JP4858062B2 - Exposure method, exposure apparatus, device manufacturing method, and film evaluation method - Google Patents

Description

The present invention relates to an exposure method, an exposure apparatus, a device manufacturing method, and a film evaluation method for exposing a substrate through a liquid.
This application claims priority based on Japanese Patent Application No. 2005-129517 filed on April 27, 2005 and Japanese Patent Application No. 2005-213319 filed on July 21, 2005, the contents of which are hereby incorporated by reference herein. Incorporate.

In a photolithography process, which is one of the manufacturing processes of microdevices such as semiconductor devices and liquid crystal display devices, an exposure apparatus that projects and exposes a pattern formed on a mask onto a photosensitive substrate is used. This exposure apparatus has a mask stage for holding a mask and a substrate stage for holding a substrate, and projects the mask pattern onto the substrate via a projection optical system while sequentially moving the mask stage and the substrate stage. is there. In the manufacture of microdevices, miniaturization of patterns formed on a substrate is required in order to increase the density of devices. In order to meet this demand, it is desired to further increase the resolution of the exposure apparatus. As one of means for realizing the higher resolution, an exposure apparatus is disclosed on the substrate as disclosed in Patent Document 1 below. An immersion exposure apparatus has been devised in which a liquid immersion area is formed and a substrate is exposed through the liquid in the immersion area.
International Publication No. 99/49504 Pamphlet

  By the way, various materials are usually used for the photoresist film provided on the surface of the substrate to be exposed or the top coat film provided on the photoresist film, but the contact surface with the liquid in the immersion region is usually used. When the type of film to be changed is changed, there is a possibility that the liquid on the optical path of the exposure light cannot be maintained in a desired state depending on the type of film. In this case, there arises a problem that the versatility of the immersion exposure apparatus is significantly reduced.

  The present invention has been made in view of such circumstances, and an exposure method, an exposure apparatus, and a device manufacture capable of satisfactorily performing immersion exposure on each of substrates provided with different types of films. It aims to provide a method.

  In order to solve the above-described problems, the present invention employs the following configurations corresponding to the respective drawings shown in the embodiments. However, the reference numerals with parentheses attached to each element are merely examples of the element and do not limit each element.

  According to the first aspect of the present invention, the liquid immersion region (LR) of the liquid (LQ) is formed on the substrate (P), and the substrate (P) is passed through the liquid (LQ) of the liquid immersion region (LR). In the exposure method in which the substrate (P) is exposed by irradiating exposure light (EL) on the top, based on the receding contact angle of the liquid (LQ) on the surface of the substrate (P) when the surface of the substrate (P) is inclined. An exposure method for determining an exposure condition when exposing the substrate (P) is provided.

  According to the first aspect of the present invention, the exposure condition for exposing the substrate is determined based on the receding contact angle of the liquid on the substrate surface when the substrate surface is tilted. Regardless, the immersion exposure can be satisfactorily performed on the substrate.

  According to the second aspect of the present invention, there is provided a device manufacturing method using the exposure method of the above aspect.

  According to the second aspect of the present invention, the substrate can be satisfactorily exposed regardless of the type of film on the surface, and a device having desired performance can be manufactured.

  According to the third aspect of the present invention, the liquid immersion region (LR) of the liquid (LQ) is formed on the substrate (P), and the substrate (P) is passed through the liquid (LQ) of the liquid immersion region (LR). In an exposure apparatus that exposes a substrate (P) by irradiating exposure light (EL) thereon, the receding contact angle of the liquid (LQ) on the substrate (P) surface when the substrate (P) surface is tilted is measured. An exposure apparatus (EX) provided with a measurement apparatus (60) is provided.

  According to the third aspect of the present invention, by measuring the receding contact angle of the liquid on the substrate surface when the substrate surface is tilted, based on the measurement result, regardless of the type of film on the surface, In contrast, immersion exposure can be performed satisfactorily.

  According to the fourth aspect of the present invention, the liquid immersion region (LR) of the liquid (LQ) is formed on the substrate (P), and the substrate (P) is passed through the liquid (LQ) of the liquid immersion region (LR). Information on the receding contact angle of the liquid (LQ) on the surface of the substrate (P) when the surface of the substrate (P) is tilted in an exposure apparatus that exposes the substrate (P) by irradiating it with exposure light (EL). An input device (INP) for inputting, and a control device (CONT) for determining exposure conditions for exposing the substrate (P) based on information on the receding contact angle input from the input device (INP) An exposure apparatus (EX) provided is provided.

  According to the fourth aspect of the present invention, the exposure condition for exposing the substrate is determined based on the information on the receding contact angle of the liquid on the substrate surface when the substrate surface input by the input device is tilted. Therefore, it is possible to satisfactorily perform immersion exposure on each of the substrates regardless of the type of film on the surface.

  According to the fifth aspect of the present invention, there is provided a device manufacturing method using the exposure apparatus (EX) of the above aspect.

  According to the fifth aspect of the present invention, each of a plurality of substrates provided with different types of films can be satisfactorily subjected to immersion exposure, and a device having desired performance can be manufactured.

  According to the sixth aspect of the present invention, there is provided a method for evaluating a film formed on a substrate (P) exposed through a liquid (LQ), the surface of the film when the substrate (P) is tilted Measuring the receding contact angle of the liquid (LQ) in the film, and comparing the measured receding contact angle value with the allowable range of the receding contact angle determined based on the exposure condition. And a method for evaluating the suitability of the film.

  According to the sixth aspect of the present invention, based on a comparison between the receding contact angle of the liquid on the surface of the film when the substrate is tilted and the allowable range of the receding contact angle determined based on the exposure conditions, Since the suitability of the film with respect to the exposure conditions is determined, immersion exposure can be satisfactorily performed on the substrate regardless of the type of film on the surface.

  According to the present invention, it is possible to satisfactorily perform immersion exposure on each of the substrates provided with different types of films.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.

<First Embodiment>
A first embodiment will be described. FIG. 1 is a schematic block diagram that shows an exposure apparatus EX according to the first embodiment. In FIG. 1, an exposure apparatus EX includes a mask stage MST that can move while holding a mask M, and a substrate holder PH that holds a substrate P, and a substrate stage PST that can move the substrate holder PH that holds the substrate P. An illumination optical system IL that illuminates the mask M held on the mask stage MST with the exposure light EL, a projection optical system PL that projects a pattern image of the mask M illuminated with the exposure light EL onto the substrate P, and And a control device CONT for controlling the entire operation of the exposure apparatus EX. The control device CONT is connected to a storage device MRY that stores information related to exposure processing, an input device INP that inputs information related to exposure processing, and a display device DY that displays information related to exposure processing. The input device INP includes, for example, a keyboard or a touch panel. The display device DY includes a display device such as a liquid crystal display. Further, the exposure apparatus EX includes a transport apparatus H that transports the substrate P to the substrate stage PST.

  The exposure apparatus EX of the present embodiment is an immersion exposure apparatus to which an immersion method is applied in order to substantially shorten the exposure wavelength to improve the resolution and substantially widen the depth of focus. A liquid immersion mechanism 1 is provided for filling the optical path space K1 of the exposure light EL in the vicinity of the PL image plane with the liquid LQ. The liquid immersion mechanism 1 is provided in the vicinity of the optical path space K1, and is provided in the nozzle member 70 having the supply port 12 for supplying the liquid LQ and the recovery port 22 for recovering the liquid LQ, the supply pipe 13, and the nozzle member 70. The liquid supply device 11 for supplying the liquid LQ through the supply port 12, the recovery port 22 provided in the nozzle member 70, and the liquid recovery device 21 for recovering the liquid LQ through the recovery pipe 23 are provided. . The nozzle member 70 has an annular shape so as to surround the final optical element LS1 closest to the image plane of the projection optical system PL among the plurality of optical elements constituting the projection optical system PL above the substrate P (substrate stage PST). Is formed.

  Further, the exposure apparatus EX of the present embodiment has an immersion region LR of the liquid LQ that is larger than the projection region AR and smaller than the substrate P in a part of the region on the substrate P including the projection region AR of the projection optical system PL. The local liquid immersion method is used to form the surface locally. The exposure apparatus EX uses the liquid immersion mechanism 1 while projecting at least the pattern image of the mask M onto the substrate P, and uses the liquid immersion mechanism 1 to provide the final optical element LS1 and the final optical element LS1 that are closest to the image plane of the projection optical system PL. A liquid LQ immersion region LR is formed on the substrate P by filling the optical path space K1 of the exposure light EL with the substrate P arranged at the opposite position with the liquid LQ, and the projection optical system PL and the liquid immersion A pattern image of the mask M is projected onto the substrate P by irradiating the substrate P with the exposure light EL that has passed through the mask M via the liquid LQ in the region LR. The control device CONT supplies a predetermined amount of the liquid LQ using the liquid supply device 11 of the liquid immersion mechanism 1 and recovers the predetermined amount of the liquid LQ using the liquid recovery device 21, so that the optical path space K <b> 1 is replaced with the liquid LQ. The liquid LQ immersion region LR is locally formed in a partial region on the substrate P.

  In the present embodiment, the liquid immersion region LR may be described as being formed on the substrate P. However, the liquid immersion region LR is disposed at a position facing the final optical element LS1 on the image plane side of the projection optical system PL. For example, it can be formed on the upper surface of the substrate stage PST including the substrate P.

  Further, the exposure apparatus EX includes a measuring device 60 that measures an adhesion force (adhesion energy) that acts between the surface of the substrate P and the liquid LQ. In the present embodiment, the measuring device 60 is provided on the transport path of the transport device H.

  In the present embodiment, the exposure apparatus EX uses a scanning exposure apparatus (so-called scanning stepper) that exposes the substrate P with a pattern formed on the mask M while moving the mask M and the substrate P synchronously in the scanning direction. An example will be described. In the following description, the synchronous movement direction (scanning direction) of the mask M and the substrate P in the horizontal plane is the Y-axis direction, the direction orthogonal to the Y-axis direction in the horizontal plane is the X-axis direction (non-scanning direction), the X-axis, and A direction perpendicular to the Y-axis direction and coincident with the optical axis AX of the projection optical system PL is defined as a Z-axis direction. Further, the rotation (inclination) directions around the X axis, Y axis, and Z axis are the θX, θY, and θZ directions, respectively. Here, the “substrate” includes a substrate in which a photosensitive material (resist) is coated on a base material such as a semiconductor wafer, and the “mask” includes a reticle on which a device pattern to be reduced and projected on the substrate is formed.

