JP4984747B2 - Optical element, exposure apparatus using the same, and microdevice manufacturing method - Google Patents

Description

The present invention relates to an exposure apparatus including an optical element including a liquid repellent functional film and a projection optical system in which a liquid immersion area is formed in a specific optical path space among a plurality of optical path spaces formed along the optical axis direction of exposure light. And a method of manufacturing a microdevice.

  Conventionally, as this type of exposure apparatus, for example, an exposure apparatus described in WO99 / 49504 has been proposed. The exposure apparatus of this document includes an illumination optical system that irradiates a mask such as a photomask or a reticle with exposure light emitted from an exposure light source, and a wafer on which a photosensitive material (resist) is applied to an exposure pattern formed on the mask. A projection optical system for projecting onto a substrate such as a glass plate. The illumination optical system and the projection optical system each have a lens barrel, and at least one optical element (such as a lens) is accommodated in each lens barrel.

  Further, in the exposure apparatus of International Publication No. 99/49504, an optical path space which is a space between the projection optical system and the substrate in order to cope with a higher density of devices and a finer pattern formed on the substrate. A liquid (pure water) having a refractive index higher than that of gas is supplied to form an immersion region. Therefore, the exposure light that has passed through the projection optical system irradiates the substrate after passing through the immersion area.

  By the way, in the exposure apparatus of International Publication No. 99/49504, among the surfaces of the optical elements arranged closest to the substrate in the projection optical system, the surface facing the substrate is in contact with the liquid. When a large amount of liquid is unexpectedly supplied in a control mechanism or the like, a part of the liquid in the liquid immersion region travels along the side surface of the optical element, and holds the optical element and the optical element in the lens barrel ( There is a possibility of passing through the gap between the holding member) and entering the lens barrel. In addition, it is desirable that an optical element used under the severe condition of immersion exposure maintains an appropriate characteristic for a long period of time.

  A first object of the present invention is to provide a novel optical element capable of effectively preventing liquid from entering the environment in which the optical element is used, an exposure apparatus including the same, and exposure using such an exposure apparatus. It is to provide a method. A second object of the present invention is to provide an exposure apparatus including a projection optical system that can prevent liquid in the immersion area from entering the lens barrel without affecting the optical characteristics of the optical element, and the exposure apparatus. It is to provide a manufacturing method of the used microdevice.

According to a first aspect of the present invention, there is provided an exposure apparatus for irradiating a substrate with an exposure beam, wherein the optical element is irradiated with the exposure beam, and the optical path space on the exit surface side of the exposure beam is filled with a liquid; A liquid repellent functional film provided on at least a part of the surface outside the effective area of the optical element, wherein the liquid repellent functional film is formed on the surface of the optical element and the surface of the light shield film. e Bei repellent film, which is, the liquid repellent film, the between the shielding film and the liquid-repellent film or between the substrate and the light-shielding film of the optical element, a third functional layer further comprising Ru exposure apparatus is provided.

  According to this exposure apparatus, the liquid repellent functional film prevents the liquid in the immersion area from flowing through the side surface of the specific optical element to the space on the light incident surface side of the specific optical element for a long period of time. Can do.

  According to the second aspect of the present invention, there is provided an exposure apparatus that exposes a substrate with a pattern formed on a mask, which has a plurality of optical elements and is provided on the light emitting surface side of the optical element closest to the photosensitive substrate. A projection optical system that forms an immersion area in an optical path space and projects the pattern onto the photosensitive substrate, and a light shield provided on a part of the surface outside the effective area of one or more optical elements of the plurality of optical elements. An exposure apparatus having a film and a liquid repellent film is provided.

  According to the exposure apparatus of the second aspect, the liquid repellent film formed on the optical element prevents the liquid in the immersion area from flowing into the space on the light incident surface side of the optical element through the side surface of the optical element. can do. Further, the function of the liquid repellent film can be maintained over a long period of time by the light shielding film.

  According to the third aspect of the present invention, an exposure process of exposing a predetermined pattern on the photosensitive substrate using the exposure apparatus of the first or second aspect, and the photosensitive substrate exposed by the exposure process And a developing process for developing the microdevice. According to this microdevice manufacturing method, a good microdevice can be manufactured over a long period of time.

According to a fourth aspect of the present invention, there is provided an optical element used in an immersion exposure apparatus that exposes a substrate through a liquid, wherein the base area of the optical element and the effective area of the flange portion of the base material A liquid repellent member provided on at least a part of the outer surface of the substrate, and a light reducing member provided between the base material and the liquid repellent member, for dimming light and protecting the liquid repellent member from light irradiation; An optical element is provided. Since the optical element of the present invention is provided with the liquid repellent member and the light reducing member for maintaining the liquid repellency at the same time, it is possible to prevent unintentional flooding into the environment where the optical element is used for a long period of time. it can.

  According to a fifth aspect of the present invention, there is provided an optical system that is used in an immersion exposure apparatus that exposes a substrate through a liquid, and includes an optical element according to the fourth aspect. By using this optical system in the immersion exposure apparatus, it is possible to prevent unintentional immersion in the immersion exposure apparatus for a long period of time.

