a liquid generated by adding the second liquid to at least a part of the first liquid to the first flow path. An exposure method is provided.

  According to a fifth aspect of the present invention, there is provided a device manufacturing method comprising exposing a substrate using the exposure method of the fourth aspect and developing the exposed substrate.

  According to the present invention, an optical path can be filled with a liquid having desired characteristics (physical properties) in immersion exposure. Further, according to the present invention, it is possible to suppress the occurrence of exposure failure and suppress the occurrence of defective devices.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited thereto. In the following description, an XYZ orthogonal coordinate system is set, and the positional relationship of each member will be described with reference to this XYZ orthogonal coordinate system. A predetermined direction in the horizontal plane is defined as an X-axis direction, a direction orthogonal to the X-axis direction in the horizontal plane is defined as a Y-axis direction, and a direction orthogonal to each of the X-axis direction and the Y-axis direction (that is, a vertical direction) is defined as a Z-axis direction. In addition, the rotation (inclination) directions around the X, Y, and Z axes are the θX, θY, and θZ directions, respectively.

  FIG. 1 is a schematic block diagram that shows an example of an exposure apparatus EX according to the present embodiment. The exposure apparatus EX of the present embodiment is an immersion exposure apparatus that exposes a substrate P with exposure light EL through a liquid LQ.

  In FIG. 1, an exposure apparatus EX includes a mask stage 1 that can move while holding a mask M, a substrate stage 2 that can move while holding a substrate P, a mask stage drive system 3 that moves the mask stage 1, A substrate stage drive system 4 that moves the substrate stage 2, an interferometer system 7 that measures positional information of the mask stage 1 and the substrate stage 2, an illumination system IL that illuminates the mask M with the exposure light EL, and an exposure light EL. A projection optical system PL that projects an image of the pattern of the illuminated mask M onto the substrate P, and a liquid that can form the immersion space LS with the liquid LQ so that at least a part of the optical path of the exposure light EL is filled with the liquid LQ. An immersion member 8 and a control device 9 for controlling the operation of the entire exposure apparatus EX are provided. The immersion space LS is a space filled with the liquid LQ.

  The mask M includes a reticle on which a device pattern projected onto the substrate P is formed. The substrate P is a substrate for manufacturing a device. The substrate P includes a substrate in which a photosensitive film is formed on a base material such as a semiconductor wafer such as a silicon wafer. The photosensitive film is a film of a photosensitive material (photoresist). Further, the substrate P may include various films other than the photosensitive film. For example, the substrate P may include a protective film (topcoat film) that protects the photosensitive film.

The illumination system IL illuminates a predetermined illumination region IR with exposure light EL having a uniform illuminance distribution. The illumination system IL illuminates at least a part of the mask M arranged in the illumination region IR with the exposure light EL having a uniform illuminance distribution. As the exposure light EL emitted from the illumination system IL, for example, far ultraviolet light (DUV light) such as bright lines (g line, h line, i line) and KrF excimer laser light (wavelength 248 nm) emitted from a mercury lamp, ArF Vacuum ultraviolet light (VUV light) such as excimer laser light (wavelength 193 nm) and F ₂ laser light (wavelength 157 nm) is used. In the present embodiment, ArF excimer laser light, which is ultraviolet light (vacuum ultraviolet light), is used as the exposure light EL.

  The mask stage 1 has a mask holding unit MH that holds the mask M. The mask stage drive system 3 includes an actuator such as a linear motor. In the present embodiment, the mask stage 1 can be moved in three directions of the X axis, the Y axis, and the θZ direction while the mask M is held by the mask holding unit MH by the operation of the mask stage driving system 3.

  The projection optical system PL irradiates the predetermined projection region PR with the exposure light EL. The projection optical system PL projects an image of the pattern of the mask M at a predetermined projection magnification onto at least a part of the substrate P arranged in the projection region PR. The projection optical system PL includes a terminal optical element 10 that can face the substrate P. The last optical element 10 is an optical element closest to the image plane of the projection optical system PL among the plurality of optical elements of the projection optical system PL. The last optical element 10 has an exit surface 11 that emits the exposure light EL toward the image plane of the projection optical system PL. The exposure light EL emitted from the emission surface 11 is applied to the substrate P. The last optical element 10 can hold the liquid LQ between the exit surface 11 and the object facing it. In the present embodiment, the object that can face the emission surface 11 includes at least a part of the substrate stage 2 and the substrate P held on the substrate stage 2.

  The plurality of optical elements of the projection optical system PL are held by a lens barrel PK. The projection optical system PL of the present embodiment is a reduction system whose projection magnification is, for example, 1/4, 1/5, or 1/8. Note that the projection optical system PL may be either an equal magnification system or an enlargement system. In the present embodiment, the optical axis AX of the projection optical system PL is substantially parallel to the Z axis. Further, the projection optical system PL may be any of a refractive system that does not include a reflective optical element, a reflective system that does not include a refractive optical element, and a catadioptric system that includes a reflective optical element and a refractive optical element. Further, the projection optical system PL may form either an inverted image or an erect image.

  Further, the exposure apparatus EX includes an imaging characteristic adjustment system 19 that adjusts the imaging characteristics of the projection optical system PL. Examples of the imaging characteristic adjusting system 19 are disclosed in US Pat. No. 4,666,273, US Pat. No. 6,235,438, US Patent Publication No. 2005/0206850, and the like. The imaging characteristic adjustment system 19 of the present embodiment includes a drive device that can move some of the plurality of optical elements of the projection optical system PL. The drive device can move a specific optical element among the plurality of optical elements of the projection optical system PL in the optical axis AX direction (Z-axis direction). In addition, the drive device can tilt a specific optical element with respect to the optical axis AX. The imaging characteristic adjustment system 19 includes various aberrations (projection magnification, distortion, spherical aberration, etc.), image plane position (focus position), and the like of the projection optical system PL by moving specific optical elements of the projection optical system PL. Adjust the imaging characteristics. The imaging characteristic adjustment system may include a pressure adjustment device that adjusts the gas pressure in the space between some of the optical elements held inside the lens barrel PK. The imaging characteristic adjustment system 19 is controlled by the control device 9.

  The substrate stage 2 has a substrate holder PH that holds the substrate P. The substrate stage drive system 4 includes an actuator such as a linear motor. In this embodiment, the substrate stage 2 has six X-axis, Y-axis, Z-axis, θX, θY, and θZ directions in a state in which the substrate P is held by the substrate holder PH by the operation of the substrate stage drive system 4. It can move in the direction.