The illumination optical system IL includes an exposure light source, an optical integrator that equalizes the illuminance of the light beam emitted from the exposure light source, a condenser lens that collects the exposure light EL from the optical integrator, a relay lens system, and the exposure light EL. A field stop for setting an illumination area on the mask M is provided. A predetermined illumination area on the mask M is illuminated with the exposure light EL having a uniform illuminance distribution by the illumination optical system IL. The exposure light EL emitted from the illumination optical system IL is, 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. Further, vacuum ultraviolet light (VUV light) such as ArF excimer laser light (wavelength 193 nm) and F ₂ laser light (wavelength 157 nm) is used. In this embodiment, ArF excimer laser light is used.

  In the present embodiment, pure water is used as the liquid LQ. Pure water is not only ArF excimer laser light, but also, for example, far ultraviolet light (DUV light) such as emission lines (g-line, h-line, i-line) emitted from a mercury lamp and KrF excimer laser light (wavelength 248 nm). It can be transmitted.

  Mask stage MST is movable while holding mask M. Mask stage MST holds mask M using a vacuum suction (or electrostatic suction) mechanism or the like. The mask stage MST is in a plane perpendicular to the optical axis AX of the projection optical system PL in a state where the mask M is held by driving a mask stage driving device MSTD including a linear motor controlled by the control device CONT, that is, XY. It can move two-dimensionally in the plane and can rotate slightly in the θZ direction. A movable mirror 91 is provided on the mask stage MST. A laser interferometer 92 is provided at a predetermined position. The position of the mask M on the mask stage MST in the two-dimensional direction and the rotation angle in the θZ direction (including rotation angles in the θX and θY directions in some cases) are measured in real time by the laser interferometer 92 using the moving mirror 91. The The measurement result of the laser interferometer 92 is output to the control device CONT. The control device CONT drives the mask stage drive device MSTD based on the measurement result of the laser interferometer 92, and controls the position of the mask M held on the mask stage MST.

  The projection optical system PL projects and exposes the pattern of the mask M onto the substrate P at a predetermined projection magnification β, and is composed of a plurality of optical elements, which are held by a lens barrel PK. . In the present embodiment, the projection optical system PL is a reduction system having a projection magnification β of, 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. 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. In the present embodiment, the plurality of optical elements constituting the projection optical system PL are held by the lens barrel PK so that only the final optical element LS1 closest to the image plane of the projection optical system PL is in contact with the liquid LQ. ing.

  The substrate stage PST has a substrate holder PH that holds the substrate P, and is movable on the base member BP on the image plane side of the projection optical system PL. The substrate holder PH holds the substrate P using, for example, a vacuum suction mechanism. A recess 96 is provided on the substrate stage PST, and a substrate holder PH for holding the substrate P is disposed in the recess 96. The upper surface 97 of the substrate stage PST other than the recess 96 is a flat surface that is substantially the same height (level) as the surface of the substrate P held by the substrate holder PH. If the optical path space K1 can continue to be filled with the liquid LQ, there may be a step between the upper surface 97 of the substrate stage PST and the surface of the substrate P held by the substrate holder PH.

  The substrate stage PST is driven in the XY plane on the base member BP in a state where the substrate P is held via the substrate holder PH by driving the substrate stage driving device PSTD including a linear motor and the like controlled by the control device CONT. Dimensional movement is possible, and minute rotation is possible in the θZ direction. Furthermore, the substrate stage PST is also movable in the Z-axis direction, the θX direction, and the θY direction. Therefore, the surface of the substrate P held on the substrate stage PST is movable in directions of six degrees of freedom in the X axis, Y axis, Z axis, θX, θY, and θZ directions.

  A movable mirror 93 is provided on the side surface of the substrate stage PST. A laser interferometer 94 is provided at a predetermined position. The position and rotation angle of the substrate P on the substrate stage PST in the two-dimensional direction are measured in real time by the laser interferometer 94 using the moving mirror 93. Although not shown, the exposure apparatus EX includes a focus / leveling detection system that detects surface position information of the surface of the substrate P held by the substrate stage PST. The focus / leveling detection system detects surface position information (position information in the Z-axis direction and inclination information in the θX and θY directions) of the surface of the substrate P. The measurement result of the laser interferometer 94 is output to the control device CONT. The detection result of the focus / leveling detection system is also output to the control device CONT. The control device CONT drives the substrate stage drive device PSTD based on the detection result of the focus / leveling detection system, and controls the focus position (Z position) and the tilt angles (θX, θY) of the substrate P to control the substrate P. While adjusting the positional relationship between the surface and the image plane via the projection optical system PL and the liquid LQ, the position of the substrate P in the X-axis direction, the Y-axis direction, and the θZ direction based on the measurement result of the laser interferometer 94 Take control.

  Next, the liquid immersion mechanism 1 will be described. The liquid supply device 11 of the liquid immersion mechanism 1 includes a tank that stores the liquid LQ, a pressure pump, a temperature adjustment device that adjusts the temperature of the supplied liquid LQ, a deaeration device that reduces the gas component of the supplied liquid LQ, and A filter unit or the like for removing foreign substances in the liquid LQ is provided. One end of a supply pipe 13 is connected to the liquid supply apparatus 11, and the other end of the supply pipe 13 is connected to a nozzle member 70. The liquid supply operation of the liquid supply device 11 is controlled by the control device CONT. The control device CONT can adjust the liquid supply amount per unit time from the supply port 12 by controlling the liquid supply device 11. The tank, pressure pump, temperature adjustment device, deaeration device, filter unit, etc. of the liquid supply device 11 do not have to be all provided in the exposure apparatus EX, such as a factory where the exposure apparatus EX is installed. Equipment may be substituted.

  The liquid recovery device 21 of the liquid immersion mechanism 1 includes a vacuum system such as a vacuum pump, a gas-liquid separator that separates the recovered liquid LQ and gas, a tank that stores the recovered liquid LQ, and the like. One end of a recovery tube 23 is connected to the liquid recovery device 21, and the other end of the recovery tube 23 is connected to a nozzle member 70. The liquid recovery operation of the liquid recovery device 21 is controlled by the control device CONT. The control device CONT can adjust the liquid recovery amount per unit time via the recovery port 22 by controlling the liquid recovery device 21. The vacuum system, the gas-liquid separator, the tank, etc. of the liquid recovery apparatus 21 do not have to be all provided in the exposure apparatus EX, and equipment such as a factory in which the exposure apparatus EX is installed may be substituted. .

  The supply port 12 for supplying the liquid LQ and the recovery port 22 for recovering the liquid LQ are formed on the lower surface 70 </ b> A of the nozzle member 70. The lower surface 70A of the nozzle member 70 is provided at a position facing the surface of the substrate P and the upper surface 97 of the substrate stage PST. The nozzle member 70 is an annular member provided so as to surround the side surface of the final optical element LS1, and the supply port 12 is provided on the lower surface 70A of the nozzle member 70 with the final optical element LS1 (projection optical system) of the projection optical system PL. A plurality of PLs are provided so as to surround the PL optical axis AX). The recovery port 22 is provided on the lower surface 70A of the nozzle member 70 on the outer side of the supply port 12 (away from the supply port 12) with respect to the final optical element LS1, and the final optical element LS1 and the supply port are provided. 12 is provided so as to surround 12.

  The control device CONT supplies a predetermined amount of the liquid LQ to the optical path space K1 using the liquid supply device 11, and collects a predetermined amount of the liquid LQ in the optical path space K1 using the liquid recovery device 21, thereby projecting optics. The optical path space K1 of the exposure light EL between the system PL and the substrate P is filled with the liquid LQ, and an immersion region LR of the liquid LQ is locally formed on the substrate P. When forming the liquid immersion region LR of the liquid LQ, the control device CONT drives each of the liquid supply device 11 and the liquid recovery device 21. When the liquid LQ is sent from the liquid supply device 11 under the control of the control device CONT, the liquid LQ sent from the liquid supply device 11 flows through the supply pipe 13 and then the supply flow path of the nozzle member 70. Then, the image is supplied from the supply port 12 to the image plane side of the projection optical system PL. When the liquid recovery device 21 is driven under the control device CONT, the liquid LQ on the image plane side of the projection optical system PL flows into the recovery flow path of the nozzle member 70 via the recovery port 22, and the recovery pipe After flowing through 23, the liquid is recovered by the liquid recovery device 21.

  FIG. 2 is a view for explaining an example of the positional relationship between the immersion region LR and the substrate stage PST holding the substrate P when the substrate P is exposed. As shown in FIG. 2, a plurality of shot areas S1 to S21 are set on the substrate P in a matrix. As described above, the exposure apparatus EX of the present embodiment projects and exposes the pattern of the mask M onto the substrate P while moving the mask M and the substrate P in the Y-axis direction (scanning direction). When exposing each of the shot areas S1 to S21, the control unit CONT, as shown by an arrow y1 in FIG. 2, for example, sets the projection area AR of the projection optical system PL, the liquid immersion area LR covering the projection area AR, and the substrate P. While moving relatively, the exposure light EL is irradiated onto the substrate P via the liquid LQ in the immersion region LR. The control device CONT controls the operation of the substrate stage PST so that the projection area AR (exposure light EL) of the projection optical system PL moves along the arrow y1 on the substrate P. After the exposure of one shot area is completed, the control device CONT moves the substrate P (substrate stage PST) by stepping and moves the next shot area to the scanning start position. Thereafter, the substrate P is moved by the step-and-scan method. The respective shot areas S1 to S21 are sequentially scanned and exposed while moving. Further, the control device CONT controls the operation of the liquid immersion mechanism 1 in order to form the liquid immersion region LR in a desired state, and performs the liquid LQ supply operation and the recovery operation in parallel.

  3A and 3B are cross-sectional views for explaining an example of the substrate P. FIG. A substrate P shown in FIG. 3A has a base material W and a first film Rg formed on the upper surface of the base material W. The substrate W includes a silicon wafer. The first film Rg is formed of a photoresist (photosensitive material), and covers a region that occupies most of the central portion of the upper surface of the substrate W with a predetermined thickness. The substrate P shown in FIG. 3B has a second film Tc that covers the surface of the first film Rg. The second film Tc is, for example, a protective film or antireflection film called a top coat film.

  Thus, on the surface of the substrate P, the first film Rg made of a photoresist or the like, or the second film Tc such as a top coat film provided on the upper layer of the first film Rg is formed. Accordingly, the film provided on the uppermost layer (the surface of the substrate P) on the substrate P forms a liquid contact surface that comes into contact with the liquid LQ during the immersion exposure.

  Next, the measuring device 60 will be described with reference to FIG. In FIG. 4, the measuring device 60 includes a holding member 61 that holds the substrate P, a dropping member 62 that can drop a liquid LQ droplet on the surface of the substrate P held by the holding member 61, and the substrate P An observation device 63 that can observe the state of the liquid LQ (droplet) on the surface of the substrate P, and an illumination device 64 that illuminates the liquid LQ (droplet) on the surface of the substrate P.

  The substrate P is loaded (carried in) on the holding member 61 by the transfer device H, and the holding member 61 holds the substrate P transferred by the transfer device H. The transport device H transports the substrate P before the exposure processing to the holding member 61. The measuring device 60 measures the substrate P before the exposure process.