  According to the sixth aspect of the present invention, there is provided an immersion exposure apparatus including the optical system according to the fifth aspect. Therefore, the immersion exposure apparatus can continue good immersion exposure over a long period of time.

  According to the seventh aspect of the present invention, there is provided an exposure method using the immersion exposure apparatus according to the sixth aspect. According to this exposure method, good immersion exposure can be continued over a long period of time.

  According to an eighth aspect of the present invention, there is provided a device manufacturing method including exposing a substrate by the exposure method according to the seventh aspect, developing the exposed substrate, and processing the developed substrate. Provided. With this device manufacturing method, a highly accurate device can be manufactured over a long period of time.

  According to a ninth aspect of the present invention, there is provided a method of manufacturing an immersion exposure apparatus, the step of providing an illumination optical system, and the step of providing a projection optical system having an optical element at a predetermined position in a lens barrel. Providing a stage for mounting the substrate; providing a liquid supply system for supplying a liquid between the projection optical system and the substrate; and light from the light source for the illumination optical system and the projection optical system. Adjusting the arrangement of the illumination optical system, the projection optical system, and the stage so as to pass through the system in order and reach the substrate, and the step of providing the projection optical system includes the step of providing a surface of the optical element. An exposure apparatus manufacturing method including a step of providing a light reducing member at least in part and a step of providing a liquid repellent member on the light reducing member is provided. With this manufacturing method, an exposure apparatus including the optical element of the present invention can be manufactured.

  Hereinafter, an exposure apparatus according to an embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 1, the exposure apparatus 11 of the present embodiment synchronously moves a reticle R as a mask and a wafer W as a substrate in a one-dimensional direction (here, left and right in the drawing in FIG. 1). The circuit pattern formed on the reticle R is transferred to each shot area on the wafer W through the projection optical system PL. That is, the exposure apparatus 11 of the present embodiment is a step-and-scan type scanning exposure apparatus, that is, a so-called scanning stepper.

  The exposure apparatus 11 includes an exposure light source (not shown), an illumination optical system 12, a reticle stage RST, a projection optical system PL, a wafer stage WST, and the like. Reticle stage RST holds reticle R, and wafer stage WST holds wafer W. The exposure light source of the present embodiment uses a light source that emits ArF excimer laser light (wavelength 193 nm) as exposure light EL.

  The illumination optical system 12 includes an optical integrator (not shown) such as a fly-eye lens and a rod lens, various lens systems such as a relay lens and a condenser lens, an aperture stop, and the like. The exposure light EL emitted from an exposure light source (not shown) is adjusted so as to uniformly illuminate the pattern on the reticle R by passing through the illumination optical system 12.

  Reticle stage RST is arranged between illumination optical system 12 and projection optical system PL so that the mounting surface of reticle R is substantially orthogonal to the optical path. That is, reticle stage RST is arranged on the object plane side of projection optical system PL (on the exposure light EL incident side, which is the upper side in FIG. 1).

  The projection optical system PL includes a plurality of lens elements LS1, LS2, LS3, LS4, LS5, LS6 and LS7 (only seven are shown in FIG. 1). Among these lens elements LS <b> 1 to LS <b> 7, lens elements LS <b> 1 to LS <b> 6 other than the lens element closest to the wafer W (hereinafter referred to as a first specific lens element) LS <b> 7 are held in the lens barrel 13. A space between the lens elements LS1 to LS6 in the lens barrel 13 is filled with a purge gas (for example, nitrogen). A lens holder 14 for holding the first specific lens element (first specific optical element) LS7 is disposed at the lower end of the lens barrel 13. Each of the lens elements LS1 to LS7 has a light incident surface on which the exposure light EL is incident and a light emission surface on which the incident exposure light EL is emitted. The lens elements LS1 to LS7 are arranged so that the optical axes (O) are substantially coincident with each other and optical path spaces are formed on the light incident surface side and the light exit surface side.

  Wafer stage WST is arranged on the image plane side of projection optical system PL so that the mounting surface of wafer W is substantially orthogonal to the optical path of exposure light EL. Then, the pattern image on reticle R illuminated by exposure light EL is projected and transferred onto wafer W on wafer stage WST while being reduced to a predetermined reduction magnification through projection optical system PL.

  Here, the exposure apparatus 11 according to the present embodiment is a so-called immersion exposure in which the immersion method is applied in order to substantially shorten the wavelength of the exposure light EL to improve the resolution and substantially widen the depth of focus. Device. Therefore, the exposure apparatus 11 includes a liquid immersion mechanism. For the liquid immersion mechanism, as a liquid supply system, a first liquid supply for individually supplying pure water LQ to the light path space 15 on the light exit surface side and the light path space 16 on the light incident surface side of the first specific lens element LS7. A device 17 and a second liquid supply device 18 are provided. Further, the liquid immersion mechanism is provided with a first liquid recovery device 19 and a second liquid recovery device 20 for individually recovering the pure water LQ supplied to the optical path space 15 and the optical path space 16.

