Member for Exposure Apparatus, Method of Manufacturing Member for Exposure Apparatus, and Member for Composite Exposure Apparatus

Abstract

To provide a member for an exposure device which is less likely to be thermally expanded while being lightweight, a method for manufacturing a member for an exposure device, and a member for a composite exposure device.SOLUTION: A member for an exposure device contains glassy carbon, wherein the member for the exposure device has a frame shape, and at least one surface of two surfaces positioned in a thickness direction of the member for the exposure device is a polished surface. A method for manufacturing a member for an exposure device includes: a molding step of molding a thermosetting resin material to produce a resin molding; and a sintering step of sintering the resin molding to obtain a glassy carbon body. A member for a composite exposure device includes the member for the exposure device.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a member for an exposure apparatus, a method for manufacturing a member for an exposure apparatus, and a member for a composite exposure apparatus.

Background Art

[0002] In a lithography process for patterning a semiconductor element or the like on a silicon wafer, patterning is performed using an exposure apparatus. In the exposure apparatus, a photomask, which is a substrate for exposure, is used to form a circuit formed on the photomask on the silicon wafer. At that time, if foreign matter adheres to the photomask or reticle, there is a risk of causing defects such as short circuits in the formed pattern. For this reason, for a member for an exposure apparatus, which is a member used in the exposure apparatus, a material that does not generate dust and does not desorb components that cause foreign matter is selected. Similarly, a highly pure material that has high resistance to exposure light and does not contaminate the silicon wafer itself is required. Main members for an exposure apparatus include: (a) a pellicle frame, which is generally a rectangular frame body and one end surface of which is a pellicle film installation surface; (b) a plate-shaped stage component on which a silicon wafer is installed; (c) a disk-shaped mirror component for position measurement; (d) a member for holding an object to be exposed, such as a transfer arm in which the transfer part has a U shape; and (e) other structural components. Note that the above-mentioned pellicle frame constitutes a pellicle having a function of preventing dust on a photomask or reticle by stretching a pellicle film on the pellicle film installation surface. Hereinafter, a silicon wafer may be simply referred to as a "wafer".

[0003] Conventionally, as the pellicle frame, those made of aluminum or an aluminum alloy have been widely used. In addition, other metal-made pellicle frames such as stainless steel and resin-made pellicle frames such as polyethylene have also been proposed (see, for example, Patent Documents 1 and 2). In addition, for the stage component, mirror component, and member for holding the object to be exposed such as a transfer arm, a ceramic material that is generally easy to purify to a high purity and can also handle complex surface shapes is generally used. For example, alumina and silicon carbide are widely used. In addition, composites with ceramics having negative thermal expansion characteristics have also been proposed (see, for example, Patent Document 3). Also, it is known that for the stage component, a material with a small coefficient of linear expansion is used for the purpose of improving the positional accuracy. Also, for the mirror component, it is known that a mirror surface is formed by vapor deposition of a metal, and reflection is reduced in parts other than the mirror surface. For the member for holding the object to be exposed such as a transfer arm, in order to reduce the influence on the wafer, it is known to make the contact surface that contacts the wafer tapered, etc.

[0004] In recent years, in order to improve the moving speed of the drive system member in the lithography process (exposure process) and the handleability of the member for an exposure apparatus, reduction of the mass of the member for an exposure apparatus has been demanded. For example, the density of aluminum, which is widely used as a material for a pellicle frame, is about 2.7 g / cm 3 However, in order to reduce the mass of the member for an exposure apparatus, it is effective to configure the pellicle frame with a material having a lower density than this. For example, as a pellicle frame made of a material having a lower density than aluminum, a resin pellicle frame as described above can be considered. However, generally, due to the large coefficient of linear expansion of the resin, when the operating environment temperature rises, the resin pellicle frame expands greatly thermally. Usually, in the patterning process, the exposure light source is installed so that the pellicle frame is not directly exposed, but stray light is generated by the exposure, and when this stray light hits the pellicle frame, the temperature of the pellicle frame rises. As described above, when the resin pellicle frame expands thermally, there is a risk that wrinkles, peeling, tearing, etc. may occur in the pellicle film stretched on the pellicle frame.