  The observation device 63 includes an optical element, an imaging device configured by a CCD, and the like. The imaging element can acquire an image (optical image) of the liquid LQ via an optical system. In the present embodiment, the observation device 63 is disposed on the + X side (one side) of the substrate P held by the holding member 61, and the liquid on the substrate P is located away from the substrate P and the holding member 61. Observe the state of the LQ droplet.

  The illumination device 64 is provided at a position facing the observation device 63 across the substrate P (holding member 61). In other words, the lighting device 64 is disposed on the −X side (the other side) of the substrate P held by the holding member 61, and the liquid LQ liquid on the substrate P is located away from the substrate P and the holding member 61. Illuminate the drops. Therefore, the observation device 63 acquires an image of the liquid LQ droplet illuminated by the illumination device 64.

  The observation device 63 and the control device CONT are connected, and the observation device 63 converts the acquired droplet image of the liquid LQ into an electrical signal and outputs the signal (image information) to the control device CONT. The control device CONT can display the image information from the observation device 63 on the display device DY. Therefore, an image of the liquid LQ droplet on the surface of the substrate P is displayed on the display device DY.

  The measuring device 60 includes a drive system 65 that rotates (tilts) the holding member 61 that holds the substrate P. The operation of the drive system 65 is controlled by the control device CONT, and the holding member 61 can rotate (tilt) while holding the substrate P. In the present embodiment, the holding member 61 holding the substrate P is rotated (inclined) in the θX direction by the drive of the drive system 65.

  The measuring device 60 has an adhesion force (adhesion energy) E acting between the surface of the substrate P and the liquid LQ, a static contact angle θ of the liquid LQ on the surface of the substrate P, and the liquid LQ on the surface of the substrate P. The sliding angle α can be measured. The adhesion force (adhesion energy) E is a force necessary to move the liquid on the surface of the object (here, the surface of the substrate P). Here, the adhesion E will be described with reference to FIG.

In FIG. 5, when the outer shape of the droplet on the substrate P is assumed to be a part of a circle, that is, when it is assumed that the surface of the droplet on the substrate P in FIG. The wearing power E is
E = (m × g × sin α) / (2 × π × R) (1)
However,
m: the mass of the liquid LQ droplet on the substrate P,
g: acceleration of gravity,
α: Sliding angle with respect to the horizontal plane,
R: radius of the liquid LQ droplet on the substrate P.

  The sliding angle α is a state in which liquid droplets are attached to the surface of the object (here, the surface of the substrate P), and the object surface is attached to the object surface when the object surface is inclined with respect to the horizontal plane. The angle at which the liquid droplet slides downward (begins moving) by the action of gravity. In other words, the sliding angle α refers to a critical angle at which the liquid droplet slides when the surface of the object to which the liquid droplet adheres is tilted.

  In FIG. 5, θ represents the static contact angle of the liquid LQ on the surface of the substrate P. The contact angle θ is the angle between the surface of the liquid droplet and the surface of the object in a stationary state (the angle inside the liquid). Take).

  Here, as described above, the outer shape of the droplet is assumed to be a part of a circle, and in FIG. 5, the contact angle of the liquid LQ on the inclined surface is illustrated as θ, but the contact angle θ is parallel to the horizontal plane. It is a contact angle on a smooth surface. Further, the dropping member 62 can adjust the mass (or volume) m of the dropped droplet, and when the mass (or volume) m is known, the contact angle θ is measured by measuring the contact angle θ. Based on the angle θ, the radius R can be derived geometrically. Furthermore, if the contact angle θ is known, the radius r of the contact surface where the droplet contacts the surface of the substrate P (hereinafter referred to as “liquid landing radius r” as appropriate) can also be derived geometrically. Similarly, if the contact angle θ is known, the height h of the droplet relative to the surface of the substrate P can be derived. That is, the radius R of the liquid LQ droplet on the surface of the substrate P is a value corresponding to the contact angle θ of the liquid LQ, and the radius R of the above equation (1) is obtained by obtaining the contact angle θ of the liquid LQ. Can be requested.

  As described with reference to FIGS. 3A and 3B, the films (first film Rg and second film Tc) provided on the uppermost layer on the substrate P are liquid at the time of immersion exposure. A liquid contact surface that contacts the LQ is formed, and the contact angle θ and the sliding angle α described above vary depending on the type (physical properties) of the film. The measuring device 60 can determine the adhesion force E for each substrate P by measuring the contact angle θ and the sliding angle α.

  Next, an example of a measurement procedure using the measurement device 60 and an exposure procedure when exposing the substrate P will be described with reference to the flowchart of FIG.

  When the substrate P before the exposure processing is loaded onto the holding member 61 of the measuring device 60 by the transport device H, the control device CONT starts a measuring operation using the measuring device 60. First, the measuring device 60 measures the static contact angle θ of the liquid LQ on the surface of the substrate P (step SA1). When measuring the static contact angle θ of the liquid LQ on the surface of the substrate P, the measuring device 60 is driven so that the surface of the substrate P held by the holding member 61 is substantially parallel to the horizontal plane (XY plane). The position (posture) of the holding member 61 is adjusted via the system 65. Then, the measuring device 60 drops a liquid LQ droplet from the dropping member 62 onto the surface of the substrate P substantially parallel to the horizontal plane. The dropping member 62 can adjust the mass (or volume) m of the droplet to be dropped, and drops a droplet of mass m on the surface of the substrate P. After the droplet of mass m is disposed on the surface of the substrate P, the measuring device 60 illuminates the droplet disposed on the surface of the substrate P with the illumination device 64 and uses the observation device 63 to image the droplet. To get. The observation device 63 outputs image information regarding the acquired image to the control device CONT. The control device CONT displays the image of the droplet on the surface of the substrate P on the display device DY based on the signal (image information) output from the observation device 63. In addition, the control device CONT performs arithmetic processing (image processing) on the signal output from the observation device 63, and obtains the contact angle θ of the liquid LQ droplet on the surface of the substrate P based on the processing result. Thus, the static contact angle θ of the liquid LQ on the surface of the substrate P is measured by the measuring device 60 including the control device CONT.

  The measuring device 60 including the control device CONT derives the radius R of the liquid LQ droplet on the substrate P (step SA2). As described above, since the dropping member 62 can adjust the mass m of the dropped droplet and the radius R can be derived geometrically, the measuring device 60 including the control device CONT has a known value. By performing a predetermined calculation process based on the mass m of a certain droplet and the contact angle θ as a measurement result, the radius R of the droplet of the liquid LQ on the substrate P can be obtained.

  Here, the dropping member 62 is described as being capable of adjusting the mass m of the dropped droplet, but the density (specific gravity) ρ of the liquid LQ is known, and the volume V of the droplet dropped by the dropping member 62 is determined. If adjustable, the mass m can be derived based on the density ρ and the volume V (m = ρ × V).

  Next, the measuring device 60 measures the sliding angle α of the liquid LQ on the surface of the substrate P (step SA3). When measuring the sliding angle α of the liquid LQ on the surface of the substrate P, the measuring device 60 holds the holding member 61 holding the substrate P in a state where a droplet of mass m is arranged on the surface of the substrate P. As shown by the arrow K1 in the middle, the drive system 65 is used to rotate (tilt) in the θX direction. As the holding member 61 rotates (tilts), the surface of the substrate P also rotates (tilts). Even while the substrate P is rotating, the observation device 63 continues to observe the droplets disposed on the surface of the substrate P. As the substrate P is rotated, as shown by an arrow K2 in FIG. 4, the droplets adhering to the surface of the substrate P slide downward (begin movement) due to the gravitational action. The observation device 63 can observe that the liquid droplet has started to slide, and outputs image information regarding the acquired image to the control device CONT. That is, the control device CONT can obtain the time point when the droplet on the surface of the substrate P starts to move (the time point when it starts to slide) based on the signal (image information) output from the observation device 63. Further, the control device CONT determines the angle (namely, sliding angle) α of the surface of the substrate P at the time when the droplet on the surface of the substrate P starts to move, by the drive amount (tilt amount) of the holding member 61 by the drive system 65. It can be obtained more. That is, the control device CONT uses the signal (image information) output from the observation device 63 and the driving amount of the holding member 61 by the driving system 65, and the sliding angle α of the liquid LQ droplet on the surface of the substrate P. Can be requested. In this way, the sliding angle α of the liquid LQ on the surface of the substrate P is measured by the measuring device 60 including the control device CONT.

  Alternatively, the state of the droplet may be displayed on the display device DY, and the angle (namely, the sliding angle) α of the surface of the substrate P when the droplet on the surface of the substrate P starts moving may be measured by visual observation.

  Next, the measuring device 60 obtains an adhesion force E that acts between the substrate P and the liquid LQ (step SA4). Since the above-described steps SA1 to SA3 determine the mass m of the liquid LQ droplet on the substrate P, the radius R of the liquid LQ droplet on the substrate P, and the sliding angle α, these values are obtained. Is substituted into the above equation (1), the adhesion force (adhesion energy) E acting between the surface of the substrate P and the liquid LQ can be obtained.

  As described above, since the radius R of the liquid LQ droplet on the substrate P is a value corresponding to the contact angle θ of the liquid LQ, the adhesion force E is the contact angle θ of the liquid LQ on the surface of the substrate P. , And a value determined according to the sliding angle α of the liquid LQ on the surface of the substrate P.

  In the above steps SA1 to SA3, when the contact angle θ and the sliding angle α are measured, the measurement operation of the contact angle θ and the sliding angle α is performed a plurality of times while changing the mass (or volume) m of the droplet, You may make it derive | lead-out the adhesive force E using the average value of contact angle (theta), radius R, and sliding-down angle (alpha) obtained by each of these measurement operation | movement.

  Next, the control device CONT determines an exposure condition for exposing the substrate P based on the measurement result of the measurement device 60 (step SA5). That is, the control device CONT determines an exposure condition for exposing the substrate P according to the adhesion force E that is derived in step SA4 and acts between the surface of the substrate P and the liquid LQ. As described above, since the adhesive force E is determined according to the static contact angle θ of the liquid LQ on the surface of the substrate P and the sliding angle α of the liquid LQ on the surface of the substrate P, the control device CONT Based on the static contact angle θ of the liquid LQ on the surface of the substrate P, which is the measurement result measured in SA1, and the sliding angle α of the liquid LQ on the surface of the substrate P, which is the measurement result measured in step SA3. The exposure conditions for exposing P will be determined.

  Here, the exposure conditions include at least one of a movement condition when moving the substrate P and a liquid immersion condition when forming the liquid immersion region LR.

  The moving condition of the substrate P includes at least a part of the moving speed, acceleration, deceleration, moving direction, and continuous moving distance in one direction of the substrate P.