  As shown in FIG. 2, in the optical path space 15 between the first specific lens element LS7 and the wafer W, the pure water LQ is supplied from the first liquid supply device 17, thereby forming the liquid immersion region LT1. The Then, the pure water LQ that forms the liquid immersion region LT1 is recovered from the optical path space 15 based on the drive of the first liquid recovery device 19. Further, in the optical path space 16 between the first specific lens element LS7 and the lens element (second specific optical element) LS6 disposed on the object plane side of the projection optical system PL with respect to the first specific lens element LS7, The liquid immersion region LT2 is formed by supplying the pure water LQ from the second liquid supply device 18. That is, the lens element LS6 is configured as a second specific lens element close to the image plane of the projection optical system PL after the first specific lens element LS7. Then, the pure water LQ that forms the liquid immersion region LT2 is recovered from the optical path space 16 based on the driving of the second liquid recovery device 20.

    Here, the second specific lens element LS6 is an optical element having refractive power (lens action), and its lower surface LS6c is planar, and its upper surface LS6b is convex toward the object plane side of the projection optical system PL. And has a positive refractive power. The second specific lens element LS6 has a substantially circular shape when viewed from above, and the outer diameter of the upper surface LS6b is larger than the outer diameter of the lower surface LS6c. That is, the second specific lens element LS6 has an exposure light passage portion (effective area) LS6A through which the exposure light EL passes, and a flange portion LS6B formed on the outer peripheral side of the exposure light passage portion LS6A. Yes. The second specific lens element LS6 is supported by the lens barrel 13 via the flange portion LS6B. In the present application, the “effective area” of an optical element is an area where light other than unnecessary light such as flare light and stray light is planned to be irradiated or emitted to the optical element. For example, when the optical element is incorporated in an imaging optical system such as a projection optical system, an aberration is practically applied on the image plane of the imaging optical system. When the beam with the maximum numerical aperture is traced back from all image points in the image field that is the corrected region (= ray tracing from the image point), the optical surface of the optical element is reached. The area of the optical surface occupied by the luminous flux (tracked by reverse rays) is defined as the effective area of the optical surface, where each effective area has its optical area when the optical element has a plurality of optical surfaces. The effective area of the optical element (Optical element is comprise a plurality of effective regions).

  The first specific lens element LS7 is a non-refractive parallel plate that can transmit the exposure light EL, and the lower surface LS7c and the upper surface LS7b are parallel to each other. The first specific lens element LS7 has a substantially circular shape when viewed from above, and the outer diameter of the upper surface LS7b is formed larger than the outer diameter of the lower surface LS7c. That is, the first specific lens element LS7 is an exposure light passage portion (effective region) LS7A that allows the exposure light EL to pass through, and a flange portion LS7B is formed on the outer peripheral side of the exposure light passage portion LS7A. Yes. The first specific lens element LS7 is supported by the lens holder 14 via the flange portion LS7B.

  In the projection optical system PL of the present embodiment, an annular nozzle member (hereinafter referred to as pure water in the second optical path space 16 from the wafer W side) is provided between the lens barrel 13 and the lens holder 14. Since LQ is supplied, it is referred to as a “second nozzle member”.) 21 is disposed so as to surround the optical path of the exposure light EL. The second nozzle member 21 is fixed to the lower end portion of the lens barrel 13 with a screw (not shown). The lens holder 14 is fixed to the lower surface side of the second nozzle member 21 by a plurality of screws SC (only two are shown in FIG. 2).

  2, the inner surface 21b of the second nozzle member 21 faces the side surface LS6a between the lower surface LS6c and the lower surface LS6d of the second specific lens element LS6, and the upper surface 21c of the second nozzle member 21 is second. The specific lens element LS6 is disposed so as to face the lower surface LS6d. Here, an annular convex portion 21d is formed on the upper surface 21c of the second nozzle member 21, and by this convex portion 21d, between the upper surface of the convex portion 21d and the lower surface LS6d of the second specific lens element LS6. A very narrow gap is formed. That is, the second nozzle member 21 is formed between the inner side surface 21b and the side surface LS6a of the second specific lens element LS6, the upper surface of the convex portion 21d of the second nozzle member 21, and the lower surface LS6d of the second specific lens element LS6. By forming a gap between them, they are arranged so as not to contact the second specific lens element LS6.

Further, the side surface LS6a of the second specific lens element LS6 and the lower surface LS6d of the flange portion LS6B, that is, the surface outside the effective area of the second specific lens element LS6, that is, the optical axis (O) of the second specific lens element LS6. A water repellent functional film 28, which is a liquid repellent functional film, is formed in a region that does not intersect. As shown in FIG. 3, the water repellent functional film 28 includes a light shielding film 28a formed on the surfaces of the side surface LS6a and the lower surface LS6d of the second specific lens element LS6, and a liquid repellent film formed on the surface of the light shielding film 28a. And the water repellent film 28b. Here, the water repellent film 28b constituting the water repellent functional film 28 is formed of a fluorine resin material that can be formed at a low temperature, a fluorine resin material such as polytetrafluoroethylene, an acrylic resin material, or a silicon resin material. The light shielding film 28a constituting the water repellent functional film 28 is a metal film or a metal oxide film having an optical density OD1 or higher. As the water repellent film 28b, for example, CYTOP (English notation CYTOP) manufactured by Asahi Glass Co., Ltd. (English notation ASAHI GLASS CO., LTD.) May be used. Specifically, the metal film can be a film formed of at least one metal selected from the group consisting of Au, Pt, Ag, Ni, Ta, W, Pd, Mo, Ti, Si, and Cr. The metal oxide film is specifically a film formed of at least one substance selected from the group consisting of ZrO ₂ , HfO ₂ , TiO ₂ , Ta ₂ O ₅ , SiO and Cr ₂ O _3. obtain. That is, it may be a single substance selected from those oxide groups, or any mixture thereof.