[0005] In addition, in members for holding objects to be exposed, such as stage parts, mirror parts, and transfer arms, alumina with low normal thermal expansion (linear expansion coefficient = 7.2×10 -6 / K, density = 3.9 g / cm 3 ), silicon carbide (linear expansion coefficient = 3.7×10 -6 / K, density = 3.2 g / cm 3 ) are used. These ceramics are materials with a smaller linear expansion coefficient and density compared to metals. However, as described above, when the temperature of the member rises due to irradiation with exposure light, the exposure accuracy may deteriorate due to thermal expansion. Therefore, in order to further improve handling performance and exposure accuracy, materials with an even smaller linear expansion coefficient and density are required. In addition, a material with a lower surface hardness compared to the wafer is expected to reduce the adverse effects on the wafer.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0007] In recent years, aiming at further improving the resolution of exposure patterns, the wavelength of exposure light during patterning has been shortened, and for example, deep ultraviolet light (DUV) and light in the region around a wavelength of 10 nm (EUV) are now being used. When these high-energy light sources are used, the temperature rise in the exposure apparatus becomes significant, and it is estimated that in some parts, it may reach several hundred degrees Celsius. In particular, when irradiating these extremely short-wavelength lights in a vacuum atmosphere, there is also concern about the desorption of impurities and the like due to gas flow from the members used in the exposure apparatus, and it is considered that the effects such as thermal expansion due to temperature rise become higher. For example, regarding the pellicle frame, it is not limited to the resin pellicle frame as described above, and even an aluminum pellicle frame may cause wrinkles, peeling, tearing, etc. in the pellicle film stretched on the pellicle frame due to expansion when heated. Also, in the case of the stage component, the mirror component, and the member for holding the object to be exposed, there is a concern about a decrease in positional accuracy due to thermal expansion. Further, for any component or member, if it comes into contact with the object to be exposed, there is a concern about the influence on the object to be exposed, and if it is a component or member facing the space where the object to be exposed is arranged, there is a concern about the influence of the detachment of impurities or the like.

[0008] Therefore, there is a demand for a member for an exposure apparatus that is lightweight, difficult to thermally expand, and can improve the moving speed of the drive system member and has excellent handling properties, and is also difficult to deform even in patterning using a high-energy light source.

[0009] In view of the above problems, an object of the present invention is to provide a member for an exposure apparatus, a method for manufacturing the member for an exposure apparatus, and a member for a composite exposure apparatus that are lightweight and difficult to thermally expand.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by making the member for an exposure apparatus contain glassy carbon, and have completed the present invention. That is, the present invention provides the following [1] to

[13] . [1] A member for an exposure apparatus containing glassy carbon. [2] The member for an exposure apparatus according to [1] above, wherein the density of the glassy carbon is 1.6 g / cm 3 or less. [3] The member for an exposure apparatus according to [1] or [2] above, wherein the Shore hardness (HS) of the glassy carbon is 100 or more. [4] The member for an exposure apparatus according to [1] or [2] above, wherein the linear expansion coefficient of the glassy carbon is 4.0×10 -6The member for an exposure apparatus according to any one of [1] to [3] above, which is at / K or lower. [5] The member for an exposure apparatus according to any one of [1] to [4] above, wherein the mass fraction of ash in the vitreous carbon is 50 ppm or less. [6] In the Raman spectrum of the vitreous carbon, in the range of 1,300 to 1,400 cm -1 The peak intensity I of the D band in the range of D And in the range of 1,550 to 1,650 cm -1 The peak intensity I of the G band in the range of G And the peak intensity ratio I of D / I G Is 1.0 to 2.5, and the full width at half maximum of the D band is 50 to 130 cm -1 The member for an exposure apparatus according to any one of [1] to [5] above. [7] The member for an exposure apparatus according to any one of [1] to [6] above, wherein at least one surface of the member for an exposure apparatus is a polished surface. [8] A method for manufacturing a member for an exposure apparatus according to any one of [1] to [7] above, A molding step of molding a thermosetting resin material to produce a resin molded body, A firing step of firing the resin molded body to obtain a vitreous carbon body, the method for manufacturing a member for an exposure apparatus including the above. [9] Further including a pre-curing step of heating the resin molded body before the firing step so that the temperature of the resin molded body becomes 150 ° C or higher to make it infusible, In the firing step, the infusible resin molded body is fired at 900 to 3,000 ° C, the method for manufacturing a member for an exposure apparatus according to [8] above.

[10] Further including at least one of a polishing step of polishing the vitreous carbon body and a grinding step of grinding the vitreous carbon body into an arbitrary shape, the method for manufacturing a member for an exposure apparatus according to [8] or [9] above.