  The substrate stage 2 can move in the XY plane along the guide surface 5 of the base member 6. The substrate stage 2 is movable to a position facing the emission surface 11. The position facing the emission surface 11 includes the irradiation position of the exposure light EL emitted from the emission surface 11. The projection region PR includes the irradiation position of the exposure light EL emitted from the emission surface 11. In the following description, the irradiation position of the exposure light EL emitted from the emission surface 11 is appropriately referred to as an exposure position EP.

  The interferometer system 7 measures positional information of the mask stage 1 and the substrate stage 2 in the XY plane. The interferometer system 7 includes a first interferometer unit 7A including a laser interferometer 13 that measures position information of the mask stage 1 in the XY plane, and a laser interferometer 14 that measures position information of the substrate stage 2 in the XY plane. Including a second interferometer unit 7B. The first interferometer unit 7A uses the laser interferometer 13 to irradiate measurement light onto the reflective surface 1R disposed on the mask stage 1, and uses the measurement light via the reflective surface 1R to generate the X-axis, Y-axis, and Position information of the mask stage 1 (mask M) in the θZ direction is measured. The second interferometer unit 7B irradiates the reflection surface 2R disposed on the substrate stage 2 with the measurement light by the laser interferometer 14, and uses the measurement light via the reflection surface 2R to generate the X-axis, Y-axis, and Position information of the substrate stage 2 (substrate P) in the θZ direction is measured.

  In the present embodiment, the exposure apparatus EX includes a focus / leveling detection system (not shown) that detects positional information on the surface of the substrate P in the Z-axis, θX, and θY directions. At least when exposing the substrate P, the position information of the mask stage 1 is measured by the first interferometer unit 7A, and the position information of the substrate stage 2 is measured by the second interferometer unit 7B. At a predetermined timing, the position information on the surface of the substrate P is detected by the focus / leveling detection system. The control device 9 performs position control of the mask M held on the mask stage 1 based on the measurement result of the first interferometer unit 7A, and the measurement result of the second interferometer unit 7B and the focus / leveling detection system. Based on this detection result, position control of the substrate P held on the substrate stage 2 is executed.

  FIG. 2 is a cross-sectional view showing the vicinity of the last optical element 10, the liquid immersion member 8, and the substrate stage 2. As shown in FIG. 2, the liquid immersion member 8 is disposed in the vicinity of the last optical element 10. The liquid immersion member 8 is an annular member. The liquid immersion member 8 is disposed around the last optical element 10. The liquid immersion member 8 has an opening 8K through which the exposure light EL can pass at a position facing the emission surface 11. The liquid immersion member 8 has a lower surface 15. The liquid immersion member 8 can hold the liquid LQ between the lower surface 15 and the object facing it. That is, the liquid immersion member 8 can hold the liquid LQ between the lower surface 15 and the object facing the liquid LQ so that the optical path K of the exposure light EL between the emission surface 11 and the substrate P is filled with the liquid LQ. . In the present embodiment, the object that can face the lower surface 15 includes at least a part of the substrate stage 2 and the substrate P held on the substrate stage 2. In the following description, the state in which the emission surface 11 and the lower surface 15 on one side and the substrate P on the other side are opposed to each other will be mainly described. However, at least a part of the upper surface of the substrate stage 2 is an emission surface. 11 and the lower surface 15 may be opposed to each other.

  The exposure apparatus EX includes a supply port 16 for supplying the liquid LQ and a recovery port 17 for recovering the liquid LQ. In the present embodiment, each of the supply port 16 and the recovery port 17 is disposed in the liquid immersion member 8. The supply port 16 is disposed in the vicinity of the optical path K and faces the optical path K. The lower surface 15 of the liquid immersion member 8 includes a recovery port 17. The collection port 17 is disposed around the opening 8K through which the exposure light EL passes. That is, the recovery port 17 is disposed around the optical path of the exposure light EL. A plate-like porous member 18 including a plurality of openings (openings or pores) is disposed in the recovery port 17. Therefore, in this embodiment, a part of the lower surface 15 of the liquid immersion member 8 includes the lower surface of the porous member 18. Note that a mesh filter, which is a porous member in which a large number of small holes are formed in a mesh shape, may be disposed in the recovery port 17.

  The exposure apparatus EX includes a liquid supply apparatus 20 that supplies the liquid LQ to the supply port 16. The supply port 16 and the liquid supply device 20 are connected via a flow path 21. The liquid LQ delivered from the liquid supply device 20 is supplied to the supply port 16 via the flow path 21. The supply port 16 supplies the liquid LQ from the liquid supply device 20 to the optical path K of the exposure light EL.

  In addition, the exposure apparatus EX includes a liquid recovery apparatus 22 that can recover the liquid LQ. The liquid recovery device 22 includes a vacuum system, and can recover the liquid LQ by suction. The recovery port 17 and the liquid recovery device 22 are connected via a flow path 23. The liquid recovered from the recovery port 17 is recovered by the liquid recovery device 22 via the flow path 23.

  In the present embodiment, the control device 9 executes a liquid recovery operation using the recovery port 17 in parallel with at least a part of the liquid supply operation using the supply port 16. As a result, an immersion space LS is formed between the last optical element 10 and the immersion member 8 on one side and the substrate P on the other side so that the optical path K is filled with the liquid LQ.

  In the present embodiment, the immersion space LS is formed so that a partial region of the surface of the substrate P including the projection region PR of the projection optical system PL is covered with the liquid LQ. Further, the interface (meniscus, edge) of the liquid LQ is formed between the lower surface 15 of the liquid immersion member 8 and the surface of the substrate P. That is, the exposure apparatus EX of the present embodiment employs a local liquid immersion method. As the liquid immersion member 8, those disclosed in US Patent Application Publication No. 2006/0087630, US Patent Application Publication No. 2006/0221315, and the like can be applied.

  In the present embodiment, the substrate stage 2 includes a plate member T disposed around the substrate holding part PH. The substrate stage 2 includes a plate member holding portion TH that can release the plate member T. The plate member holding portion TH is disposed around the substrate holding portion PH. The plate member T has an opening TK in which the substrate P can be placed. The plate member T held by the plate member holding portion TH is disposed around the substrate P held by the substrate holding portion PH. Therefore, the upper surface of the substrate stage 2 includes the upper surface 12 of the plate member T held by the plate member holding portion TH. In the present embodiment, the surface of the substrate P held by the substrate holding part PH and the upper surface 12 of the plate member T held by the plate member holding part TH are substantially parallel. Further, in the present embodiment, the surface of the substrate P held by the substrate holding part PH and the upper surface of the plate member T held by the plate member holding part TH are arranged in substantially the same plane (substantially) Is the same). The upper surface 12 of the plate member T is liquid repellent with respect to the liquid LQ.