  The following example is given as an example of the combination of the water repellent film / light shielding film.

Fluororesin 1.0μm / Si: 200nm
Fluororesin 1.0μm / Ta200nm
Fluorine resin 0.5μm / Cr2O3: 50nm / Cr: 150nm
Fluorine resin 0.5μm / W: 100nm / Cr: 100nm
Any of these combinations can be set to an optical density OD1 or higher.

  A method of providing the liquid repellent functional film 28 on the second specific lens element LS6 will be described below. First, the light shielding film 28b is formed outside the effective area on the surface of the optical element LS6. When the above-described metal film or metal oxide film is formed as the light shielding film 28b, vacuum vapor deposition method, ion beam assisted vapor deposition method, gas cluster ion beam assisted vapor deposition Gas cluster ion assisted vapor deposition method, ion plating method, ion beam sputtering method, magnetron sputtering method, bias sputtering method Further, a dry film forming method such as an RF sputtering method (radio frequency sputtering method) can be used. It is preferable to adjust the film thickness according to the film formation conditions such as the film formation rate and the film formation time, and to obtain an optical density of OD1 or more from the reflection and absorption of the resulting film. The light shielding film 28b can be typically 100 nm to 300 nm. In order to provide a film outside the effective area of the surface, a masking method in which the effective area of the optical element LS6 is previously masked with a seal or the like, or a shielding member is provided in an apparatus such as a vapor deposition apparatus, and the effective area of the optical element LS6 is provided. For example, a method for preventing deposits can be used.

  Next, a method for forming the liquid repellent film 28a on the light shielding film will be described. As a wet film formation method, a spin coating method, a dip coating method, or the like can be used. At this time, a film having an appropriate liquid repellent function can be formed by adjusting the concentration of the resin solution, the number of rotations during coating, the pulling speed, and the like. The liquid repellent film 28a can typically be 0.1 μm to 2.0 μm. In the present invention, it can be said that the liquid repellent function is sufficient if the contact angle is 90 degrees or more with respect to the liquid used in immersion exposure. After applying the liquid repellent film by these methods, the durability may be improved by improving the strength of the film by heating.

  Since the water repellent functional film 28 has a light shielding film 28a formed on the surface of the second specific lens element LS6, the water repellent film 28b is prevented from being irradiated with light caused by laser light or the like as the exposure light EL. can do. Since the water repellent film 28b is formed outside the effective area of the second specific lens element LS6, the exposure light EL is not normally irradiated directly. However, unintended reflected light or stray light may be applied to the water-repellent film 28b, and the light-shielding film 28a can prevent light deterioration of the water-repellent film 28b. In particular, in order to prevent stray light entering the water repellent film 28b through the second specific lens element LS6, the light shielding film 28a needs to be provided between the water repellent film 28b and the light exit surface of the second specific lens element LS6. There is. Here, when a metal film is used for the light shielding film 28a, since the metal film is a reflective film, the energy absorption of the light shielding film 28a can be suppressed, and the optical characteristics of the second specific lens element LS6 accompanying the temperature rise of the light shielding film 28a. Can be prevented. Further, when a metal oxide film is used for the light shielding film 28a, stray light that may be caused by reflection from the light shielding film 28a can be prevented because the metal oxide film is an absorption film.

  The second nozzle member 21 is connected to the second liquid supply device 18 via the liquid supply pipe 22. A liquid supply passage 23 communicating with the liquid supply pipe 22 is formed in the second nozzle member 21, and the pure water LQ that has flowed through the liquid supply pipe 22 and the liquid supply passage 23 is the inner surface of the second nozzle member 21. It flows into the optical path space 16 through the supply opening 24 formed on the 21b side. The second nozzle member 21 is connected to the second liquid recovery device 20 via the liquid recovery pipe 25. A liquid recovery passage 26 communicating with the liquid recovery pipe 25 is formed in the second nozzle member 21. The pure water LQ that forms the liquid immersion region LT2 in the optical path space 16 passes through a recovery opening 27 formed on the inner surface 21b side of the second nozzle member 21 on the side facing the supply opening 24. Then, it is recovered by the second liquid recovery device 20. The recovery opening 27 is formed on the object plane side (above in FIG. 2) with respect to the liquid immersion region LT2.