[11] A composite member for an exposure apparatus including the member for an exposure apparatus according to any one of [1] to [7] above and a component made of a material different from the member for an exposure apparatus.

[12] The pellicle frame made of the member for an exposure apparatus according to any one of [1] to [7] above.

[13] A composite pellicle frame including the pellicle frame according to

[12] above and a component made of a material different from that of the pellicle frame.

Effect of the Invention

[0011] According to the present invention, it is possible to provide a member for an exposure apparatus, a method for manufacturing the member for an exposure apparatus, and a composite member for an exposure apparatus that are lightweight and hardly thermally expandable.

Brief Description of the Drawings

[0012]

Figure 1

Mode for Carrying Out the Invention

[0013] Hereinafter, the configuration and manufacturing method of the member for an exposure apparatus according to the embodiment of the present invention, and the composite member for an exposure apparatus will be described in order. The member for an exposure apparatus is not limited to a pellicle frame, and any member used in the exposure apparatus may be used. For example, it may be an object to be exposed holding member such as the above-described stage component, mirror component, transfer arm, or other structural components. In the following description, for easy understanding, the drawings are appropriately referred to and each surface of the pellicle frame is described using the reference numerals shown in the drawings, but the present invention is not limited to the illustrated embodiments. Also, the drawings are schematically and exaggeratedly shown for easy understanding.

[0014] 1. Member for Exposure Apparatus The member for an exposure apparatus according to the embodiment of the present invention contains glassy carbon. The members for the exposure apparatus include movable parts within the exposure apparatus, parts that come into contact with objects to be exposed such as wafers, and parts that face the space where the objects to be exposed are placed. Specific parts included in the members for the exposure apparatus include a pellicle frame, a stage part having, for example, a plate-like shape, a mirror part having, for example, a disk-like shape and used for position measurement, a member for holding an object to be exposed such as a transfer arm having a U-shaped transfer part, and other structural parts.

[0015] The glassy carbon included in the members for the exposure apparatus is obtained by molding a thermosetting resin material into a predetermined shape to produce a resin molded body, and then heat-treating (firing) this resin molded body at a high temperature. The process of producing the resin molded body by molding (molding process), and the process of firing the resin molded body to obtain a glassy carbon body (firing process) will be described later.

[0016] The density of the glassy carbon is less than 60% of the density of aluminum. Also, the linear expansion coefficient of the glassy carbon is smaller than that of resins and aluminum. For example, the linear expansion coefficient of polyethylene constituting the above-mentioned resin-made pellicle frame is 110 - 130×10 -6 / K, and the linear expansion coefficient of aluminum is about 24×10 -6 / K, while the linear expansion coefficient of the glassy carbon can be, for example, 4.0×10 -6 / K or less as will be described later. Therefore, the pellicle frame containing glassy carbon, which is one of the members for the exposure apparatus, is lighter than metal-made pellicle frames such as aluminum that have been widely used conventionally, and can be less likely to thermally expand (that is, have a smaller linear expansion coefficient) compared to resin-made pellicle frames and metal-made pellicle frames. The above-mentioned pellicle frame containing glassy carbon is lightweight and less likely to thermally expand. When a pellicle film is stretched to form a pellicle, the moving speed of the pellicle can be improved, and the handling property can be made excellent. Also, in pattern patterning using a high-energy light source, deformation of the pellicle film can be made less likely to occur. That is, when the member for an exposure apparatus containing the above glassy carbon is a movable part that can move within the exposure apparatus, or a part that contacts the object to be exposed, such as a part that supports the object to be exposed, it is possible to achieve both weight reduction and low thermal expansion. Therefore, it is possible to enhance the high-speed mobility and handling performance of the member for an exposure apparatus, and to suppress the influence on the object to be exposed and the decrease in dimensional accuracy when the temperature rises.

[0017] In addition, due to its unique cross-linked structure, glassy carbon has high tissue uniformity, has a higher hardness than ordinary graphite, and is less likely to generate dust due to particle detachment.

[0018] The glassy carbon constituting the above member for an exposure apparatus is obtained by molding a thermosetting resin material into a predetermined shape to produce a resin molded body, and then heat-treating (firing) this resin molded body at a high temperature. Since the glassy carbon has already received a high-temperature heat history through the above heat treatment, even if it is heated by exposure, the components desorbing from the glassy carbon are extremely few. Therefore, it is possible to suppress the generation of growth foreign matters (hazes) that cause obstacles to patterning.