  Further, the liquid immersion conditions include at least one of a supply condition when supplying the liquid LQ to form the liquid immersion region LR and a recovery condition when recovering the liquid LQ forming the liquid immersion region LR. The supply condition includes a liquid supply amount per unit time from the supply port 12 to the optical path space K1. The recovery condition includes the amount of liquid recovered from the recovery port 22 per unit time.

  The exposure conditions include not only during exposure in which each shot area on the substrate P is irradiated with the exposure light EL but also before and / or after exposure of each shot area.

  In addition, the pressure of the liquid LQ changes according to the static contact angle θ between the film on the surface of the substrate P and the liquid LQ, and the projection optical system PL caused by fluctuations in the projection optical system PL (final optical element LS1). In the case where there is a possibility that the optical characteristics change, the adjustment conditions of the projection optical system PL for compensating the optical characteristics fluctuation may be stored in the storage device MRY as the exposure conditions.

  In the storage device MRY, information related to the optimum exposure condition corresponding to the adhesive force E is stored in advance. Specifically, the storage device MRY includes an adhesion force E that acts between the film formed on the liquid contact surface that contacts the liquid LQ on the substrate P and the liquid LQ during immersion exposure, and the adhesion force. The relationship with the optimum exposure condition corresponding to E is stored as a plurality of map data. Information (map data) relating to the optimum exposure condition corresponding to the adhesion force E can be obtained in advance by experiments or simulations and stored in the storage device MRY.

  In the present embodiment, in order to simplify the description, the storage device MRY includes, as the optimum exposure condition corresponding to the adhesion force E, information on the optimum moving speed of the substrate P corresponding to the adhesion force E, and the adhesion force. Information on the optimum liquid supply amount per unit time corresponding to E is stored.

  The control device CONT determines the exposure condition for exposing the substrate P based on the measurement result of the measurement device 60 and the stored information of the storage device MRY. That is, the control device CONT relates to the adhesion force E acting between the surface of the substrate P and the liquid LQ obtained in step SA4, and the optimum exposure condition corresponding to the adhesion force E stored in advance in the storage device MRY. Based on the information (map data), the optimum exposure condition for the substrate P to be exposed is selected and determined from the stored information (map data) of the storage device MRY.

  In the present embodiment, the control device CONT determines the moving speed of the substrate P and the liquid supply amount per unit time for the optical path space K1 by the liquid immersion mechanism 1 according to the adhesion force E.

  Then, the control device CONT loads the substrate P, which has been measured by the measuring device 60, onto the substrate stage PST using the transfer device H, and performs immersion exposure on the substrate P based on the exposure conditions determined in step SA5 ( Step SA6).

  In the present embodiment, the control device CONT adjusts the moving speed of the substrate P and the liquid supply amount per unit time with respect to the optical path space K1 by the liquid immersion mechanism 1 based on the exposure condition determined in step SA5. Then, each shot area of the substrate P is exposed.

  For example, when the adhesion force E acting between the surface of the substrate P to be exposed and the liquid LQ is large, it is difficult to satisfactorily fill the optical path space K1 with the liquid LQ if the moving speed of the substrate P is increased. Therefore, the control device CONT slows down the moving speed of the substrate P in accordance with the adhesion force E. By doing so, the substrate P can be exposed in a state where the optical path space K1 is satisfactorily filled with the liquid LQ. On the other hand, when the adhesion force E is small, the moving speed of the substrate P can be increased and the throughput can be improved.

  Here, the moving speed of the substrate P includes not only the moving speed in the Y-axis direction (scanning direction) but also the moving speed in the X-axis direction (stepping direction).

Further, the control device CONT controls the operation of the liquid immersion mechanism 1 based on the determined exposure condition, and adjusts the liquid supply amount per unit time for the optical path space K1. For example, when the adhesion force E acting between the surface of the substrate P to be exposed and the liquid LQ is small, bubbles may be easily generated in the liquid LQ. Therefore, when the adhesion force E is small, the control device CONT increases the amount of liquid supplied per unit time to the optical path space K1 according to the adhesion force E, and supplies the liquid LQ deaerated from the supply port 12. A large amount is supplied to the optical path space K1. By doing so, even when bubbles are present in the liquid LQ in the optical path space K1, the bubbles can be dissolved in the degassed liquid LQ and reduced or eliminated. Therefore, the substrate P can be exposed in a state where the optical path space K1 is filled with the desired liquid LQ.
Even if bubbles are generated in the optical path space K1, the bubbles can be immediately retreated from the optical path space K1 by the liquid LQ supplied in large quantities. On the other hand, when the adhesive force E is large, the amount of liquid supplied per unit time to the optical path space K1 can be reduced, and the amount of liquid LQ to be used can be suppressed.

  As described above, since the exposure conditions for exposing the substrate P are determined according to the adhesive force E acting between the surface of the substrate P and the liquid LQ, different types of films are formed. In addition, it is possible to satisfactorily perform immersion exposure on each of the plurality of substrates P. Therefore, the versatility of the immersion exposure apparatus EX can be improved.

  As described above, the movement conditions of the substrate P can include acceleration / deceleration when moving the substrate P, a movement direction (movement locus) with respect to the optical path space K1, and the like. The control device CONT determines the acceleration / deceleration and the movement direction (movement locus) based on the adhesion force E, and controls the operation of the substrate stage PST based on the determined acceleration / deceleration and movement direction (movement locus). Meanwhile, the substrate P can be subjected to immersion exposure. Also in this case, the storage device MRY stores in advance information regarding the optimum acceleration corresponding to the adhesion force E, the movement direction (movement locus), and the like, and the control device CONT stores the adhesion force E and the storage device MRY. Based on the information, it is possible to determine the optimum acceleration and movement direction (movement locus) when the substrate P is exposed. As an example, when the adhesion force E is large, if the acceleration of the substrate P is increased, it may be difficult to satisfactorily fill the optical path space K1 with the liquid LQ. Therefore, the acceleration of the substrate P is reduced. On the other hand, when the adhesion force E is small, the acceleration of the substrate P can be increased.

  Further, the above-described supply conditions may include the liquid supply position (distance) with respect to the optical path space K1, the supply direction, and the like. That is, the supply conditions can include the position, distance, number, and the like of the supply port 12 with respect to the optical path space K1. The control device CONT can determine these supply conditions based on the adhesion force E, and can perform immersion exposure of the substrate P while controlling the operation of the liquid immersion mechanism 1 based on the determined supply conditions. . Also in this case, the storage device MRY stores in advance information on the optimum supply position (distance) corresponding to the adhesion force E, the supply direction, etc., and the control device CONT stores the adhesion force E and the storage device MRY. Based on the information, it is possible to determine an optimum supply condition when exposing the substrate P. The control device CONT can supply the liquid LQ satisfactorily by adjusting the supply conditions when supplying the liquid LQ according to the adhesive force E, and can form the immersion region LR in a desired state.

  Further, as described above, the immersion condition includes a recovery condition for recovering the liquid LQ in the optical path space K1. The recovery conditions include not only the amount of liquid recovered per unit time from the optical path space K1, but also the liquid recovery position (distance) with respect to the optical path space K1, the recovery direction, and the like. That is, the recovery conditions can include the recovery force (suction force) of the liquid recovery device 21, the position, distance, number, and the like of the recovery port 22 with respect to the optical path space K1. The control device CONT can determine these recovery conditions based on the adhesion force E, and can perform immersion exposure of the substrate P while controlling the operation of the liquid immersion mechanism 1 based on the determined recovery conditions. . Also in this case, the storage device MRY stores in advance information on the optimum liquid recovery amount per unit time corresponding to the adhesion force E, the recovery position (distance), the recovery direction, and the like. Based on the adhesion force E and the information stored in the storage device MRY, it is possible to determine the optimum recovery conditions for exposing the substrate P. There is a possibility that the recoverability (recovery capability) of the liquid immersion mechanism 1 when recovering the liquid LQ varies depending on the adhesion force E, but the control device CONT recovers the liquid LQ according to the adhesion force E. By adjusting the recovery conditions when performing the above, it is possible to recover the liquid LQ satisfactorily and form the immersion region LR in a desired state.

  In the present embodiment, it goes without saying that the conditions stored in the storage device MRY are optimized for the conditions for moving the substrate P and the liquid immersion conditions. For example, when the moving speed of the substrate P is high, the liquid supply amount per unit time is increased, and the liquid LQ is recovered with a liquid recovery amount corresponding to the liquid supply amount, whereby the optical path space K1 is liquidated. Satisfy well with LQ. On the other hand, when the moving speed of the substrate P is relatively low, the liquid supply amount per unit time can be reduced.

  In the above embodiment, the single measurement device 60 measures the static contact angle θ of the liquid LQ on the surface of the substrate P and the sliding angle α of the liquid LQ on the surface of the substrate P. A first measuring device that measures the static contact angle θ of the liquid LQ on the surface of the substrate P and a second measuring device that measures the sliding angle α of the liquid LQ on the surface of the substrate P are provided separately. Also good.

  In the above-described embodiment, the measurement device 60 is provided on the conveyance path of the conveyance device H, but the installation position of the measurement device 60 may be a position other than the conveyance route of the conveyance device H.

  In the above-described embodiment, measurement is performed by the measurement device 60 for each substrate P. However, when the film formed on the surface is the same as the substrate P previously measured, the measurement device 60 is used. Measurement at may be omitted. For example, only the head substrate P of one lot composed of a plurality of substrates P may be measured by the measuring device 60.

  In the above-described embodiment, the exposure condition for the substrate P after the measurement is determined based on the measurement result of the measurement device 60. However, the exposure differs for each shot area on the substrate P after the measurement. Conditions may be set.

  In the above-described embodiment, pure water is used as the liquid LQ, the adhesion force E of the substrate P to the liquid LQ is obtained, and the exposure condition for exposing the substrate P is determined according to the adhesion force E. However, the adhesive force E may be set to a desired value by changing the type (physical properties) of the liquid LQ, for example, by changing the liquid LQ to fluorinated oil. The exposure conditions may be determined according to the adhesion force E. Alternatively, the physical properties of the liquid (pure water) LQ may be changed by adding a predetermined material (additive) to the liquid (pure water) LQ.

  In the first embodiment described above, a liquid LQ droplet is disposed on the surface of the substrate P that is actually exposed to manufacture a device, and the state of the droplet when the substrate P is tilted is shown. The measurement device 60 has been described as measuring, but for example, a droplet is placed on an object (for example, a test substrate) having a surface substantially similar to the surface of the substrate P to be actually exposed, and the surface of the object is inclined. You may make it measure the state of the droplet when it is made to do.

<Second Embodiment>
Next, a second embodiment will be described. In the following description, the same or equivalent components as those of the above-described embodiment are denoted by the same reference numerals, and the description thereof is simplified or omitted.