  Further, since the lens holder 14 and the wafer W are provided with an annular nozzle member (hereinafter referred to as pure water LQ is supplied to the first optical path space 15 from the wafer W side, “first nozzle member”). 30) is disposed so as to surround the optical path of the exposure light EL. The first nozzle member 30 is supported by a support member (not shown) so as not to contact the first specific lens element LS7 and the lens holder 14.

  Further, the inner surface 30b of the first nozzle member 30 faces the side surface LS7a between the lower surface LS7c and the lower surface LS7d of the first specific lens element LS7, and the upper surface 30c of the first nozzle member 30 has a flange portion in the first specific lens element LS7. It is arranged so as to face the lower surface LS7d of LS7B. The first nozzle member 30 is disposed so as not to contact the first specific lens element LS7 by forming a gap between the inner side surface 30b and the side surface LS7a of the first specific lens element LS7.

  Here, the peripheral edge LS7e on the upper surface of the first specific lens element LS7, that is, the circumference provided along the edge of the first specific lens element LS7 outside the effective area on the light incident surface side of the first specific lens element LS7. A step shape 50 that is a circular boundary shape, and a water-repellent film 51 that is formed on a surface of the first specific lens element LS7 outside the circumferential step shape 50 and is made of a fluororesin that can be formed at a low temperature. It has. A water repellent film or a light shielding film and a water repellent film may be provided outside the effective area of the first specific lens element LS7 (for example, the side surface LS7a).

  The first nozzle member 30 is connected to the first liquid supply device 17 via a liquid supply pipe 31. A liquid supply passage 32 communicating with the liquid supply pipe 31 is formed in the first nozzle member 30, and a supply opening 33 communicating with the liquid supply passage 32 is annular on the lower surface side of the first nozzle member 30. It is formed to make. The first nozzle member 30 is connected to the first liquid recovery device 19 via the liquid recovery pipe 34. A liquid recovery passage 35 communicating with the liquid recovery pipe 34 is formed in the first nozzle member 30, and a recovery opening 36 communicating with the liquid recovery passage 35 has an annular shape on the lower surface side of the first nozzle member 30. It is formed to make. The collection opening 36 is formed outside the supply opening 33 so as to surround the supply opening 33. The recovery opening 36 is provided with a porous member 37 in which a large number of holes are formed.

  Next, the operation when pure water LQ is supplied to the optical path spaces 15 and 16 of the exposure apparatus 11 of the present embodiment will be described. When wafer W placed on wafer stage WST is placed on the optical path of exposure light EL, first liquid supply device 17 and second liquid supply device 18 start driving. Then, pure water LQ is supplied from the first liquid supply device 17, and this pure water LQ flows in the liquid supply pipe 31 and the liquid supply passage 32 and enters the optical path space 15 through the supply opening 33. Supplied. At the same time, pure water LQ is supplied from the second liquid supply device 18, and this pure water LQ flows in the liquid supply pipe 22 and the liquid supply passage 23 and enters the optical path space 16 through the supply opening 24. Supplied.

  The first liquid supply device 17 stops driving when supplying a predetermined volume of pure water LQ into the optical path space 15. As a result, a liquid immersion region LT1 made of pure water LQ is formed in the optical path space 15. The second liquid supply device 18 stops driving when a predetermined volume of pure water LQ is supplied into the optical path space 16. As a result, a liquid immersion region LT2 made of pure water LQ is formed in the optical path space 16.

  At this time, a part of the pure water LQ in the optical path space 16 enters the gap between the second specific lens element LS6 and the second nozzle member 21, but the surface of the second specific lens element LS6 Since the water repellent functional film 28 is formed, the water repellent effect of the water repellent functional film 28 prevents the pure water LQ from entering the upper optical path space. When the pure water LQ enters the upper optical path space because the water repellent functional film 28 is not formed on the surface of the second specific lens element LS6, it is convex toward the object plane side of the second specific lens element LS6. There is a concern that the pure water LQ permeates into the optical thin film formed on the upper surface LS6b formed on the upper surface LS6b and the optical characteristics of the optical thin film deteriorate. Further, the optical thin film is dissolved by the pure water LQ, and the desired performance cannot be maintained. Therefore, the water repellent functional film 28 is necessary to prevent the pure water LQ from entering the optical path space above the second specific lens element LS6.

  In the exposure apparatus according to the above-described embodiment, the illumination optical device illuminates the mask (reticle) R (illumination process), and the transfer pattern formed on the mask R using the projection optical system PL is transferred to the photosensitive substrate ( By transferring the wafer (wafer) W (transfer process), a microdevice (semiconductor element, imaging element, liquid crystal display element, thin film magnetic head, etc.) can be manufactured. FIG. 4 shows an example of a technique for obtaining a semiconductor device as a micro device by forming a predetermined circuit pattern on a wafer W as a photosensitive substrate using the exposure apparatus according to the above-described embodiment. This will be described with reference to a flowchart.