[0019] In addition, vitreous carbon is close to an ideal black body and is prone to suppressing light reflection. Therefore, for example, there is an advantage that it is easy to inspect for foreign matter adhering to a member for an exposure apparatus. Note that it is known to blacken an aluminum-made pellicle frame by anodic oxidation coating treatment (anodizing treatment) and a dye in an acidic solution. However, in such an anodized aluminum-made pellicle frame, sulfate ions, nitrate ions, etc. contained in the acidic solution remain, and during the use of the pellicle frame, for example, when exposed to a high vacuum, the desorbed nitrate ions, etc. react with ammonia to generate foreign substances with growth, which may cause an obstacle to patterning. In addition, since the surface of the anodic oxidation coating is porous, there is also a problem that it is prone to generating dust. In order to prevent these, it has been proposed to cover aluminum or its anodic oxidation coating with a polymer by electrodeposition coating or the like, but another problem occurs that the electrodeposition coating film peels off due to friction during handling, or the film deteriorates due to exposure. As described above, the member for an exposure apparatus containing the above-mentioned vitreous carbon is less likely to generate dust, and the generation of gas is extremely small even under high vacuum or high temperature environment, and moreover, it itself is close to a black body. Therefore, even when the member for the exposure apparatus is a pellicle frame, no additional treatment such as that for an aluminum-made pellicle frame is required, and there is no need to cover it with a polymer film. Furthermore, a ceramic-made wafer holding member, for example, a transfer arm has a higher surface hardness than a wafer and has an adverse effect due to impact when contacting the wafer, but an exposed object holding member such as a transfer arm containing vitreous carbon has a lower surface hardness compared to a ceramic-made one, and can reduce the influence on the wafer. That is, when the member for an exposure apparatus containing the above-mentioned vitreous carbon is a component facing the space where the object to be exposed is arranged, it is less likely to generate dust or gas generation, and thus less likely to cause problems such as foreign matter generation.

[0020] In addition, as will be described later, the member for an exposure apparatus containing vitreous carbon can have its flatness improved by polishing. Therefore, when the member for an exposure apparatus is a pellicle frame, elastic deformation of the pellicle frame is suppressed when a pellicle film is stretched over the pellicle frame or when a photomask is adhered, and consequently, distortion of the pellicle film or photomask can be suppressed.

[0021] In addition, the pellicle frame containing the vitreous carbon is advantageous in terms of rigidity compared to a resin-made pellicle frame, and deformation or breakage of the pellicle film is less likely to occur during the production or use of the pellicle. In addition, vitreous carbon has high chemical resistance to all acids, bases, and organic solvents. Therefore, the member for an exposure apparatus containing vitreous carbon also has the advantage that corrosion or the like is less likely to occur.

[0022] Vitreous carbon may contain components (for example, ash content) inevitably included in the manufacturing process, but from the viewpoint of causing the desired physical properties to be exhibited in vitreous carbon and preventing elution of the above impurities under high temperature and high vacuum, it is preferable that the content of the above components is small. Here, the ash content means components mainly derived from impurity metals mixed into vitreous carbon in the manufacturing process of vitreous carbon. In this specification, "vitreous carbon" also includes vitreous carbon containing the above ash content. From the viewpoint of suppressing the mixing of impurities as much as possible and preventing their elution, the mass fraction of the ash content in the above vitreous carbon is preferably 50 ppm or less, more preferably 20 ppm or less, still more preferably 10 ppm or less, and most preferably 5 ppm or less. In order to make the mass fraction of the ash content in vitreous carbon within the above range, when obtaining vitreous carbon by heat-treating a thermosetting resin at a high temperature, for example, it can be achieved by appropriately selecting the type of thermosetting resin material or making engineering improvements such as reducing the mixing of metal components.

[0023] The density of the vitreous carbon constituting the member for the exposure apparatus is preferably 1.6 g / cm from the viewpoint of weight reduction. 3 More preferably, it is 1.58 g / cm or less. 3 Still more preferably, it is 1.56 g / cm or less. 3 It is as follows. There is no particular limitation on the lower limit of the density of the vitreous carbon, but from the viewpoints of ensuring the hardness of the vitreous carbon and a sufficient cross-linked structure between carbons and the ease of manufacturing, for example, it is 1.45 g / cm. 3 It is as follows. As a method for setting the density within the above numerical range, for example, appropriately setting the reaching temperature when obtaining vitreous carbon by heat-treating a thermosetting resin at a high temperature can be mentioned.