  In the above-described embodiment, the exposure conditions for exposing the substrate P are determined (adjusted) according to the adhesion E between the substrate P to be exposed and the liquid (pure water) LQ. Before setting the allowable range of the adhesion force E and exposing the substrate P, it is determined whether or not the substrate P has a film having the allowable adhesion force E with respect to the liquid (pure water) LQ, that is, an immersion exposure process. It may be determined whether or not the substrate P has an appropriate film. For example, an index value (allowable value) for determining whether or not the adhesion force E is appropriate for the immersion exposure process is stored in the storage device MRY, and the immersion exposure process is performed according to the index value. It is possible to determine whether or not the adhesion force E is appropriate for this. This index value can be obtained in advance by, for example, experiments or simulations. Based on the above determination result, the substrate P having an inappropriate film can be prevented from being exposed. For example, when the adhesion force E to the liquid (pure water) LQ of the substrate P conveyed to the measuring device 60 by the conveyance device H is measured and the measured adhesion force E is outside a predetermined allowable range, The substrate P is not loaded on the substrate stage PST. This eliminates the need to expose the substrate P having a film inappropriate for the immersion exposure process, prevents the liquid LQ from leaking out, and contributes to improving the operating rate of the exposure apparatus EX. .

  Also in this embodiment, the type (physical properties) of the liquid LQ may be changed so that the adhesion force E acting between the surface of the substrate P and the liquid LQ falls within an allowable range. Alternatively, by adding a predetermined material (additive) to the liquid (pure water) LQ, the adhesive force E acting between the surface of the substrate P and the liquid LQ may be within an allowable range.

<Third Embodiment>
Next, a third embodiment will be described. In the first and second embodiments described above, the static contact angle θ of the liquid LQ on the surface of the substrate P and the sliding angle α of the liquid LQ on the surface of the substrate P are measured by the measuring device 60 in the exposure apparatus EX. Although the measurement is performed, the static contact angle θ and the sliding angle α can be measured by an apparatus different from the exposure apparatus EX without mounting the measurement apparatus 60 in the exposure apparatus EX. In this embodiment, in order to determine the exposure condition when exposing the substrate P, information on the static contact angle θ of the liquid LQ on the surface of the substrate P and the sliding angle α of the liquid LQ on the surface of the substrate P Information is input to the control device CONT via the input device INP. The control device CONT determines the exposure conditions for exposing the substrate P based on the information on the contact angle θ input from the input device INP and the information on the sliding angle α. That is, the control device CONT derives the adhesive force E based on the information on the contact angle θ and the information on the sliding angle α input from the input device INP, as in the above-described embodiment. The optimum exposure condition for the substrate P to be exposed is determined based on the information (map data) relating to the optimum exposure condition corresponding to the adhesive force E stored in advance in the storage device MRY.

  The data input to the input device INP may be an adhesion force E calculated based on the measured static contact angle θ and sliding angle α. Alternatively, physical property value data (static contact angle θ and sliding angle α or adhesion force E) that is known in advance may be used without performing measurement.

  In the first to third embodiments described above, the relationship between the adhesive force (static contact angle and sliding angle) and the optimum exposure condition is stored in the storage device MRY, but based on the results of experiments or simulations. The function determined in this manner may be stored in the storage device MRY, and the optimum exposure condition for the adhesive force E may be obtained using the function.

<Fourth embodiment>
Next, a fourth embodiment will be described. In the first to third embodiments described above, the adhesion force E is derived based on the static contact angle θ of the liquid LQ on the surface of the substrate P and the sliding angle α of the liquid LQ on the surface of the substrate P. The exposure conditions for exposing the substrate P are determined according to the adhesion force E. The characteristic part of this embodiment is that the exposure conditions for exposing the substrate P are expressed by the equation (θ− t × α).

In the present embodiment, the control device CONT has a value U defined by the following equation (2).
U = (θ−t × α) (2) The exposure conditions for exposing the substrate P are determined based on (2).
However,
θ: static contact angle of the liquid LQ on the surface of the substrate P,
α: Sliding angle of the liquid LQ on the surface of the substrate P,
t: a predetermined constant.

  The inventor changes the exposure conditions (the movement conditions of the substrate P, the immersion conditions, etc.) that can maintain the immersion region LR in the desired state on the substrate P according to the value U (= θ−t × α). I found out. That is, when the optical path space K1 between the final optical element LS1 of the exposure apparatus EX and the film of the substrate P is filled with the liquid LQ and the liquid immersion region LR of the liquid LQ is formed on the substrate P, the liquid immersion region LR is changed. It has been found that the exposure conditions that can be maintained in a desired state change according to the value U corresponding to the film of the substrate P and the liquid LQ. Therefore, by setting optimal exposure conditions according to the value U, the substrate P can be exposed without causing problems such as outflow of the liquid LQ and generation of bubbles in the liquid LQ.

  For example, the above-described exposure conditions include conditions for moving the substrate P. That is, the substrate P (film) is moved while the optical path space K1 between the final optical element LS1 of the exposure apparatus EX and the film of the substrate P is filled with the liquid LQ and the liquid LQ immersion region LR is formed on the film. When this is done, the maximum speed at which the immersion region LR can be maintained in a desired state (hereinafter referred to as an allowable speed) varies according to the value U corresponding to the film of the substrate P and the liquid LQ. Therefore, if the substrate P is moved at an allowable speed corresponding to the value U or less, the substrate P can be exposed while suppressing occurrence of problems such as outflow of the liquid LQ and generation of bubbles in the liquid LQ.

  In the present embodiment, the control device CONT determines a moving condition (moving speed of the substrate P) when moving the substrate P based on the value U described above.

  FIG. 7 shows an example of the result of an experiment conducted to derive the relationship between the value U and the allowable speed. In the experiment, the type of film provided on the uppermost layer (the surface of the substrate P) on the substrate P is changed, and the static contact angle θ of the liquid LQ and the sliding angle α of the liquid LQ in each of the plurality of types of films. Was measured, and the value U for each film and the permissible speed of the substrate P for each film were determined. Note that the permissible speed of the substrate P shown in the experimental example of FIG. 7 is that the optical path space K1 is filled with the liquid LQ and the liquid LQ does not flow out (drops and films of the liquid LQ are left on the substrate P). The speed at which the substrate P can be moved. Further, as shown in FIG. 7, in this experimental example, 26 types of films were prepared, and data for each of the plurality of films was acquired.

  As described above, the measuring device 60 can measure the static contact angle θ of the liquid LQ on the surface of the substrate P and the sliding angle α of the liquid LQ on the surface of the substrate P. In this experimental example, each film A predetermined amount (for example, 50 microliters) of liquid LQ was dropped on the surface of the film, and the static contact angle θ and sliding angle α of the liquid LQ in each film were obtained using the measuring device 60. The predetermined constant t is a value determined according to, for example, the structure and capability (liquid supply capability, liquid recovery capability, etc.) of the nozzle member 70, and can be derived by experiment or simulation.

  In this experimental example, a predetermined constant t = 1 is set, and a value U (that is, θ−α) for each film is derived based on the measurement result of the measuring device 60, and for each film. The allowable speed was determined. As described above, the film on the substrate P forms a liquid contact surface in contact with the liquid LQ at the time of immersion exposure. Therefore, as shown in FIG. 7, depending on the type (physical properties) of the film, that is, the value U The allowable speed changes accordingly.

  FIG. 8 is a graph showing the relationship between the value U (where t = 1) and the allowable speed, that is, a graph of the experimental results of FIG. FIG. 8 shows points corresponding to the above experimental results and approximate curves obtained by fitting these experimental results. As shown in FIG. 8, it can be seen that the allowable speed changes according to the value U = (θ−t × α). Specifically, it can be seen that the allowable speed increases as the value U increases. Accordingly, by providing a film having a large value U on the substrate P, the substrate P is moved at a high speed while the substrate L is filled with the liquid LQ between the final optical element LS1 and the substrate P (film). Can be exposed.

  Next, an example of a measurement procedure using the measurement apparatus 60 and an exposure procedure when exposing the substrate P will be described. When exposing the substrate P having a predetermined film, the controller CONT uses the measuring device 60 to expose the static contact angle θ of the liquid LQ on the surface (film) of the substrate P before exposing the substrate P. Measure. Further, the control device CONT uses the measuring device 60 to measure the sliding angle α of the liquid LQ on the surface (film) of the substrate P. Then, the control device CONT obtains the value U (= θ−t × α) based on the measurement result of the measuring device 60. In the storage device MRY, information (function, map data, etc.) for deriving an allowable speed of the substrate P corresponding to the value U (static contact angle θ and sliding angle α) is stored in advance. In the present embodiment, the storage device MRY stores a function (for example, a function corresponding to the approximate curve in FIG. 8) for deriving an allowable speed of the substrate P corresponding to the value U, using the value U as a parameter. As described above, the information regarding the allowable speed of the substrate P corresponding to the value U can be obtained in advance by experiment or simulation, and is stored in the storage device MRY.

  The control device CONT determines an exposure condition (moving speed of the substrate P) when exposing the substrate P based on the measurement result of the measuring device 60 and the stored information of the storage device MRY. That is, the control device CONT obtains the obtained value U (information on the static contact angle θ and sliding angle α) and information on the allowable speed of the substrate P corresponding to the value U stored in the storage device MRY in advance. Based on the above, the moving speed of the substrate P to be exposed is determined so as not to exceed the allowable speed.

  Then, the control device CONT performs immersion exposure of the substrate P based on the determined exposure condition (movement speed of the substrate P). For example, when the value U corresponding to the surface of the substrate P to be exposed and the liquid LQ is small, it is difficult to satisfactorily fill the optical path space K1 with the liquid LQ if the moving speed of the substrate P is increased. Therefore, the control device CONT slows down the moving speed of the substrate P according to the value U. By doing so, the substrate P can be exposed in a state where the optical path space K1 is satisfactorily filled with the liquid LQ. On the other hand, when the value U is large, the moving speed of the substrate P can be increased and the throughput can be improved.

  In consideration of the throughput, it is desirable that the moving speed of the substrate P is set to an allowable speed corresponding to the value U.

  The moving speed of the substrate P includes not only the moving speed (scanning speed) during exposure in which the exposure light EL is irradiated onto the substrate P but also the moving speed (stepping speed) during stepping performed between shots. .

  As described above, since the exposure conditions for exposing the substrate P are determined based on the equation (θ−t × α), each of the plurality of substrates P on which different types of films are formed is determined. In contrast, immersion exposure can be performed satisfactorily. Therefore, the versatility of the immersion exposure apparatus EX can be improved.