  FIG. 3 is a configuration diagram illustrating an example of the liquid supply apparatus 20 according to the present embodiment. In FIG. 3, the liquid supply apparatus 20 includes a liquid adjustment apparatus 24, a first flow path 25 to which the liquid LQ from the liquid adjustment apparatus 24 is supplied, a branch from the first flow path 25, and the first flow path 25. Of the liquid LQ branched from the first flow path 25 and supplied to the first flow path 25, the second flow path 26 for guiding at least a part of the supplied liquid LQ to the optical path K of the exposure light EL, A third flow path 27 is provided for returning at least part of the liquid LQ that has not flowed into the second flow path 26 to the liquid adjusting device 24 as the first liquid LQ1. The liquid adjustment device 24 supplies the liquid LQ generated by adding the second liquid LQ2 (LQ2a, LQ2b) having optical characteristics different from that of the first liquid LQ1 to at least a part of the first liquid LQ1. Can be supplied.

  The first liquid LQ1 is a liquid in which a predetermined substance is contained in the predetermined liquid at a first ratio. The second liquid LQ2 is a liquid in which the predetermined substance is contained in the predetermined liquid at a second ratio different from the first ratio. The optical characteristics change as the ratio of the predetermined substance contained in the predetermined liquid changes. The first liquid LQ1 and the second liquid LQ2 have different ratios of predetermined substances and different optical characteristics.

  In the present embodiment, the predetermined liquid is pure water. In the present embodiment, the first liquid LQ1 is a liquid in which fine particles of a predetermined substance are contained in a predetermined liquid (pure water) at a first ratio. The second liquid LQ2 is a liquid in which fine particles of a predetermined substance are contained in a predetermined ratio (pure water) at a second ratio.

  The fine particles have a size (particle diameter) of about 1 to 100 nm, for example. In general, ultrafine particles having a diameter (particle diameter) of about 1 to 100 nm are called nanoparticles. In the following description, fine particles of a predetermined substance are appropriately referred to as nanoparticles. In the present embodiment, fine particles (nanoparticles) having a size (particle diameter) of about 1 to 10 nm are used.

  As the fine particles of the predetermined substance, fullerene derivatives, carbon nanotubes, and the like can be used.

  As the fine particles of the predetermined substance, fine particles of inorganic material (inorganic fine particles) may be used, or fine particles of organic material (organic fine particles) may be used. Examples of the inorganic fine particles include metal oxide fine particles, inorganic acid metal salt fine particles (sulfate, carbonate, phosphate, etc.), metal halide fine particles, metal nitride fine particles, metal carbide fine particles, metal boride fine particles, metal At least one of fine particles and ceramic fine particles can be used. Moreover, you may use together 2 or more types of the above-mentioned microparticles | fine-particles.

  As the metal oxide, for example, at least one of alumina, tin oxide, titanium oxide, zinc oxide, zirconium oxide, cerium oxide, diiron trioxide, antimony oxide, magnesium oxide, chromium oxide, and silicon oxide can be used. . As the inorganic acid metal salt, for example, at least one of calcium sulfate, barium sulfate, calcium carbonate, calcium phosphate, and potassium chloride can be used. As the metal nitride, for example, at least one of titanium nitride, aluminum nitride, zirconium nitride, chromium nitride, tungsten nitride, and silicon nitride can be used. As the metal carbide, for example, at least one of titanium carbide, zirconium carbide, tungsten carbide, chromium carbide, niobium carbide, and silicon carbide can be used. As the metal boride, for example, at least one of titanium boride, zirconium boride, tungsten boride, chromium boride, and molybdenum boride can be used. As the metal, at least one of silver and copper can be used. Moreover, you may use 2 or more types of each above-mentioned material together. Moreover, surface treatment of fine particles (nanoparticles) may be performed as necessary.

  In the present embodiment, the first liquid LQ1 is a liquid in which the above-described fine particles (nanoparticles) are dispersed in a predetermined liquid (pure water) at a first ratio. The second liquid LQ2 is a liquid in which the above-described fine particles (nanoparticles) are dispersed in a predetermined liquid (pure water) at a second ratio.

  In the present embodiment, the liquid adjusting device 24 adds the second liquid LQ2 (LQ2a, LQ2b) to at least a part of the first liquid LQ1, so that the predetermined substance of the liquid LQ supplied to the first flow path 25 is increased. Adjust the percentage.

  The liquid adjusting device 24 includes generating devices 28 and 29 that generate the second liquid LQ2. In the present embodiment, the liquid adjustment device 24 generates the first generation device 28 that can generate the second liquid LQ2a whose second ratio is higher than the first ratio, and the second liquid LQ2b whose second ratio is lower than the first ratio. And a possible second generation device 29. In the following description, the second liquid LQ2a is appropriately referred to as concentrated liquid LQ2a, and the second liquid LQ2b is appropriately referred to as diluted liquid LQ2b.

  In the present embodiment, the first generator 28 generates the concentrated liquid LQ2a from a part of the first liquid LQ1, and the second generator 29 generates the diluted liquid LQ2b from a part of the first liquid LQ1. The first and second generation devices 28 and 29 generate the second liquids LQ2a and LQ2b from a part of the first liquid LQ1 returned to the liquid adjustment device 24 from the third flow path 27. A pressure pump 34 is disposed in the third flow path 27. By operating the pressurizing pump 34, the control device 9 can return at least a part of the liquid LQ that has not flowed into the second flow path 26 to the liquid adjusting device 24 as the first liquid LQ1. In the present embodiment, a measuring device 47 is disposed in the third flow path 27. The measuring device 47 can measure the refractive index of the first liquid LQ1 supplied to the liquid adjusting device 24 with respect to the exposure light EL. The measuring device 47 will be described later. In the present embodiment, fresh predetermined liquid (pure water) is appropriately supplied (supplemented) to the second flow path 27 from a predetermined supply source via the fourth flow path 51. Therefore, in the present embodiment, the liquid LQ that did not flow into the second flow path 26 from the first flow path 25 and the pure water supplied from the fourth flow path 51 to the third flow path 27 are the first liquid LQ1. To the liquid adjusting device 24. The pure water replenished from the fourth channel 51 to the third channel 27 may contain fine particles (nanoparticles). Further, the amount of pure water replenished from the fourth channel 51 to the third channel 27 is determined according to the amount of the liquid LQ that has flowed into the second channel 26. In addition, the liquid which flowed into the 3rd flow path 27 from the 1st flow path 25 between the connection part of the 1st flow path 25 and the 3rd flow path 27, and the 3rd flow path 27 and the 4th flow path 51. A part of LQ may be discharged. In this case, what is necessary is just to increase the quantity of the pure water replenished from the 4th flow path 51 according to discharge amount.