  First, in step S301 in FIG. 4, a metal film is deposited on one lot of wafers W. In the next step S302, a photoresist is applied on the metal film on the wafer W of one lot. Thereafter, in step S303, using the exposure apparatus according to the above-described embodiment, the image of the pattern on the mask R is sequentially exposed to each shot area on the wafer W of one lot via the projection optical system PL. Transcribed. After that, in step S304, the photoresist on the one lot of wafers W is developed, and in step S305, etching is performed on the mask M by using the resist pattern as a mask on the one lot of wafers W. A circuit pattern corresponding to this pattern is formed in each shot area on each wafer W.

  Thereafter, a device pattern such as a semiconductor element is manufactured by forming a circuit pattern of an upper layer. According to the semiconductor device manufacturing method described above, since the exposure apparatus according to the above-described embodiment is used, a fine pattern can be satisfactorily exposed on the wafer. In steps S301 to S305, a metal is deposited on the wafer W, a resist is applied onto the metal film, and exposure, development, and etching processes are performed. Prior to these processes, the wafer is processed. It goes without saying that after a silicon oxide film is formed on W, a resist is applied onto the silicon oxide film, and each step such as exposure, development, and etching may be performed.

  In the exposure apparatus according to the above-described embodiment, a liquid crystal display element as a micro device can be obtained by forming a predetermined pattern (circuit pattern, electrode pattern, etc.) on a plate (glass substrate). Hereinafter, an example of the technique at this time will be described with reference to the flowchart of FIG. In FIG. 5, in the pattern forming step S401, a so-called photolithography step is performed in which the pattern of the mask R is transferred and exposed to a photosensitive substrate (such as a glass substrate coated with a resist) using the exposure apparatus according to the above-described embodiment. Executed. By this photolithography process, a predetermined pattern including a large number of electrodes and the like is formed on the photosensitive substrate. Thereafter, the exposed substrate undergoes steps such as a developing step, an etching step, and a resist stripping step, whereby a predetermined pattern is formed on the substrate, and the process proceeds to the next color filter forming step S402.

  Next, in the color filter forming step S402, a large number of groups of three dots corresponding to R (Red), G (Green), and B (Blue) are arranged in a matrix or three of R, G, and B A color filter is formed by arranging a plurality of stripe filter sets in the horizontal scanning line direction. Then, after the color filter formation step S402, a cell assembly step S403 is executed. In the cell assembly step S403, a liquid crystal panel (liquid crystal cell) is assembled using the substrate having the predetermined pattern obtained in the pattern formation step S401, the color filter obtained in the color filter formation step S402, and the like. In the cell assembly step S403, for example, liquid crystal is injected between the substrate having the predetermined pattern obtained in the pattern formation step S401 and the color filter obtained in the color filter formation step S402, and a liquid crystal panel (liquid crystal cell ).

  Thereafter, in a module assembly step S404, components such as an electric circuit and a backlight for performing a display operation of the assembled liquid crystal panel (liquid crystal cell) are attached to complete a liquid crystal display element. According to the method for manufacturing a liquid crystal display element described above, since the exposure apparatus according to the above-described embodiment is used, a fine pattern can be satisfactorily exposed on the wafer.

  In the above-described embodiment, the first specific lens element LS7 and the second specific lens element LS6 are integrally formed, and the liquid immersion region is formed only in the space on the light emission surface side of the integrally formed optical element. And a water repellent functional film may be provided on at least a part of the surface outside the effective region of the optical element formed integrally.

  In the above embodiment, the structure having only the light shielding film and the liquid repellent film (water repellent film) on the base material (lens element) of the optical element has been described. However, the present invention is not limited thereto, and the optical element of the present invention is not limited thereto. Is a layer between the light-shielding film and the liquid-repellent film, another film between the base material and the light-shielding film, for example, a protective layer, a layer that improves the adhesion of the light-shielding film and the liquid-repellent film, Such another functional film may be provided. Note that a liquid repellent film is present in the uppermost layer of the liquid repellent functional layer because of its function.

  In the above embodiment, the light shielding film and the liquid repellent film are formed on the substrate (lens element) of the optical element. However, the present invention is not limited to the film shape, and various forms of the light shielding member and the liquid repellent member can be provided. For example, it may be a frame-shaped molded member that covers the outer portion of the lens element (outside the effective area). Such a molded member may be an integral member formed from the light-shielding substance and the liquid-repellent substance, or a member made from the light-shielding substance and a member formed from the liquid-repellent substance. You may superimpose and use. Further, the light-reducing member is not limited to a light-shielding substance, and any light-reducing member that reduces incident light to the liquid repellent member can be used.

  In the above embodiment, the light shielding film and the liquid repellent film are formed outside the effective area of the lens element. However, it is not necessary to form the light shielding film and the liquid repellent film in all the areas outside the effective area, and it is a partial area. May be. For example, the light-shielding film and the liquid-repellent film may be formed only in the annular region near the outermost periphery of the lens element in the radially outer region of the effective region of the lens element. Further, the light shielding film and the liquid repellent film may be provided on the side surface other than the light emitting surface of the lens element.

  In the above embodiment, the light shielding film and the liquid repellent film are applied as the optical elements to the second lens element of the projection optical system PL. However, the present invention is not limited to this, and another lens of the projection optical system that may come into contact with the liquid. It can also be applied to elements. Further, the optical element including the light shielding film and the liquid repellent film according to the present invention is not limited to the lens element of the projection optical system PL, and is provided in various sensors provided in the alignment optical system and the substrate stage (or a measurement stage described later). It can be applied to optical elements such as lenses and light transmission plates.