  In this embodiment, the moving speed of the substrate P is determined based on the value U. However, the acceleration, deceleration, moving direction (moving locus), and continuous moving distance in one direction of the substrate P are determined. Can be determined at least in part. That is, the relationship between at least a part of the maximum acceleration, the maximum deceleration, and the maximum movement distance that can maintain the immersion region LR in a desired state on the substrate P and the value U is obtained in advance. And at least a part of the acceleration, deceleration, and movement distance may be determined so as not to exceed the allowable value obtained from the value U corresponding to the liquid LQ. If the value U is small, the immersion region LR may not be maintained in a desired state depending on the movement direction of the substrate P. Therefore, depending on the value U, the movement direction of the substrate P may be limited, The speed when moving in a predetermined direction may be made smaller than the speed when moving in other directions.

  In addition, based on the value U, the liquid immersion region including supply conditions for supplying the liquid LQ to form the liquid immersion region LR and recovery conditions for recovering the liquid LQ forming the liquid immersion region LR The immersion conditions for forming the LR can be determined. For example, if the relationship between the maximum liquid supply amount that can maintain the liquid immersion region LR in a desired state on the substrate P and the value U is obtained in advance, the liquid LQ is set so as not to exceed the allowable value obtained from the value U. The supply amount may be determined.

  In the fourth embodiment, before setting the allowable range of the value U and exposing the substrate P, whether or not the substrate P has a film having the allowable range value U with respect to the liquid (pure water) LQ. In other words, it may be determined whether or not the substrate P has a film suitable for the immersion exposure process.

  In the fourth embodiment, the first measurement device that measures the static contact angle θ of the liquid LQ on the surface of the substrate P and the second measurement that measures the sliding angle α of the liquid LQ on the surface of the substrate P. The apparatus may be provided separately.

  In the above-described fourth embodiment, a liquid LQ droplet is disposed on the surface of the substrate P that is actually exposed to manufacture a device, and the state of the droplet when the substrate P is tilted is shown. The measurement device 60 has been described as measuring, but for example, a droplet is placed on an object (for example, a test substrate) having a surface substantially similar to the surface of the substrate P to be actually exposed, and the surface of the object is inclined. You may make it measure the state of the droplet when it is made to do.

<Fifth Embodiment>
In the fourth embodiment described above, the static contact angle θ and the sliding angle α can be measured by an apparatus different from the exposure apparatus EX without mounting the measurement apparatus 60 in the exposure apparatus EX. Then, in order to determine the exposure condition when exposing the substrate P, information on the static contact angle θ of the liquid LQ on the surface of the substrate P and information on the sliding angle α of the liquid LQ on the surface of the substrate P are obtained. And input to the control device CONT via the input device INP. The control device CONT determines the exposure conditions for exposing the substrate P based on the information on the contact angle θ input from the input device INP and the information on the sliding angle α. That is, the control device CONT derives the value U based on the information on the contact angle θ and the information on the sliding angle α input from the input device INP, and stores the derived value U and the storage as in the above embodiment. The optimum exposure condition for the substrate P to be exposed is determined based on information that is stored in advance in the apparatus MRY and that derives a condition for maintaining the immersion region LR in a desired state from the value U. Of course, the optimum exposure condition may be determined by inputting the value U from the input device INP.

<Sixth Embodiment>
Next, a sixth embodiment will be described. The characteristic part of the present embodiment is that the exposure condition for exposing the substrate P is determined based on the receding contact angle of the liquid LQ on the surface of the substrate P when the surface of the substrate P is inclined. .

In the present embodiment, the control unit CONT determines the exposure conditions when based on the receding contact angle theta _R of the liquid LQ on the surface of the substrate P when tilting the surface of the substrate P, the substrate P is exposed .

With reference to the schematic diagram of FIG. 9 will be described receding contact angle theta _R. The receding contact angle θ _R is the surface of the object when the surface of the object is inclined with respect to the horizontal plane with the liquid LQ droplet attached to the surface of the object (here, the surface of the substrate P). The contact angle on the rear side of the droplet when the droplet of the liquid LQ that has adhered slides downward (begins moving) due to the action of gravity. In other words, the receding contact angle θ _R is the contact angle of the back side of the droplet at the critical angle of the sliding angle α when the surface of the object to which the droplet of the liquid LQ adheres is tilted. To tell. The liquid LQ droplet adhering to the surface of the object slides downward (starts moving) due to the gravitational action means the moment when the liquid droplet starts moving, but starts moving. It may be at least a part of the state immediately before and immediately after the start of movement.

The present inventor has also depending on the receding contact angle theta _R of the liquid LQ on the front surface of the substrate P, can exposure conditions maintain the liquid immersion area LR in the desired state on the substrate P (movement conditions of the substrate P, the liquid immersion conditions Etc.) was found to change. That is, when the present inventor EX fills the space between the final optical element LS1 of the exposure apparatus EX and the film of the substrate P with the liquid LQ to form the liquid immersion region LR of the liquid LQ on the substrate P, the liquid immersion region LR. exposure conditions can be maintained in the desired state is found that changes in accordance with the receding contact angle theta _R corresponding to the film and the liquid LQ of the substrate P. Therefore, by setting the optimum exposure conditions in accordance with the receding contact angle theta _R, outflow of the liquid LQ, and without causing a problem such as occurrence of bubbles in the liquid LQ, it is possible to expose the substrate P .

For example, the exposure conditions include the moving speed of the substrate P. That is, when the space between the final optical element LS1 of the exposure apparatus EX and the film of the substrate P is filled with the liquid LQ, and the liquid immersion area LR of the liquid LQ is formed on the substrate P, the liquid immersion area LR is brought into a desired state. maximum speed can be maintained (permissible speed) is changed in accordance with the receding contact angle theta _R corresponding to the film and the liquid LQ of the substrate P. Accordingly, if the substrate P moves within the allowable speed corresponding to the receding contact angle theta _R, outflow of the liquid LQ, and while suppressing the occurrence of problems such as generation of bubbles in the liquid LQ, exposing the substrate P Can do.

The receding contact angle θ _R can be measured using the above-described measuring device 60. When measuring the receding contact angle theta _R of the liquid LQ on the surface of the substrate P, firstly, the measuring unit 60, so that the surface of the substrate P held by the holding member 61 is substantially parallel to the horizontal plane (XY plane), The position (posture) of the holding member 61 is adjusted via the drive system 65. Then, the measuring device 60 drops a liquid LQ droplet from the dropping member 62 onto the surface of the substrate P substantially parallel to the horizontal plane. Similar to the procedure described with reference to FIG. 4, the measuring device 60 uses the drive system 65 to hold the holding member 61 holding the substrate P in a state where the droplets are arranged on the surface of the substrate P. Rotate (tilt) in the direction. As the holding member 61 rotates (tilts), the surface of the substrate P also rotates (tilts). As the surface of the substrate P is rotated (tilted), the liquid droplets adhering to the surface of the substrate P slide downward (begin movement) due to the gravitational action. At this time, the measuring device 60 illuminates the droplets arranged on the surface of the substrate P with the illumination device 64 and acquires an image of the droplets using the observation device 63. The observation device 63 can observe that the liquid droplet has started to slide, and outputs image information regarding the acquired image to the control device CONT. Based on the signal (image information) output from the observation device 63, the control device CONT can determine the time point when the droplet on the surface of the substrate P starts to move (the time point when it starts to slide). Then, the control unit CONT, the output from the observation apparatus 63 signal processing (image processing), based on the processing result, to obtain the receding contact angle theta _R of droplets of the liquid LQ on the front surface of the substrate P Can do. Thus, receding contact angle theta _R of the liquid LQ on the front surface of the substrate P is measured by the measuring device 60 which includes a control unit CONT.

  Further, the control device CONT determines the angle (namely, sliding angle) α of the surface of the substrate P at the time when the droplet on the surface of the substrate P starts to move, by the drive amount (tilt amount) of the holding member 61 by the drive system 65. It can be obtained more. That is, the control device CONT uses the signal (image information) output from the observation device 63 and the driving amount of the holding member 61 by the driving system 65, and the sliding angle α of the liquid LQ droplet on the surface of the substrate P. Can be requested. In this way, the sliding angle α of the liquid LQ on the surface of the substrate P is measured by the measuring device 60 including the control device CONT.

Further, the control device CONT can display an image of a droplet on the surface of the substrate P on the display device DY based on a signal (image information) output from the observation device 63. Thus, to display the status of the droplet on the display device DY, visually, it may be measured receding contact angle theta _R of the liquid LQ on the surface of the substrate P when the droplet on the surface of the substrate P starts to move .

Figure 10 shows the results of an experiment conducted in order to derive the relationship between the receding contact angle theta _R and permissible speed. Experiments changing the type of film provided on the uppermost layer of the substrate P (the surface of the substrate P), while measuring the receding contact angle theta _R of the liquid LQ on each of the plurality of types of films, each of the films The permissible speed of the substrate P was determined. Note that the permissible speed of the substrate P shown in the experimental example of FIG. 10 is that the optical path space K1 is filled with the liquid LQ and the liquid LQ does not flow out (drops and films of the liquid LQ are left on the substrate P). The speed at which the substrate P can be moved. Further, as shown in FIG. 10, in this experimental example, 24 types of films were prepared, and each data for each of the plurality of films was acquired.

As described above, the measuring apparatus 60 is capable of measuring a receding contact angle theta _R of the liquid LQ on the front surface of the substrate P, in this experimental example, a few tens of microliters on the surface of the film (e.g., 50 microliters) Pour the drops of the liquid LQ, using the measurement device 60 to determine the receding contact angle theta _R of the liquid LQ on each film.

Figure 11 is a graph of the figure, i.e. the experimental results of FIG. 10 showing the relationship between the receding contact angle theta _R and permissible speed. In FIG. 11, points corresponding to the above-described experimental results and approximate curves obtained by fitting these experimental results are shown. As shown in FIG. 11, in accordance with the receding contact angle theta _R of the liquid LQ on the front surface of the substrate P, it can be seen that the permissible speed varies. Specifically, the larger the receding contact angle theta _R is, it can be seen that the permissible speed is increased. Therefore, on the substrate P, by providing the receding contact angle theta _R is large film for liquid LQ, the space between the final optical element LS1 and the substrate P (film) in a state filled with the liquid LQ, the substrate P at a high speed The substrate P can be exposed while moving.

Next, an example of a measurement procedure using the measurement apparatus 60 and an exposure procedure when exposing the substrate P will be described. When exposing the substrate P having a predetermined film, the controller CONT uses the measuring device 60 to set the receding contact angle θ _R of the liquid LQ on the surface (film) of the substrate P before exposing the substrate P. measure. Then, the control unit CONT, the measurement result of the measuring device 60, i.e. based on the receding contact angle theta _R, to determine the exposure conditions to be used during the exposure of the substrate P. In the present embodiment, the control device CONT determines a moving condition (moving speed of the substrate P) when moving the substrate P as one of the exposure conditions.