  In the present embodiment, of the liquid LQ supplied to the first flow path 25, the amount of liquid LQ flowing in the third flow path 27 (flow rate per unit time) is the amount of liquid LQ flowing in the second flow path 26. More than (flow rate per unit time). As an example, the amount of the liquid LQ flowing from the first channel 25 to the third channel 27 is about 100 times the amount of the liquid LQ flowing from the first channel 25 to the second channel 26.

  As shown in FIG. 3, the liquid adjustment device 24 is branched from the third flow path 27, the main flow path 30 to which at least a part of the first liquid LQ <b> 1 from the third flow path 27 is supplied, and the third flow path. 27, the first branch flow path 31 for guiding at least a part of the first liquid LQ1 from the third flow path 27 to the first generation device 28, the third flow path 27, and the third flow And a second branch channel 32 for guiding at least part of the first liquid LQ1 from the channel 27 to the second generator 29. In the present embodiment, most (eg, 90%) of the first liquid LQ 1 from the third flow path 27 is supplied to the main flow path 30. The first generator 28 generates the concentrated liquid LQ2a from the first liquid LQ1 supplied from the first branch flow path 31. The second generator 29 generates the diluted liquid LQ2b from the first liquid LQ1 supplied from the second branch flow path 32.

  FIG. 4 is a diagram illustrating an example of the first generation device 28. In FIG. 4, the 1st production | generation apparatus 28 is provided with the concentration apparatus 28A which concentrates the 1st liquid LQ1 in order to make a 2nd ratio high. The concentrating device 28 </ b> A includes a housing 35 and a semipermeable membrane 36 disposed inside the housing 35. The semipermeable membrane 36 includes, for example, cellulose. The semipermeable membrane 36 divides the inside of the housing 35 into a first space 35A and a second space 35B. The first liquid LQ1 from the first branch channel 31 is supplied to the first space 35A. The first liquid LQ1 is supplied to the first space 35A in a pressurized state. Since the semipermeable membrane 36 transmits pure water and does not transmit fine particles (nanoparticles), only the pure water is semipermeable from the first space 35A by supplying the first liquid LQ1 to the first space 35A. It moves to the second space 35B through the film 36. Thereby, the concentrated liquid LQ2a in which the second ratio is increased to a predetermined ratio in the first space 35A is generated. That is, the concentration device 28A generates the concentrated liquid LQ2a by the reverse osmosis membrane method. The concentrated liquid LQ2a produced by the concentrating device 28A is supplied to the flow path 37. On the other hand, the pure water in the second space 35 </ b> B is discharged to the outside through the discharge flow path 38.

  In addition, the 1st production | generation apparatus 28 may be provided with the stirring apparatus 28B as shown in FIG. In FIG. 5, the stirrer 28B includes a housing 35B and a stirrer 36B including a rotatable blade member disposed inside the housing 35B. The first branch channel 31 supplies the first liquid LQ1 to the space inside the housing 35B. Further, the nanoparticles are supplied from the predetermined supply channel 39 to the internal space of the housing 35B. The stirrer 36B stirs and mixes the first liquid LQ1 and the nanoparticles supplied to the space inside the housing 35B. Thereby, the concentrated liquid LQ2a with the second ratio increased is generated. The produced concentrated liquid LQ2a is supplied to the flow path 37. Note that a liquid having a sufficiently high proportion of nanoparticles may be supplied to the space inside the housing 35B via the supply flow path 39.

  The second generator 29 includes a diluter 29A for diluting the first liquid LQ1 in order to reduce the second ratio. In the present embodiment, the dilution device 29A supplies pure water to the first liquid LQ1 flowing through the second branch flow path 32, thereby diluting the first liquid LQ1 and generating the diluted liquid LQ2b. As shown in FIG. 3, the diluting device 29 </ b> A includes a supply channel 40 connected to the second branch channel 32 in order to supply pure water to the second branch channel 32. Pure water is supplied to the supply channel 40 from a predetermined supply source. The pure water supplied to the supply channel 40 is supplied to the second branch channel 32. Thereby, the diluted liquid LQ2b is generated. Although not shown, a stirrer that mixes the first liquid LQ1 and pure water is disposed at the junction 48 between the supply channel 40 and the second branch channel 32. The stirring device includes a rotatable blade member. In addition, it can also stir by adjusting the shape of a flow path and generating a turbulent flow in the flow path.

  In the present embodiment, a mass flow controller (flow rate control device) 41 is disposed in the supply flow path 40. The control device 9 can adjust the amount of pure water per unit time supplied to the second branch flow path 32 by controlling the mass flow controller 41. The control device 9 can adjust the second ratio of the dilution liquid LQ2b by adjusting the amount of pure water per unit time supplied to the second branch flow path 32. The diluted liquid LQ2b generated by the dilution device 29A is supplied to the flow path.

  Each of the main flow path 30, the flow path 37, and the flow path 42 is connected to the first flow path 25. The first liquid LQ1 flowing through the main flow path 30 joins and is mixed with the concentrated liquid LQ2a flowing through the flow path 37 or the diluted liquid LQ2b flowing through the flow path 42 at the merging portion 46. In other words, the liquid adjusting device 24 supplies the concentrated liquid LQ2a from the flow path 37 or the diluted liquid LQ2 from the flow path 42 as the second liquid LQ2 to the first liquid LQ1 flowing in the main flow path 30 at the junction 46. Can be added. By adding the concentrated liquid LQ2a or the diluted liquid LQ2b to at least a part of the first liquid LQ1, it is possible to generate a liquid LQ containing a predetermined substance (fine particles) at a desired ratio. Note that both the concentrated liquid LQ2a and the diluted liquid LQ2b may be mixed in the first liquid LQ1 from the main flow path 30 as the second liquid LQ2. In addition, a stirring device that mixes the first liquid LQ1 and the second liquid LQ2 may be disposed in the junction 46. Thereby, the predetermined substance (fine particles) can be uniformly distributed (dispersed) in the liquid LQ. For example, the stirring device includes a rotatable blade member. In addition, it can also stir by adjusting the shape of a flow path and generating a turbulent flow in the flow path.

  In the present embodiment, mass flow controllers 43, 44, and 45 are disposed in the main flow path 30, the flow path 37, and the flow path 42, respectively. The controller 9 can adjust at least one of the amount of the concentrated liquid LQ2a and the amount of the diluted liquid LQ2b added to the first liquid LQ1 by controlling the mass flow controllers 43, 44, and 45. Thereby, the quantity (ratio) of the nanoparticle contained in the liquid LQ can be adjusted.