[0024] The Shore hardness (HS) of the vitreous carbon constituting the member for the exposure apparatus is preferably 100 or more from the viewpoint of facilitating the suppression of dust generation. Vitreous carbon has a higher Shore hardness compared to that of general graphite (the Shore hardness (HS) is about 50 to 80). This is due to the characteristic cross-linked structure of vitreous carbon. When the Shore hardness (HS) of vitreous carbon is 100 or more, the uniformity of the structure increases due to the development of the cross-linked structure, and dust generation due to particle detachment like graphite becomes less likely to occur. Therefore, even when a member for an exposure apparatus containing vitreous carbon comes into contact with other members, the generation of particles due to friction is small.

[0025] The Shore hardness (HS) of the vitreous carbon constituting the member for the exposure apparatus is more preferably 100 to 150, still more preferably 110 to 140, and even more preferably 115 to 135.

[0026] In this specification, the Shore hardness (HS) is a value measured with a Shore hardness tester in the D shape, and specifically, it is measured by the method described in the examples. In addition, as a method for setting the Shore hardness (HS) within the above numerical range, for example, appropriately setting the heat treatment temperature when obtaining vitreous carbon by heat-treating a thermosetting resin at a high temperature can be mentioned.

[0027] From the viewpoints of suppressing dimensional changes of the member for the exposure apparatus and reducing the influence on members other than the member for the exposure apparatus, the coefficient of linear expansion of the vitreous carbon constituting the member for the exposure apparatus preferably has a coefficient of linear expansion at 200 °C of -6 4.0×10 -6 / K or less, more preferably 3.5×10 -6 / K or less, and still more preferably 3.0×10 / K or less. By setting the coefficient of linear expansion of the vitreous carbon within the above range, for example, when the member for the exposure apparatus is a pellicle frame, it becomes easy to suppress dimensional changes of the pellicle and ensure the adhesiveness between the pellicle frame and the pellicle film. Further, for example, when the member for the exposure apparatus is a stage component, it becomes easy to ensure the accuracy during driving of the stage component and the dimensional accuracy of the entire holding portion for holding the object to be exposed. There is no particular limitation on the lower limit of the coefficient of linear expansion. From the viewpoints of ensuring the hardness of the vitreous carbon and a sufficient crosslinked structure between carbons and the ease of manufacturing, for example, it is 2.0×10 -6 / K. As a method for setting the coefficient of linear expansion within the above numerical range, for example, appropriately setting the temperature reached when heat-treating a thermosetting resin at a high temperature to obtain vitreous carbon can be mentioned.

[0028] The vitreous carbon constituting the member for the exposure apparatus preferably has a peak intensity I -1 of the D band in the range of 1,300 to 1,400 cm D in the Raman spectrum, and a peak intensity I -1 of the G band in the range of 1,550 to 1,650 cm G such that the peak intensity ratio I D / I G is 1.0 to 2.5, and the full width at half maximum of the D band is 50 to 130 cm -1 . The D band is a peak derived from defects in the graphite structure, and the G band is a peak derived from the ideal graphite structure of the carbon material. I D / I GThe fact that the value of D / I G and the half-value width of the D band are within the above ranges means that the carbon structure has many disordered and cross-linked structures and the crystal growth does not proceed as far as that of graphite. Therefore, I More preferably, I D / I G is 1.0 to 2.0, and the half-value width of the above D band is 70 to 130 cm -1 . As a method for making the above peak intensity ratio I D / I G fall within the above numerical range, for example, appropriately setting the reaching temperature when obtaining glassy carbon by heat-treating a thermosetting resin at a high temperature can be mentioned.

[0029] At least one of the surfaces of the member for the exposure apparatus is preferably a polished surface. For example, when the member for the exposure apparatus is a pellicle frame, it is preferable that at least one of the pellicle film installation surface and the mask bonding surface is a polished surface. When the member for the exposure apparatus is a member for holding an object to be exposed such as a stage component or a transfer arm, it is preferable that the surface in contact with the object to be exposed is a polished surface. When the member for the exposure apparatus is a mirror component, it is preferable that the surface including the region that becomes the mirror surface is a polished surface. The above polished surface may be a surface having a predetermined surface roughness, or may be a mirror-finished surface. In this specification, the "mirror-finished surface" means a surface that has been mirror-finished using an abrasive such as mirror-finishing abrasive grains.