Here, the storage device MRY, information (function, map data, etc.) for deriving the permissible speed of the substrate P corresponding to the receding contact angle theta _R of the liquid LQ is previously stored. In the present embodiment, the storage unit MRY may receding contact angle theta _R of the liquid LQ as a parameter, the approximation curve of the function (e.g., Fig. 11 for deriving the permissible speed of the substrate P that corresponds to the receding contact angle theta _R Is stored). Information about the permissible speed of the substrate P corresponding to the receding contact angle theta _R may be determined in advance by experiments or simulations, it is stored in the storage apparatus MRY.

The control device CONT determines an exposure condition (moving speed of the substrate P) when exposing the substrate P based on the measurement result of the measuring device 60 and the stored information of the storage device MRY. That is, the control unit CONT based on the receding contact angle theta _R of the liquid LQ obtained are previously stored in the storage device MRY, and the information on the allowable speed of the substrate P corresponding to the receding contact angle theta _R of the liquid LQ Thus, the optimum moving speed of the substrate P to be exposed is determined so as not to exceed the allowable speed.

Then, the control device CONT performs immersion exposure of the substrate P based on the determined exposure condition (movement speed of the substrate P). For example, if the receding contact angle theta _R of the liquid LQ is small, the speed of the movement of the substrate P, since the optical path space K1 can be difficult to meet satisfactorily with the liquid LQ, the controller CONT, depending on the receding contact angle theta _R of the liquid LQ, slowing the movement speed of the substrate P. By doing so, the substrate P can be exposed in a state where the optical path space K1 is satisfactorily filled with the liquid LQ. On the other hand, if the receding contact angle theta _R of the liquid LQ is large, the movement speed of the substrate P can speed, throughput can be improved.

Incidentally, in consideration of throughput, the moving speed of the substrate P is desirably set to the allowable speed corresponding to the receding contact angle theta _R.

  The moving speed of the substrate P includes not only the moving speed (scanning speed) during exposure in which the exposure light EL is irradiated onto the substrate P but also the moving speed (stepping speed) during stepping performed between shots. .

As described above, based on the receding contact angle theta _R of the liquid LQ on the front surface of the substrate P, since so as to determine the exposure conditions for exposing the substrate P, a plurality of different types of films are formed The immersion exposure can be satisfactorily performed on each of the substrates P. Therefore, the versatility of the immersion exposure apparatus EX can be improved.

In the present embodiment, based on the receding contact angle theta _R of the liquid LQ, but determines the moving speed of the substrate P, the acceleration of the substrate P, the deceleration, movement direction (movement trajectory), and one direction At least a portion of the continuous travel distance can be determined. That is, the relationship between the maximum acceleration, maximum deceleration, at least a part of the maximum movement distance and the receding contact angle θ _R that can maintain the immersion region LR in a desired state on the substrate P is determined in advance. You may determine at least one part of an acceleration, deceleration, and a movement distance so that the allowable value calculated | required from receding contact angle (theta) _R corresponding to the film | membrane of P and the liquid LQ may not be exceeded. Also, if the receding contact angle theta _R is small, depending on the direction of movement of the substrate P, because the liquid immersion area LR is a possibility can not be maintained in the desired state, in accordance with the receding contact angle theta _R, the direction of movement of the substrate P You may restrict | limit or make it the speed when moving the board | substrate P to a predetermined direction be smaller than the speed when moving to another direction.

Further, based on the value theta _R, including the supply condition for supplying the liquid LQ to form the liquid immersion area LR, and the recovery conditions for recovering the liquid LQ for forming the liquid immersion area LR, immersion The immersion conditions when forming the region LR can be determined. For example, if previously obtained relation between the maximum liquid supply rate can be maintained in the desired state of the liquid immersion region LR on the substrate P and the receding contact angle theta _R, exceeds an allowable value determined from the receding contact angle theta _R The supply amount of the liquid LQ may be determined so as not to occur.

Further, in the sixth embodiment, to set the permissible range of the receding contact angle theta _R of the liquid LQ, before exposing the substrate P, the receding contact angle of tolerance that substrate P is the liquid (pure water) LQ It may be determined whether or not the film has θ _R , that is, whether or not the substrate P has a film suitable for the immersion exposure process.

  In the above-described sixth embodiment, a liquid LQ droplet is disposed on the surface of the substrate P that is actually exposed to manufacture a device, and the state of the droplet when the substrate P is tilted is shown. The measurement device 60 has been described as measuring, but for example, a droplet is placed on an object (for example, a test substrate) having a surface substantially similar to the surface of the substrate P to be actually exposed, and the surface of the object is inclined. You may make it measure the state of the droplet when it is made to do.

<Seventh embodiment>
Further, in the sixth embodiment described above, without mounting the measuring device 60 in the exposure apparatus EX, it is measured in a different device than the receding contact angle theta _R of the exposure apparatus EX of the liquid LQ on the surface of the substrate P Can do. Then, in order to determine the exposure conditions to be used during the exposure of the substrate P, the information of the receding contact angle theta _R of the liquid LQ on the front surface of the substrate P is input to the control unit CONT via the input apparatus INP. The control unit CONT based on the information of the receding contact angle theta _R inputted from the input device INP, determines the exposure conditions to be used during the exposure of the substrate P. That is, the control unit CONT, the information of the receding contact angle theta _R inputted from the input device INP, it is previously stored in the storage device MRY, sustainable from receding contact angle theta _R immersion region LR in a desired state Based on the information for deriving the condition, the optimum exposure condition for the substrate P to be exposed is determined.

  In the above first to seventh embodiments, the storage information of the storage device MRY may be updated as needed. For example, when exposing a substrate P having a different type of film that is not stored in the storage device MRY, the new film is subjected to experiments or simulations to cope with the adhesive force (static contact angle and sliding angle). What is necessary is just to obtain | require exposure conditions and to update the memory | storage information memorize | stored in the memory | storage device MRY. Similarly, an experiment or simulation is performed on a new film to obtain an exposure condition corresponding to the receding contact angle, and the stored information stored in the storage device MRY may be updated. The stored information can be updated from a remote location with respect to the exposure apparatus EX (storage apparatus MRY) via a communication apparatus including the Internet, for example.

  In the first to seventh embodiments described above, when the movement condition of the substrate P is determined based on the adhesive force E (static contact angle and sliding angle) or the receding contact angle, based on the movement condition. The dose control parameter is adjusted. That is, based on the determined movement condition of the substrate P, the control device CONT determines the light amount (intensity) of the exposure light EL, the pulse oscillation period of the laser light, and the width in the scanning direction of the projection area AR irradiated with the exposure light EL. Are adjusted to optimize the dose amount for each shot region on the substrate P.

Further, in the first to seventh embodiments described above, adhesion of the film of the substrate P surface E, the static contact angle theta, sliding angle alpha, such as receding contact angle theta _R is, before and after the irradiation of the exposure light EL In the case of change, the moving condition and immersion condition of the substrate P may be changed before and after the exposure light EL irradiation. The adhesion force E of the film on the surface of the substrate P, the static contact angle θ, the sliding angle α, the receding contact angle θ _R, etc., whether or not the exposure light EL is irradiated, the contact time with the liquid LQ, and the film on the surface of the substrate P is formed In the case of changing in accordance with at least one of the elapsed time since the exposure, at least one of the presence / absence of irradiation of the exposure light EL, the contact time with the liquid LQ, and the elapsed time after the film on the surface of the substrate P is formed. It is desirable to determine exposure conditions such as the movement condition and immersion condition of the substrate P in consideration of the above.

Further, in the first through seventh embodiments discussed above, the adhesive force E (the static contact angle θ and sliding angle alpha), or receding contact angle θ on the basis of the _R are adapted to determine the exposure conditions, the liquid Other physical properties of LQ (viscosity, volatility, liquid resistance, surface tension, temperature dependence of refractive index (dn / dT), atmospheric solubility (ease of dissolving gas in contact with liquid LQ in liquid LQ The exposure conditions may be determined in consideration of the above.

Further, in the first through seventh embodiments discussed above, the adhesive force E (the static contact angle θ and sliding angle alpha), or receding contact angle θ on the basis of the _R are adapted to determine the exposure conditions, the substrate Sliding state at the interface between the film formed on the P surface and the liquid (for example, when the substrate P is moved at a predetermined speed substantially parallel to the surface of the substrate P in a state where an immersion region is formed on the substrate P) The exposure condition may be determined based on the generated relative velocity between the film and the liquid at the interface between the film and the liquid.

  In the first to seventh embodiments described above, the movement condition and the immersion condition of the substrate P are determined according to the film on the surface of the substrate P. However, the upper surface 97 of the substrate stage PST and the like other than the substrate P are determined. When forming an immersion area on another object, it is desirable to determine the moving condition of the substrate stage PST, the immersion condition on the substrate stage PST, and the like according to the film on the object surface.

  As described above, the liquid LQ in this embodiment is pure water. Pure water can be easily obtained in large quantities at a semiconductor manufacturing factory or the like, and has an advantage that there is no adverse effect on the photoresist on the substrate P and / or the optical element (lens). In addition, pure water has no adverse effects on the environment, and since the impurity content is extremely low, it can be expected to clean the surface of the substrate P and the surface of the optical element provided on the front end surface of the projection optical system PL. .

  The refractive index n of pure water (water) with respect to the exposure light EL having a wavelength of about 193 nm is said to be about 1.44, and when ArF excimer laser light (wavelength 193 nm) is used as the light source of the exposure light EL On the substrate P, the wavelength is shortened to 1 / n, that is, about 134 nm, and a high resolution can be obtained. Furthermore, since the depth of focus is enlarged by about n times, that is, about 1.44 times compared with that in the air, the projection optical system PL can be used when it is sufficient to ensure the same depth of focus as that in the air. The numerical aperture can be further increased, and the resolution is improved in this respect as well.

  In the present embodiment, the optical element LS1 is attached to the tip of the projection optical system PL, and the optical characteristics of the projection optical system PL, for example, aberration (spherical aberration, coma aberration, etc.) can be adjusted by this optical element. . The optical element attached to the tip of the projection optical system PL may be an optical plate used for adjusting the optical characteristics of the projection optical system PL. Alternatively, it may be a plane parallel plate that can transmit the exposure light EL.

  When the pressure between the optical element at the tip of the projection optical system PL generated by the flow of the liquid LQ and the substrate P is large, the optical element is not exchangeable but the optical element is moved by the pressure. It may be fixed firmly so that there is no.

  In the present embodiment, the space between the projection optical system PL and the surface of the substrate P is filled with the liquid LQ. However, for example, the liquid with the cover glass made of a plane-parallel plate attached to the surface of the substrate P is used. The structure which satisfy | fills LQ may be sufficient.

  In the projection optical system of the above-described embodiment, the optical path space on the image plane side of the optical element at the tip is filled with liquid, but as disclosed in International Publication No. 2004/019128, the optical at the tip is used. It is also possible to employ a projection optical system in which the optical path space on the object plane side of the element is filled with liquid.