  In the present embodiment, the optical characteristics of the liquid LQ can be adjusted by adjusting the amount (ratio) of the nanoparticles contained in the liquid LQ. The optical characteristics include the refractive index of the liquid LQ with respect to the exposure light EL. That is, by adjusting the amount (ratio) of nanoparticles contained in the liquid LQ, the optical characteristics of the liquid LQ (the refractive index of the liquid LQ with respect to the exposure light EL) can be adjusted to a desired state.

  For example, the refractive index of the liquid LQ with respect to the exposure light EL can be increased by increasing the ratio of the nanoparticles. That is, the refractive index of the liquid LQ with respect to the exposure light EL can be increased as the amount of nanoparticles dispersed in the predetermined liquid is increased, in other words, as the mixing ratio of the nanoparticles to the predetermined liquid is increased. When the transmittance of the liquid LQ with respect to the exposure light EL is reduced by increasing the proportion of the nanoparticles, the amount of nanoparticles (in consideration of the target value of refractive index and the target value of transmittance) Ratio) is adjusted.

  Therefore, the liquid adjusting device 24 adjusts the amount of the second liquid LQ2 added to the first liquid LQ1 from the main flow channel 30, thereby adjusting the amount of the liquid LQ supplied from the liquid adjusting device 24 to the first flow channel 25. Optical characteristics (refractive index) can be adjusted. The control device 9 can adjust the optical characteristics (refractive index) of the liquid LQ with high accuracy by controlling the mass flow controllers 43, 44, and 45.

  As described above, in the present embodiment, the liquid supply device 20 includes the measurement device 47 that measures the optical characteristics of the first liquid LQ1 supplied to the liquid adjustment device 24. The measuring device 47 can measure the refractive index of the liquid LQ with respect to the exposure light EL. In the liquid adjustment device 24, based on the measurement result of the measurement device 47, the amount of at least one of the concentrated liquid LQ2a and the dilution liquid LQ2b added to the first liquid LQ1 from the main channel 30 is adjusted.

  6 is a schematic perspective view showing an example of the measuring device 47, and FIG. 7 is a cross-sectional view. 6 and 7, the measuring device 47 is provided in the middle of the third flow path 27, and a flow path forming member 133 that forms a flow path 137 through which the first liquid LQ <b> 1 flows, and the flow path forming member 133. The light projecting unit 134 that irradiates the measurement light La, the optical element (condensing optical system) 135 that condenses the measurement light La that has passed through the flow path forming member 133, and the measurement light La that passes through the optical element 135 are received. And an imaging device 136 such as a CCD. It can be said that the flow path 137 is a part of the third flow path 27. The measurement light La emitted from the light projecting unit 134 to the flow path forming member 133 is a parallel light beam having an appropriate cross-sectional area. The distance between the optical element 135 and the imaging element 136 is substantially equal to the focal length of the optical element 35. The optical element 135 condenses the measurement light La that has passed through the optical element 135 on the imaging element 136. The measurement light La emitted from the light projecting unit 134 has substantially the same wavelength as the exposure light EL (193 nm, which is the wavelength of ArF excimer laser light). The flow path forming member 133 is formed of a member that can pass the measurement light La (exposure light EL), such as quartz or fluorite. The flow path forming member 133 is a tubular member having a triangular cross section. The flow path forming member 133 functions as a prism.

  When measuring the optical characteristics of the first liquid LQ1 using the measuring device 47, the control device 9 is applied to the first surface 133A of the flow path forming member 133 while the flow path 137 is filled with the liquid LQ. The measurement light La is emitted from the light projecting unit 134. The measurement light La applied to the flow path forming member 133 is applied to the first liquid LQ1 flowing through the flow path 137. The measurement light La irradiated to the first liquid LQ1 passes through the first liquid LQ, and then is emitted to the outside from the second surface 133B of the flow path forming member 133. The measurement light La emitted from the second surface 133B is condensed on the image sensor 136 by the optical element 135. The condensing position of the measurement light La on the image sensor 136 changes according to the optical characteristics of the liquid LQ flowing through the flow path 137. That is, since the optical path of the measurement light La that passes through the liquid LQ varies according to the refractive index of the liquid LQ with respect to the measurement light La, the condensing position of the measurement light La on the image sensor 136, that is, the measurement light by the image sensor 136 The light receiving position of La changes as indicated by an arrow F1 in FIG. The light reception result of the image sensor 136 is output to the control device 9. The control device 9 stores in advance the relationship between the light receiving position of the measurement light La on the image sensor 136 and the refractive index of the liquid LQ in the flow path 137. The control device 9 can obtain the refractive index of the liquid LQ with respect to the measurement light La based on the light reception result of the image sensor 136 and the stored information. In the present embodiment, the measuring device 47 constantly monitors the optical characteristics of the first liquid LQ1 while the first liquid LQ1 is being supplied to the liquid adjusting device 24. However, the measurement timing can be determined as appropriate. .

  The control device 9 adjusts the amount of the second liquid LQ2 added to the first liquid LQ1 from the main channel 30 based on the measurement result of the measuring device 47. That is, the control device 9 uses the mass flow controller 44 and / or the mass flow controller 45 so that the liquid LQ has a desired optical characteristic (refractive index) based on the measurement result of the measurement device 47, and uses the first liquid LQ1. The amount (addition amount) of at least one of the concentrated liquid LQ2a and the diluted liquid LQ2b added to is adjusted. The control device 9 has control information related to the relationship between the adjustment amount of the optical characteristic (refractive index) and the addition amount, and is added to the first liquid LQ1 based on the measurement result of the measurement device 47 and the control information. The amount of the second liquid LQ2 is adjusted. The control information is determined in advance based on experiments, simulations, and the like. For example, when the measurement value of the measurement device 47 is lower than the target value of the refractive index, the control device 9 adds the concentrated liquid LQ2a to the first liquid LQ1. On the other hand, when the measured value of the measuring device 47 is higher than the target value of the refractive index, the control device 9 adds the diluted liquid LQ2b to the first liquid LQ1.

  The second flow path 26 is connected to the flow path 21, and the liquid LQ supplied to the second flow path 26 is supplied from the supply port 16 to the optical path K through the flow path 21. A mass flow controller 50 is disposed in the second flow path 26. The controller 9 can control the mass flow controller 50 to adjust the supply amount of the liquid LQ per unit time to the supply port 16. In other words, the control device 9 can control the mass flow controller 50 to adjust the amount of the liquid LQ that flows from the first flow path 25 to the third flow path 27. Therefore, by controlling the mass flow controller 50 to stop the supply of the liquid LQ to the supply port 16, all of the liquid LQ sent to the first flow path 25 can be flowed to the third flow path 27.