[0030] The member for the exposure apparatus may be composed only of a member for the exposure apparatus made of glassy carbon, or may be a composite including the member for the exposure apparatus and a component made of a material different from that of the member for the exposure apparatus, as described later. In this specification, the above composite is referred to as a "composite member for the exposure apparatus". The composite member for the exposure apparatus will be described later.

[0031] The member for the exposure apparatus may be composed only of vitreous carbon, or other components other than vitreous carbon may be included in the member for the exposure apparatus for the purpose of enhancing the strength and other physical properties of the member for the exposure apparatus. Examples of the other components include carbon fiber, graphite, silicon, and the like. From the viewpoints of ensuring the hardness of vitreous carbon and a sufficient cross-linked structure between carbons and the ease of manufacturing, the mass fraction of the components other than vitreous carbon in the member for the exposure apparatus is preferably 50% by mass or less, more preferably 20% by mass or less, and still more preferably 5% by mass or less.

[0032] 2. Pericle Frame The pericle frame according to an embodiment of the present invention is one of the members for the exposure apparatus. The pericle frame may consist only of the pericle frame, or may be a composite including the pericle frame and a component made of a material different from the pericle frame, as will be described later. In this specification, the composite is referred to as a "composite pericle frame". The composite pericle frame will be described later. Next, an example of the pericle frame according to an embodiment of the present invention is shown in FIG. 1. As shown in the plan view of FIG. 1(a), the pericle frame 10 shown in FIG. 1 has a rectangular frame shape in plan view, and an opening 10c is provided in the central portion. Each corner portion 10d where the long straight portion 10e and the short straight portion 10f intersect is in an R shape. Although not shown in FIG. 1, the pericle frame may be provided with a counterbore portion and a through hole, which will be described later. Then, as shown in the cross-sectional view of FIG. 1(b), of the two surfaces located in the thickness direction of the pericle frame 10, one is the pericle film installation surface 10a which is the surface on which the pericle film is installed, and the other is the mask bonding surface 10b which is the surface to which the photomask is bonded. Note that an adhesive layer or an adhesive layer, which will be described later, may be provided on the pericle film installation surface 10a or the mask bonding surface 10b of the pericle frame 10, but these layers are not shown in FIG. 1(b).

[0033] A pellicle frame containing vitreous carbon is lighter than a metal pellicle frame and is less likely to thermally expand compared to a resin pellicle frame or a metal pellicle frame. Therefore, when a pellicle film is stretched to form a pellicle, the moving speed of the pellicle can be improved, and the handling property can be made excellent. Also, in patterning using a high-energy light source, deformation of the pellicle film can be made less likely to occur. Further, due to the crosslinked structure peculiar to vitreous carbon, generation of dust due to particle detachment is less likely to occur, and since it has received a high-temperature heat history during manufacturing, the components that desorb even when heated are extremely few. Furthermore, it is advantageous in terms of rigidity compared to a resin pellicle frame, and deformation or breakage of the pellicle film is less likely to occur during the production or use of the pellicle. In addition, since it has high chemical resistance, corrosion etc. are less likely to occur, and since vitreous carbon is close to an ideal black body, it is easy to suppress light reflection.

[0034] At least one of the pellicle film installation surface (reference numeral 10a in Fig. 1(b)) and the mask bonding surface (reference numeral 10b in Fig. 1(b)) of the above-mentioned pellicle frame is preferably a polished surface. More preferably, both the pellicle film installation surface and the mask bonding surface are polished surfaces. The above-mentioned polished surface may be a mirror-finished surface. By making at least one of the pellicle film installation surface and the mask bonding surface a polished surface, these surfaces can be smoothed, and the flatness can be enhanced. As a result, the flatness of the pellicle frame is increased, and it becomes easier to suppress distortion during adhesion of the pellicle film or the photomask.

[0035] From the viewpoint of suppressing elastic deformation of the frame and suppressing distortion of the pellicle film or the photomask when the pellicle film is stretched on the pellicle frame or when the photomask is adhered, the flatness of the above-mentioned pellicle frame is preferably 50 μm or less. In this specification, when the pellicle frame has a polygonal frame shape, the flatness of the pellicle frame is calculated as the difference between the highest point and the lowest point among the distances from each measurement point to the virtual plane derived by the least squares method from the measured heights, for all of the straight portions (reference numerals 10e and 10f in Fig. 1(a)) between each corner of the pellicle frame and a pair of adjacent corners (reference numeral 10d in Fig. 1(a)). Specifically, it is measured by the method described in the examples. In order to make the flatness within the above numerical range, for example, polishing the pellicle film installation surface or the mask bonding surface of the pellicle frame containing glassy carbon can be mentioned.