The liquid LQ of the present embodiment is water, but may be a liquid other than water as described above. For example, when the light source of the exposure light EL is an F ₂ laser, the F ₂ laser light is water. The liquid LQ may be, for example, a fluorine-based fluid such as perfluorinated polyether (PFPE) or fluorine-based oil that can transmit the F ₂ laser light. In this case, the lyophilic treatment is performed by forming a thin film with a substance having a molecular structure having a small polarity including fluorine, for example, at a portion in contact with the liquid LQ. In addition, the liquid LQ is transparent to the exposure light EL, has a refractive index as high as possible, and is stable to the projection optical system PL and / or the photoresist applied to the surface of the substrate P. (For example, cedar oil) can also be used.

  Moreover, as the liquid LQ, a liquid having a refractive index of about 1.6 to 1.8 may be used. Furthermore, the optical element LS1 may be formed of a material having a higher refractive index than quartz and fluorite (for example, 1.6 or more).

  In addition, 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 (reticle) used in an exposure apparatus ( Synthetic quartz, silicon wafer) or the like is applied.

  As the exposure apparatus EX, 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 Can be applied to a step-and-repeat type projection exposure apparatus (stepper) in which the pattern of the mask M is collectively exposed while the substrate P is stationary and the substrate P is sequentially moved stepwise.

  Further, as the exposure apparatus EX, a reduced image of the first pattern is projected with the first pattern and the substrate P being substantially stationary (for example, a refraction type projection optical system that does not include a reflecting element at 1/8 reduction magnification). The present invention can also be applied to an exposure apparatus that performs batch exposure on the substrate P using the above. In this case, after that, with the second pattern and the substrate P substantially stationary, a reduced image of the second pattern is collectively exposed onto the substrate P by partially overlapping the first pattern using the projection optical system. It can also be applied to a 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.

  The present invention also relates to a twin stage type exposure apparatus having a plurality of substrate stages as disclosed in JP-A-10-163099, JP-A-10-214783, JP-T 2000-505958, and the like. It can also be applied to.

  Further, as disclosed in JP-A-11-135400 and JP-A-2000-164504, a measurement stage equipped with a substrate stage for holding a substrate, a reference member on which a reference mark is formed, and various photoelectric sensors. The present invention can also be applied to an exposure apparatus including the above.

  In the above-described embodiment, an exposure apparatus that locally fills the liquid between the projection optical system PL and the substrate P is employed. However, the present invention is disclosed in JP-A-6-124873 and JP-A-10. -303114, US Pat. No. 5,825,043, etc., and can be applied to an immersion exposure apparatus that performs exposure in a state where the entire surface of the substrate to be exposed is immersed in the liquid. is there.

  The type of exposure apparatus EX is not limited to an exposure apparatus for manufacturing a semiconductor element that exposes a semiconductor element pattern onto a substrate P, but an exposure apparatus for manufacturing a liquid crystal display element or a display, a thin film magnetic head, an image sensor (CCD). Alternatively, it can be widely applied to an exposure apparatus for manufacturing a reticle or a mask.

  In the above-described embodiment, a light-transmitting mask in which a predetermined light-shielding pattern (or phase pattern / dimming pattern) is formed on a light-transmitting substrate is used. As disclosed in Japanese Patent No. 6,778,257, an electronic mask 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, as disclosed in International Publication No. 2001/035168, an exposure apparatus (lithography system) that exposes a line-and-space pattern on a substrate P by forming interference fringes on the substrate P. The present invention can also be applied.

  The exposure apparatus EX according to the embodiment of the present application is manufactured by assembling various subsystems including the respective constituent elements recited in the claims of the present application so as to maintain predetermined mechanical accuracy, electrical accuracy, and optical accuracy. Is done. 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. 12, a microdevice such as a semiconductor device includes a step 201 for designing a function / performance of the microdevice, a step 202 for producing a mask (reticle) based on the design step, and a substrate which is a base material of the device. Manufacturing step 203, step 204 including processing of exposing the mask pattern onto the substrate by the exposure apparatus EX of the above-described embodiment, device assembly step (including dicing process, bonding process, packaging process) 205, inspection step 206, etc. It is manufactured through.

It is a schematic block diagram which shows one Embodiment of exposure apparatus. It is a figure for demonstrating the positional relationship of the immersion area | region and substrate when exposing a board | substrate. It is sectional drawing which shows an example of a board | substrate. It is a figure which shows one Embodiment of a measuring device. It is a figure for demonstrating adhesive force. It is a flowchart for demonstrating one Embodiment of the exposure method. It is a figure which shows the experimental result performed in order to derive | lead-out the relationship between a static contact angle, sliding-down angle, and permissible speed. It is a figure which shows the relationship between a static contact angle, sliding-down angle, and permissible speed. It is a figure for demonstrating a receding contact angle. It is a figure which shows the experimental result performed in order to derive | lead-out the relationship between receding contact angle and permissible speed. It is a figure which shows the relationship between receding contact angle, sliding angle, and permissible speed. It is a flowchart figure for demonstrating an example of the manufacturing process of a microdevice.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Immersion mechanism, 60 ... Measuring device, CONT ... Control device, EL ... Exposure light, EX ... Exposure device, INP ... Input device, LQ ... Liquid, LR ... Immersion area, MRY ... Storage device, P ... Substrate, PST ... Substrate stage

Claims (20)

An exposure method of irradiating the substrate with exposure light through a liquid in an immersion area formed on the substrate while moving the substrate,
Determining a moving condition of the substrate capable of maintaining the immersion region in a desired state based on a receding contact angle of the liquid on the surface of the substrate when the substrate is tilted;
Have a, a step of exposing the substrate through the liquid of the liquid immersion area while moving the substrate on the basis of the moving condition,
The movement condition of the substrate includes a maximum movement speed of the substrate, and the step of determining the movement condition determines the maximum movement speed based on a relationship in which the maximum movement speed increases with an increase in the receding contact angle. exposure method for.   The exposure method according to claim 1, wherein the substrate is moved and exposed at a moving speed of the substrate not exceeding the maximum moving speed.   The exposure light is irradiated to the shot area on the substrate while moving the substrate in the scanning direction,
  The exposure method according to claim 2, wherein the moving speed of the substrate includes a moving speed during exposure in which exposure light is irradiated onto the substrate.   The exposure light is sequentially irradiated to a plurality of shot areas on the substrate while moving the substrate,
  4. The exposure method according to claim 2, wherein the moving speed of the substrate includes a moving speed during stepping when moving the next shot area to the exposure start position after completion of exposure of one shot area.   The exposure according to any one of claims 1 to 4, wherein at least a part of acceleration, deceleration, movement locus, and continuous movement distance in one direction of the substrate is determined based on the receding contact angle. Method.   An exposure method for supplying a liquid onto a substrate and irradiating the substrate with exposure light through a liquid in an immersion region formed on the substrate by the supplied liquid,
  Obtaining a maximum liquid supply amount on the substrate that can maintain the immersion region in a desired state based on a receding contact angle of the liquid on the surface of the substrate when the substrate is inclined;
  Determining a liquid immersion condition when forming the liquid immersion region based on the maximum liquid supply amount;
  Forming an immersion area based on the immersion condition, and exposing the substrate through the liquid in the immersion area.   The exposure method according to claim 6, wherein the immersion condition includes a supply amount of liquid per unit time.   The exposure method according to claim 7, wherein the liquid supply amount per unit time is determined so as not to exceed the maximum liquid supply amount.   The exposure method according to claim 6, wherein at least a part of a liquid supply position and a supply direction with respect to the optical path of the exposure light is determined based on the receding contact angle.   The exposure method according to claim 6, wherein a recovery condition for recovering the liquid forming the liquid immersion area is determined based on the receding contact angle.   The exposure method according to claim 10, wherein the recovery condition includes at least part of a liquid recovery amount per unit time from the optical path of the exposure light, a liquid recovery position with respect to the optical path, and a recovery direction. A device manufacturing method using the exposure method of any one of claims 1 to claim 11. In an exposure apparatus that exposes the substrate through liquid in an immersion area formed on the substrate while moving the substrate,
A measuring device for measuring the receding contact angle of the liquid on the surface of the substrate when the substrate is inclined ;
Based on the measurement result of the measuring device, the maximum movement speed of the substrate capable of maintaining the immersion area in a desired state is obtained, and the movement of the substrate when exposing the substrate based on the obtained maximum movement speed A control device for determining conditions, and an exposure apparatus provided. In an exposure apparatus that exposes the substrate through liquid in an immersion area formed on the substrate while moving the substrate,
A measuring device for measuring the receding contact angle of the liquid on the surface of the substrate when the substrate is inclined;
A storage device that stores in advance information corresponding to the receding contact angle;
Based on the measurement result of the measurement device and the storage information of the storage device, the maximum movement speed of the substrate that can maintain the immersion area in a desired state is obtained, and the substrate is obtained based on the obtained maximum movement speed. And a control device for determining a moving condition of the substrate when exposing the substrate . In an exposure apparatus that exposes the substrate through liquid in an immersion area formed on the substrate while moving the substrate,
An input device for inputting information on the receding contact angle of the liquid on the surface of the substrate when the substrate surface is inclined;
Based on the information of the receding contact angle that was input from the input device, and a control unit for determining a movement condition of the substrate to maintain the liquid immersion area in a desired state,
The substrate moving condition includes a maximum moving speed of the substrate, and the control device determines the maximum moving speed based on a relationship in which the maximum moving speed increases as the receding contact angle increases . The exposure apparatus according to claim 15, wherein the movement condition includes at least a part of acceleration, deceleration, movement locus, and continuous movement distance in one direction of the substrate. A storage device for storing information corresponding to the receding contact angle;
The exposure apparatus according to claim 16 , wherein the control device determines a moving condition of the substrate based on information on a receding contact angle input from the input device and information stored in the storage device.   In an exposure apparatus for supplying a liquid onto a substrate and exposing the substrate through a liquid in an immersion region formed on the substrate by the supplied liquid.
  A measuring device for measuring the receding contact angle of the liquid on the surface of the substrate when the substrate is inclined;
  Based on the measurement result of the measuring device, the maximum liquid supply amount on the substrate that can maintain the liquid immersion region in a desired state is obtained, and the liquid immersion region is formed based on the maximum liquid supply amount. An exposure apparatus comprising: a control device that determines immersion conditions. Device manufacturing method using the exposure apparatus according to any one of claims 13 to claim 18. A method for evaluating a film formed on a substrate exposed through a liquid,
Measuring the receding contact angle of the liquid on the surface of the film when the substrate is tilted;
Determining a suitability of the film for the exposure condition based on a comparison between the measured value of the receding contact angle and an allowable range of the receding contact angle determined based on the exposure condition. Evaluation method.

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