  Next, a method for exposing the substrate P using the exposure apparatus EX having the above-described configuration will be described. In order to fill the optical path K with the liquid LQ having a desired refractive index, the control device 9 measures the refractive index of the liquid LQ with the measuring device 47, and changes the first liquid LQ1 with the liquid adjusting device 24 based on the measurement result. The amount of the second liquid LQ2 to be added is determined, and the mass flow controller (44, 45) is controlled based on the determined result. Thereby, the liquid LQ having a desired refractive index is supplied from the liquid adjusting device 24 to the supply port 16 via the first flow path 25 and the second flow path 26. Further, in order to expose the substrate P, the substrate P held on the substrate stage 2 is disposed at the exposure position EP, and an immersion space LS is formed so as to fill the optical path K with the liquid LQ.

  The exposure apparatus EX of the present embodiment is a scanning exposure apparatus (so-called scanning stepper) that projects an image of the pattern of the mask M onto the substrate P while synchronously moving the mask M and the substrate P in a predetermined scanning direction. In the present embodiment, the scanning direction (synchronous movement direction) of the substrate P is the Y-axis direction, and the scanning direction (synchronous movement direction) of the mask M is also the Y-axis direction. The control device 9 moves the substrate P in the Y-axis direction with respect to the projection region PR of the projection optical system PL in a state where the immersion space LS is formed, and synchronizes with the movement of the substrate P in the Y-axis direction. Thus, the substrate P is exposed with the exposure light EL through the projection optical system PL and the liquid LQ while moving the mask M in the Y-axis direction with respect to the illumination region IR of the illumination system IL.

  In this embodiment, since the optical path K is filled with the liquid LQ having a high refractive index, the resolution and the depth of focus can be substantially improved. Therefore, a fine pattern can be satisfactorily formed on the substrate P.

  Even during the exposure of the substrate P, the refractive index of the liquid LQ is measured (monitored) by the measuring device 47, and the control device 9 executes the adjusting operation by the liquid adjusting device 24 based on the measurement result. Thereby, the substrate P can always be exposed through the liquid LQ having the optimum refractive index.

  In the present embodiment, of the liquid LQ supplied to the first flow path 25, the amount of the liquid LQ (first liquid LQ 1) flowing through the third flow path 27 is the amount of the liquid LQ flowing through the second flow path 26. Greater than. In other words, the amount of liquid circulated in the circulation system including the first flow path 25, the third flow path 27, the pressure pump 34, and the liquid adjustment device 24 is compared with the amount of liquid supplied to the supply port 16. There is much more. Further, the amount of the first liquid LQ1 flowing through the main channel 30 is much larger than the amount of liquid flowing through the first and second branch channels 31 and 32. In other words, the adjustment of the optical characteristics of the liquid LQ delivered from the liquid adjustment device 24 is executed by adding a small amount of the second liquid LQ2 to the large amount of the first liquid LQ1. Thereby, the quantity of the nanoparticle contained in the liquid LQ supplied to the supply port 16, and also the refractive index of the liquid LQ can be adjusted with high precision.

  Note that a measurement device similar to the measurement device 47 is arranged in the first flow path 25, and the optical characteristics (for example, refractive index) of the liquid LQ delivered from the liquid adjustment apparatus 24 to the first flow path 25 are confirmed. May be. In this case, when a deviation occurs between the measured value of the optical characteristic (refractive index) of the liquid LQ delivered to the first flow path 25 and the target value, the control information stored in the control device 9 based on the deviation. May be modified. Further, the exposure condition may be adjusted based on the measurement result of the optical characteristic (refractive index) of the liquid LQ sent to the first flow path 25. The adjustment of the exposure condition includes adjustment of the imaging characteristics of the projection optical system PL. The control device 9 can adjust the imaging characteristic of the projection optical system PL using the imaging characteristic adjustment system 19 based on the measurement result of the measuring device arranged in the first flow path 25. Even when the refractive index of the liquid LQ supplied from the supply port 16 in order to satisfy the optical path K fluctuates or deviates from the target value, the measurement result of the measuring device arranged in the first flow path 25 is obtained. Based on this, by adjusting the imaging characteristics of the projection optical system PL, the substrate P can be exposed with a pattern image in a desired state. For example, when the image plane position of the projection optical system PL changes or various aberrations such as coma aberration occur due to the deviation of the refractive index of the liquid LQ from the target value, the control device 9 causes the aberration to occur. The imaging characteristic adjustment system 19 is used to adjust the imaging characteristic of the projection optical system PL so as to correct the above. For example, when the image plane position of the projection optical system PL changes according to the refractive index of the liquid LQ, the substrate stage 2 is controlled based on the measurement result of the measurement device arranged in the first flow path 25. The positional relationship between the image plane and the surface of the substrate P (exposure plane) may be adjusted.

  As described above, according to the present embodiment, the optical path K of the exposure light EL can be satisfactorily filled with the liquid LQ having a high refractive index. In addition, fluctuations in the optical characteristics of the liquid LQ supplied from the supply port 16 can be suppressed. Therefore, it is possible to suppress the change in the imaging characteristics through the liquid LQ, and it is possible to suppress the occurrence of defective exposure and the generation of defective devices.

  In the above-described embodiment, the case where the second liquid LQ2 (dilution liquid LQ2b) includes a predetermined substance (nanoparticle) has been described as an example. However, even if the liquid does not include the predetermined substance (nanoparticle), Good. That is, the second ratio may be zero, and the second liquid LQ2 (diluted liquid LQ2b) may be pure water not containing nanoparticles. That is, pure water may be supplied to the flow path 42 without providing the second branch flow path 32.

  In the above-described embodiment, the case where the predetermined liquid is pure water has been described as an example, but a liquid other than pure water may be used.

  In each of the above-described embodiments, the case where the first liquid LQ1 (or the second liquid LQ2) is generated by mixing fine particles (nanoparticles) of the predetermined substance with the predetermined liquid has been described as an example. The predetermined substance may not be mixed in the state of fine particles (nanoparticles).

  In each of the above-described embodiments, the projection optical system PL fills the optical path on the exit side (image plane side) of the last optical element with a liquid, but this is disclosed in US Patent Application Publication No. 2005/0248856 and the like. As described above, it is possible to employ a projection optical system in which the optical path on the incident side (object plane side) of the last optical element is filled with liquid. By filling the optical path on the incident side (object plane side) of the last optical element with the liquid LQ adjusted by the liquid adjusting device 24, desired imaging characteristics can be obtained.