[0036] The shape of the pellicle frame in plan view is not limited to the rectangular frame shape shown in Fig. 1(a), and can be any shape. For example, it can be a polygonal frame shape such as a square or a hexagon.

[0037] There is no particular limitation on the size of the pellicle frame in plan view. It may be set to an appropriate size according to the size of the exposure target area, the configuration of the exposure apparatus, etc., and also considering ease of manufacturing. For a rectangular pellicle frame, for example, the outer length (refer to reference numeral L1 in Fig. 1(a)) can be 50 to 300 mm, the width (refer to reference numeral L2 in Fig. 1(b)) can be 50 to 300 mm, and the width of the frame portion (refer to reference numeral W in Fig. 1(b)) can be 1 to 50 mm.

[0038] There is also no particular limitation on the thickness of the pellicle frame (refer to reference numeral D in Fig. 1(b)). It may be set to an appropriate thickness according to the strength and the specifications of the apparatus to be introduced, etc., and also considering ease of manufacturing. The thickness of the pellicle frame can be, for example, 0.5 to 6.0 mm.

[0039] The pellicle frame according to an embodiment of the present invention has, for example, a polygonal frame shape and has corners. Generally, it has a rectangular frame shape such as shown in Fig. 1(a). The corners where the straight portions of the above-mentioned pellicle frame intersect may be in an R shape like the corner 10d shown in Fig. 1(a), or may be chamfered with a plane extending in the thickness direction (the direction indicated by the symbol D in Fig. 1(b)). Further, the above-mentioned pellicle frame may be provided with, for example, through holes or countersunk portions. The above-mentioned through holes can be used, for example, for ventilation. Further, the above-mentioned countersunk portions can be used, for example, as gripping portions or positioning portions during conveyance.

[0040] 3. Method for manufacturing a member for an exposure apparatus The member for an exposure apparatus according to an embodiment of the present invention can be manufactured by a manufacturing method including the following respective steps. · Step of molding a thermosetting resin material to produce a resin molded body (molding step) · Step of firing the above resin molded body to obtain a glassy carbon body (firing step)

[0041] The manufacturing method of the above member for an exposure apparatus preferably further includes at least one of the step of polishing the above glassy carbon body (polishing step) and the step of grinding the above glassy carbon body into an arbitrary shape (grinding step). For example, when the member for an exposure apparatus is a pellicle frame, it is preferable to process at least one of the pellicle film installation surface and the mask bonding surface in the above polishing step. When the member for an exposure apparatus is a stage component, it is preferable to process the surface on which the object to be exposed is placed in the above polishing step. When the member for an exposure apparatus is a mirror component, it is preferable to process the surface including the region to be the mirror surface in the above polishing step. When the member for an exposure apparatus is a member for holding an object to be exposed such as a transfer arm, it is preferable to process the contact surface with the object to be exposed in the above polishing step. By subjecting each of the above-described surfaces to a polishing process to form polished surfaces, the surface roughness of these surfaces can be controlled to an arbitrary level, providing high smoothness or a predetermined surface roughness. For example, when the member for an exposure apparatus is a pellicle frame, by enhancing the smoothness of the pellicle film installation surface and the mask bonding surface, it is possible to make it less likely for distortion or the like to occur in the reticle film or photomask. Also, when the member for an exposure apparatus is a member for holding an object to be exposed, such as a stage component or a transfer arm, by making the contact surface with the object to be exposed have a predetermined surface roughness, it is possible to more easily suppress the influence on the object to be exposed. Further, when the member for an exposure apparatus is a mirror component, by enhancing the smoothness of the region that becomes the mirror surface and making the other regions have a predetermined surface roughness, it is possible to reflect the exposure light with high accuracy by the mirror surface and suppress reflection in the other regions, making it easier to reflect the exposure light as intended. Also, for example, when the member for an exposure apparatus is a pellicle frame, formation of the outer shape of the pellicle frame, machining to the frame shape, formation of through holes or countersunk portions, etc. can be performed in the above grinding process. Also, when the member for an exposure apparatus is a member for holding an object to be exposed, such as a stage component, a mirror component, and a transfer arm, machining for forming the outer shapes of those components can be performed in the above grinding process.