In addition, as disclosed in, for example, International Publication No. 2006/64900, the present invention can be applied to an exposure apparatus that exposes a pattern on a photosensitive substrate using a plurality of diffraction gratings. Specifically, at least one of the light-transmitting flat plates P1 and P2 on which diffraction gratings are formed, as shown in FIGS. 18 and 19 of International Publication No. 2006/64900, In the above-described embodiment, as the exposure light source, in addition to the F ₂ laser (157 nm), for example, a KrF excimer laser (248 nm), a Kr ₂ laser (146 nm), an Ar ₂ laser ( 126 nm) or the like may be used.

In the above-described embodiment, the liquid may be other than pure water LQ. For example, when the exposure light source is an F ₂ laser, since the F ₂ laser light does not pass through the pure water LQ, the exposure light source is a fluorine-based liquid such as perfluorinated polyether (PFPE = perfluoropolyether) or fluorine-based oil. Is desirable. In this case, a functional film that repels a fluorinated liquid is required, and a liquid repellent functional film made of a substance having a high contact angle with respect to the liquid to be used must be provided. Further, one or a plurality of optical elements constituting the illumination optical system 12 or the projection optical system PL have a liquid repellent functional film having a light shielding film and a liquid repellent film on the surface outside the effective area of the exposure light EL. It is good also as a structure.

  In the above embodiment, the exposure apparatus having a single substrate stage has been described as an example. However, the present invention is applied to a multi-stage (twin stage) type exposure apparatus in which two substrate stages move between an exposure station and a measurement station. An optical system and an optical element may be applied. Such multi-stage type exposure apparatuses are disclosed in US Pat. Nos. 6,341,007, 6,400,441, 6,549,269 and 6,590,634, 5,969,441. US patents are incorporated herein by reference.

  Further, as disclosed in, for example, International Publication No. 1999/23692, US Pat. No. 6,897,963, etc., a reference stage and / or various photoelectric sensors on which a substrate stage for holding a substrate and a reference mark are formed are provided. The present invention can also be applied to an exposure apparatus that includes a mounted measurement stage. US Pat. No. 6,897,963 is incorporated herein by reference.

  In the above-described embodiment, an exposure apparatus that locally fills the liquid between the projection optical system PL and the substrate P is adopted. However, the present invention is disclosed in, for example, JP-A-6-124873 and JP-A-6-124873. 10-303114, US Pat. No. 5,825,043, etc. are also applicable to an immersion exposure apparatus that performs exposure while the entire surface of the substrate to be exposed is immersed in the liquid. It is.

  In the above embodiment, 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 in this way, the exposure light is irradiated onto the substrate via an optical member such as a diffractive optical element or a lens, and a predetermined space between the optical member and the substrate. An immersion region is formed in the substrate.

  Further, as disclosed in, for example, International Publication No. 2001/035168, an exposure apparatus that exposes a line-and-space pattern on a substrate by forming interference fringes on the substrate, for example, JP-T-2004-2004 As disclosed in US Pat. No. 51,850 (corresponding US Pat. No. 6,611,316), a pattern of two masks is synthesized on a substrate via a projection optical system, and is scanned on the substrate by one scanning exposure. The present invention can also be applied to an exposure apparatus that double-exposes one shot area almost simultaneously.

  Further, the type of exposure apparatus is not limited to an exposure apparatus for manufacturing a micro device such as a semiconductor element that exposes a semiconductor element pattern on the substrate P. An exposure apparatus for manufacturing a liquid crystal display element or a display, a thin film magnetic head, The present invention can be widely applied to an exposure device for manufacturing an imaging device (CCD), a micromachine, a MEMS, and a DNA chip.

  In addition, exposure for transferring a circuit pattern from a mother reticle to a glass substrate, a silicon wafer or the like to manufacture a reticle or mask used in an optical exposure apparatus, EUV exposure apparatus, X-ray exposure apparatus, electron beam exposure apparatus, etc. The present invention can also be applied to an apparatus. Here, in an exposure apparatus using DUV (deep ultraviolet) or VUV (vacuum ultraviolet) light, a transmission type reticle is generally used. As a reticle substrate, quartz glass, quartz glass doped with fluorine, fluorite, fluoride, and the like are used. Magnesium or quartz is used. Further, in proximity type X-ray exposure apparatuses and electron beam exposure apparatuses, a transmission type mask (stencil mask, member mask) is used, and a silicon wafer or the like is used as a mask substrate.

  In the above-described embodiment, a light transmissive mask in which a predetermined light shielding pattern (or phase pattern / dimming pattern) is formed on a light transmissive substrate is used. As disclosed in US Pat. No. 6,778,257, an electronic mask (also known as a variable molding mask) that forms a transmission pattern, a reflection pattern, or a light emission pattern based on electronic data of a pattern to be formed on a substrate 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.