  In each of the above-described embodiments, the case where the optical path K is the optical path of the exposure light EL has been described as an example. However, the optical path of the measurement light may be used.

  As the substrate P in each of the above embodiments, not only a semiconductor wafer for manufacturing a semiconductor device, but also a glass substrate for a display device, a ceramic wafer for a thin film magnetic head, or an original mask or reticle used in an exposure apparatus. (Synthetic quartz, silicon wafer) or the like is applied.

  As the exposure apparatus, in addition to the step-and-scan type scanning exposure apparatus (scanning stepper) that scans and exposes the pattern of the mask M by moving the mask M and the substrate P synchronously, the mask M and the substrate P are The present invention can also be applied to a step-and-repeat projection exposure apparatus (stepper) in which the pattern of the mask M is collectively exposed in a stationary state and the substrate P is sequentially moved stepwise.

  Furthermore, in the step-and-repeat exposure, after the reduced image of the first pattern is transferred onto the substrate P using the projection optical system while the first pattern and the substrate P are substantially stationary, the second pattern With the projection optical system, the reduced image of the second pattern may be partially overlapped with the first pattern and collectively exposed on the substrate P (stitch type batch exposure apparatus). ). Further, the stitch type exposure apparatus can be applied to a step-and-stitch type exposure apparatus in which at least two patterns are partially transferred on the substrate P, and the substrate P is sequentially moved.

  Further, as disclosed in, for example, US Pat. No. 6,611,316, two mask patterns are synthesized on a substrate via a projection optical system, and one shot area on the substrate is obtained by one scanning exposure. The present invention can also be applied to an exposure apparatus that performs double exposure almost simultaneously. The present invention can also be applied to proximity type exposure apparatuses, mirror projection aligners, and the like.

  Further, as the exposure apparatus EX, a twin stage type having a plurality of substrate stages as disclosed in US Pat. No. 6,590,634, US Pat. No. 6,208,407, US Pat. No. 6,262,796, etc. An exposure apparatus can also be employed.

  Further, as disclosed in, for example, US Pat. No. 6,897,963 and European Patent Application No. 1713113, a reference stage on which a substrate is held and a reference mark are formed, a measurement member (optical member) ), And an exposure apparatus provided with a measurement stage on which various photoelectric sensors and the like are mounted. The above-described embodiments can also be applied to an exposure apparatus that includes a plurality of substrate stages and measurement stages.

 Further, in each of the above-described embodiments, an immersion exposure apparatus that performs exposure in a state where the entire surface of a substrate to be exposed is immersed in a liquid as disclosed in US Pat. Applicable.

  The type of the exposure apparatus is not limited to an exposure apparatus for manufacturing a semiconductor element that exposes a semiconductor element pattern onto the substrate P. An exposure apparatus for manufacturing a liquid crystal display element or a display, a thin film magnetic head, an image sensor (CCD) In addition, the present invention can be widely applied to an exposure apparatus for manufacturing a micromachine, MEMS, DNA chip, reticle, mask, or the like.

  In each of the above-described embodiments, each position information of each stage is measured using an interferometer system including a laser interferometer. However, the present invention is not limited to this. For example, a scale (diffraction grating) provided in each stage. ) May be used.

  In each of the above-described embodiments, 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 Japanese Patent No. 6778257, a variable shaped mask (also known as an electronic mask, an active mask, or an image generator) that forms a transmission pattern, a reflection pattern, or a light emission pattern based on electronic data of a pattern to be exposed. May be used). Further, a pattern forming apparatus including a self-luminous image display element may be provided instead of the variable molding mask including the non-luminous image display element.

  In each of the above embodiments, the exposure apparatus provided with the projection optical system PL has been described as an example. However, the present invention can be applied to an exposure apparatus and an exposure method that do not use the projection optical system PL. Even when the projection optical system PL is not used as described above, the exposure light is irradiated onto the substrate via an optical member such as a lens, and the liquid is held between the optical member and the substrate.

  Further, as disclosed in, for example, International Publication No. 2001/035168, an exposure apparatus (lithography system) that exposes a line and space pattern on the substrate P by forming interference fringes on the substrate P. The present invention can also be applied to.

  As described above, the exposure apparatus according to the present embodiment assembles various subsystems including the constituent elements recited in the claims of the present application so as to maintain predetermined mechanical accuracy, electrical accuracy, and optical accuracy. It is manufactured by. In order to ensure these various accuracies, before and after assembly, various optical systems are adjusted to achieve optical accuracy, various mechanical systems are adjusted to achieve mechanical accuracy, and various electrical systems are Adjustments are made to achieve electrical accuracy. The assembly process from the various subsystems to the exposure apparatus includes mechanical connection, electrical circuit wiring connection, pneumatic circuit piping connection and the like between the various subsystems. Needless to say, there is an assembly process for each subsystem before the assembly process from the various subsystems to the exposure apparatus. When the assembly process of the various subsystems to the exposure apparatus is completed, comprehensive adjustment is performed to ensure various accuracies as the entire exposure apparatus. The exposure apparatus is preferably manufactured in a clean room where the temperature, cleanliness, etc. are controlled.

  As shown in FIG. 8, a microdevice such as a semiconductor device includes a step 201 for designing a function / performance of the microdevice, a step 202 for manufacturing a mask (reticle) based on the design step, and a substrate which is a base material of the device. Substrate processing step 204 including substrate processing (exposure processing) including exposing the substrate with exposure light using a mask pattern and developing the exposed substrate according to the above-described embodiment. The device is manufactured through a device assembly step (including processing processes such as a dicing process, a bonding process, and a package process) 205, an inspection step 206, and the like.

  Note that the requirements of the above-described embodiments can be combined as appropriate. In addition, the disclosures of all published publications and US patents related to the exposure apparatus and the like cited in the above-described embodiments and modifications are incorporated herein by reference.

It is a schematic block diagram which shows an example of the exposure apparatus which concerns on this embodiment. It is an enlarged view which shows an example of the exposure apparatus which concerns on this embodiment. It is a block diagram which shows an example of the liquid supply apparatus which concerns on this embodiment. It is a schematic diagram which shows an example of a 1st production | generation apparatus. It is a schematic diagram which shows an example of a 1st production | generation apparatus. It is a perspective view which shows an example of a measuring device. It is sectional drawing which shows an example of a measuring device. It is a flowchart figure which shows an example of the manufacturing process of a microdevice.