It is a schematic block diagram which shows the exposure apparatus which concerns on embodiment. It is the schematic block diagram which expanded a part of exposure apparatus which concerns on embodiment. It is a figure which shows the structure of the water-repellent functional film which concerns on embodiment. It is a flowchart which shows the manufacturing method of the microdevice which concerns on embodiment. It is a flowchart which shows the manufacturing method of the microdevice which concerns on embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 ... Exposure apparatus, 13 ... Lens barrel, 14 ... Lens holder, 15 ... Optical path space, 16 ... Optical path space, 17 ... 1st liquid supply apparatus, 18 ... 2nd liquid supply apparatus, 19 ... 1st liquid recovery apparatus, 20 DESCRIPTION OF SYMBOLS 2nd liquid collection | recovery apparatus, 21 ... 2nd nozzle member, 28 ... Water repellent functional film, 28a ... Light-shielding film, 28b ... Water repellent film, 30 ... 1st nozzle member, 51 ... Water repellent film, EL ... Exposure light LS1 to LS5: Lens element, LS6: Second specific lens element, LS7: First specific lens element, LT1, LT2: Immersion area, LQ: Pure water (liquid), PL: Projection optical system, R: Reticle (mask) ), W ... wafer.

Claims (22)

An exposure apparatus that irradiates a substrate with an exposure beam,
An optical element that is irradiated with the exposure beam, and an optical path space on the exit surface side of the exposure beam is filled with a liquid;
A liquid repellent functional film provided on at least a part of the surface outside the effective area of the optical element,
The liquid repellent film, e Bei liquid repellent film formed on the surface of the light-shielding film and the light-shielding film formed on a surface of the optical element,
The exposure apparatus, wherein the liquid repellent functional film further includes a third functional film between the light shielding film and the liquid repellent film or between a base material of the optical element and the light shielding film. The exposure apparatus according to claim 1, wherein the third functional film has any one of a protective function, a function of improving adhesion, and a function of reinforcing mechanical strength. The exposure apparatus according to claim 1, wherein the optical element has a flange portion formed on an outer periphery of an effective area, and the flange portion includes a liquid repellent functional film. The exposure apparatus according to claim 1, wherein the light shielding film has an optical density OD1 or more. The exposure apparatus according to any one of claims 1 to 4, wherein the light shielding film is formed of a metal film or a metal oxide film. 6. The exposure apparatus according to claim 5 , wherein the metal film is formed of at least one metal selected from the group consisting of Au, Pt, Ag, Ni, Ta, W, Pd, Mo, Ti, Si, and Cr. . 6. The exposure apparatus according to claim 5 , wherein the metal oxide film is formed of at least one material selected from the group consisting of ZrO ₂ , HfO ₂ , TiO ₂ , Ta ₂ O ₅ , SiO, and Cr ₂ O _3. . The exposure apparatus according to claim 1, wherein the liquid repellent film is a fluororesin. The exposure apparatus according to claim 8, wherein the liquid repellent film is a fluororesin formed by a wet film forming method. The exposure apparatus according to claim 9, wherein the fluororesin has a thickness of 0.1 μm to 2.0 μm. An exposure step of exposing a predetermined pattern on a photosensitive substrate using the exposure apparatus according to any one of claims 1 to 10 ,
A developing step of developing the photosensitive substrate exposed by the exposing step;
A method for manufacturing a microdevice, comprising: An optical element used in an immersion exposure apparatus that exposes a substrate through a liquid,
A substrate of the optical element;
A liquid repellent member provided on at least a part of the outer surface of the effective area of the flange portion of the substrate;
An optical element provided between the base material and the liquid repellent member, and a light reducing member that attenuates light and protects the liquid repellent member from light irradiation. The optical element according to claim 12 , wherein the dimming member is provided on a side surface of the optical element. 13. The optical element according to claim 12, wherein the light reducing member is a light reducing film formed of a thin film, or the liquid repellent member is a liquid repellent film formed of a thin film. The optical element according to claim 12, further comprising a third functional film between the light reducing member and the liquid repellent member, or between a substrate of the optical element and the light reducing member. The optical element according to claim 15, wherein the third functional film has any one of a protective function, a function of improving adhesion, and a function of reinforcing mechanical strength. The dimming member is a light blocking member,
The optical element according to any one of claims 12 to 16 , wherein the light shielding member has an optical density OD1 or more. The optical element according to claim 12 , wherein the dimming member is formed of a metal film or a metal oxide film. The metal film is formed of at least one metal selected from the group consisting of Au, Pt, Ag, Ni, Ta, W, Pd, Mo, Ti, Si, and Cr. 18. The optical element according to 18 . The optical element according to claim 18 , wherein the metal oxide film is formed of at least one selected from the group consisting of ZrO ₂ , HfO ₂ , TiO ₂ , Ta ₂ O ₅ , SiO, and Cr ₂ O ₃ . The optical element according to claim 14 , wherein the liquid repellent member is a fluororesin formed by a wet film forming method . An immersion exposure apparatus that exposes a substrate through a liquid, the immersion exposure apparatus including the optical element according to any one of claims 12 to 21 .

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