Explanation of symbols

DESCRIPTION OF SYMBOLS 2 ... Substrate stage, 9 ... Control apparatus, 10 ... End optical element, 11 ... Ejection surface, 16 ... Supply port, 17 ... Recovery port, 19 ... Imaging characteristic adjustment system, 20 ... Liquid supply device, 24 ... Liquid adjustment device 25 ... 1st flow path, 26 ... 2nd flow path, 27 ... 3rd flow path, 28 ... 1st production | generation apparatus, 28A ... Concentration apparatus, 29 ... 2nd production | generation apparatus, 29A ... Dilution apparatus, 47 ... Measurement apparatus ,
EL ... exposure light, EX ... exposure device, K ... optical path, LQ ... liquid, LQ1 ... first liquid, LQ2 ... second liquid, P ... substrate

Claims (33)

An immersion system used for immersion exposure for exposing a substrate with exposure light,
A liquid conditioner;
A first flow path to which the liquid from the liquid adjusting device is supplied;
A second flow path that is branched from the first flow path and that guides at least part of the liquid supplied to the first flow path to the optical path of the exposure light;
For returning at least a part of the liquid branched from the first flow path and supplied to the first flow path to the second flow path as the first liquid to the liquid adjustment device. A third flow path,
The liquid adjusting device is capable of supplying a liquid generated by adding a second liquid having optical characteristics different from that of the first liquid to at least a part of the first liquid to the first flow path. system. The first liquid includes a predetermined substance at a first ratio to the predetermined liquid;
2. The liquid immersion system according to claim 1, wherein the predetermined liquid is contained in the predetermined liquid at a second ratio different from the first ratio. The first liquid includes fine particles of the predetermined substance at the first ratio in the predetermined liquid;
The liquid immersion system according to claim 2, wherein the second liquid includes the fine particles at the second ratio in the predetermined liquid. In the first liquid, the fine particles are dispersed in the first liquid in the first ratio,
The liquid immersion system according to claim 3, wherein the fine particles are dispersed in the second liquid at the second ratio.   The immersion system according to claim 4, wherein the fine particles include nanoparticles.   The liquid immersion system according to any one of claims 2 to 5, wherein the first ratio or the second ratio includes zero.   The liquid immersion system according to claim 2, wherein the predetermined liquid is pure water.   The liquid adjustment device adjusts a ratio of the predetermined substance in the liquid supplied to the first flow path by adding the second liquid to at least a part of the first liquid. The immersion system according to any one of the above.   The liquid immersion system according to claim 2, wherein the liquid adjustment device includes a generation device that generates the second liquid.   The liquid immersion system according to claim 9, wherein the generation device generates the second liquid from a part of the first liquid.   The immersion system according to claim 10, wherein the generating device includes a concentrating device that concentrates the first liquid to increase the second ratio.   The immersion system according to claim 11, wherein the concentrating device includes a semipermeable membrane.   The liquid immersion system according to claim 11 or 12, wherein the concentration device includes a stirring device.   The immersion system according to any one of claims 10 to 13, wherein the generation device includes a dilution device that reduces the second ratio.   The liquid according to claim 1, wherein the amount of liquid flowing in the third flow path out of the liquid supplied to the first flow path is larger than the amount of liquid flowing in the second flow path. Immersion system.   The said liquid adjustment apparatus adjusts the optical characteristic of the liquid supplied to the said 1st flow path from the said liquid adjustment apparatus by adding a said 2nd liquid to at least one part of the said 1st liquid. The liquid immersion system according to claim 15.   The liquid immersion system according to claim 16, wherein the optical characteristic includes a refractive index of the liquid with respect to the exposure light. A measuring device for measuring the optical characteristics of the liquid supplied from the liquid adjusting device;
The liquid immersion system according to any one of claims 1 to 16, wherein the liquid adjustment device adds the second liquid based on a measurement result of the measurement device.   The liquid immersion system according to claim 18, wherein the liquid adjustment device adjusts an amount of the second liquid added to at least a part of the first liquid based on a measurement result of the measurement device.   20. The immersion system according to claim 18, wherein the optical characteristic includes a refractive index of the liquid with respect to the exposure light. An immersion system according to claim 18-20,
An exposure apparatus that exposes a substrate with exposure light via liquid supplied from the liquid adjustment apparatus of the liquid immersion system via the first flow path and the second flow path. The immersion system according to claim 1 to 17,
An exposure apparatus that exposes a substrate with exposure light via liquid supplied from the liquid adjustment apparatus of the liquid immersion system via the first flow path and the second flow path. A measuring device for measuring the optical characteristics of the liquid supplied from the liquid adjusting device;
The exposure apparatus according to claim 22, wherein an exposure condition is adjusted based on a measurement result of the measurement apparatus. A projection optical system;
An imaging characteristic adjusting system for adjusting the imaging characteristic of the projection optical system,
24. The exposure apparatus according to claim 23, wherein the adjustment of the exposure condition includes adjustment of an imaging characteristic of the projection optical system. Exposing the substrate using the exposure apparatus according to any one of claims 21 to 24;
Developing the exposed substrate; and a device manufacturing method. An exposure method for exposing a substrate with exposure light,
Supplying liquid from the liquid regulating device to the first flow path;
Supplying a part of the liquid supplied to the first flow path to the optical path of the exposure light via the second flow path;
Exposing the substrate with exposure light through a liquid supplied to the optical path of the exposure light;
Returning at least part of the liquid that has not flowed into the second flow path out of the liquid supplied to the first flow path as a first liquid to the liquid adjustment device via the third flow path;
Adding a second liquid having optical characteristics different from that of the first liquid to at least a part of the first liquid;
Supplying a liquid generated by adding the second liquid to at least a part of the first liquid to the first flow path. The first liquid includes a predetermined substance at a first ratio to the predetermined liquid;
27. The exposure method according to claim 26, wherein the second liquid includes the predetermined substance in the predetermined liquid at a second ratio different from the first ratio. The first liquid includes fine particles of the substance at the first ratio in the predetermined liquid,
28. The exposure method according to claim 27, wherein the second liquid contains the fine particles at the second ratio in the predetermined liquid. In the first liquid, the fine particles are dispersed in the first liquid in the first ratio,
29. The exposure method according to claim 28, wherein the second liquid has the fine particles dispersed in the second liquid at the second ratio.   30. The exposure method according to claim 28 or 29, wherein the fine particles include nanoparticles.   The exposure method according to any one of claims 27 to 30, wherein the first ratio or the second ratio includes zero.   32. The exposure method according to claim 27, wherein the predetermined liquid is pure water. Exposing the substrate using the exposure method according to any one of claims 26 to 32;
Developing the exposed substrate; and a device manufacturing method.

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