[0042] There is no particular limitation on the order of the above polishing process and the above grinding process. For example, (i) grinding may be performed after polishing, or (ii) polishing may be performed after grinding. Also, (iii) at least a part of the polishing process and the grinding process may be performed in parallel. In the case of (i) above, polishing can be performed relatively easily in the polishing process. In the case of (ii) above, the portion to be polished in the polishing process can be reduced. In the case of (iii) above, it is easy to shorten the time required for the entire process.

[0043] In addition, there are no particular restrictions on the order of the firing process, the polishing process, and the grinding process. For example, (iv) the polishing process and the grinding process may be performed after the firing process, (v) at least a part of the polishing process may be performed before the firing process, or (vi) at least a part of the grinding process may be performed before the firing process. In the case of (iv) above, the operations and setting of manufacturing conditions in the firing process become easier. Also, in the cases of (v) and (vi) above, it becomes easier to simplify the processes performed after the firing process. In this specification, the vitreous carbon body obtained by firing the resin molded body and before being subjected to the polishing process and the grinding process may be referred to as the "original body for members of an exposure apparatus".

[0044] The method for manufacturing the member for an exposure apparatus preferably further includes an infusibilization process of heating the resin molded body to a temperature of 150°C or higher so that the resin molded body becomes infusible before the firing process. And in the firing process, it is preferable to fire the infusibilized resin molded body at 900 to 3,000°C. In this case, there are no particular restrictions on the order of the infusibilization process, the polishing process, and the grinding process.

[0045] [Molding process] In the molding process, a thermosetting resin material that serves as a carbon source for vitreous carbon is molded to produce a resin molded body. The raw material for vitreous carbon is a thermosetting resin material containing a resin component that becomes graphitizable carbon by heat treatment. Specifically, examples include phenol-formaldehyde resins, furan resins, polycarbodiimide resins, and the like. The above thermosetting resin materials generally exhibit a powdery or liquid state. Therefore, it is desirable to obtain a resin molded body by molding using a molding method suitable for each resin property, such as mold molding or cast molding.

[0046] In order to obtain a dense resin molded body suitable for a member for an exposure apparatus, it is desirable to use a liquid thermosetting resin material as the above thermosetting resin material, pour this liquid thermosetting resin material into a mold, heat it to a predetermined temperature, and perform cast molding to produce a resin molded body. The liquid thermosetting resin material may contain a resin component and a solvent. Examples of the liquid thermosetting resin material include a resol type phenol-formaldehyde resin solution, a polycarbodiimide resin solution, a furfuryl alcohol polymer, and the like. Examples of the solvent used together with the resin component include alcohols such as methanol, chlorine-based organic solvents such as perchloroethylene, toluene, N,N-dimethylformamide (DMF), water, and the like. From the viewpoint of moldability and the like, alcohols such as methanol, toluene, DMF, water, and the like are preferable.

[0047] In the molding step, it is preferable to heat at least a part of the above thermosetting resin material by bringing a breathable member into contact therewith. Furthermore, it is more preferable to arrange the thermosetting resin material in a planar shape and heat the thermosetting resin material by bringing a sheet-like breathable member into contact with at least one surface of the thermosetting resin material arranged in the planar shape. It is also possible to arrange the thermosetting resin material between a pair of sheet-like breathable members and perform heating. A breathable member having a shape surrounding the thermosetting resin material may be used to heat the inner edge of the breathable member in contact with the thermosetting resin material. A breathable member having a shape surrounding the thermosetting resin material and a sheet-like breathable member may be used in combination. In the molding step, preferably, a liquid thermosetting resin material is used as the thermosetting resin material, this liquid thermosetting resin material is poured into a mold, heated at a predetermined temperature, and cast molded to obtain a solid resin molded body. By heating a thermosetting resin material in contact with a breathable member, the thermosetting resin material is uniformly heated and degassed uniformly through the breathable member. In particular, when the thermosetting resin material is arranged in a planar shape and heated in contact with a sheet-like breathable member on at least one of its surfaces, uniform heating and degassing are performed on the surface in contact with the breathable member. By performing heating and degassing uniformly in this way, it becomes easier to obtain a homogeneous glassy carbon body, and it also becomes less likely for cracks or the like to occur in the thermosetting resin material due to the gas remaining inside.

[0048] In the molding process, from the viewpoint of preventing the generation of bubbles due to the volatilization of the solvent, it is preferable to heat while gradually raising the temperature until a predetermined reaching temperature is reached. The above-mentioned reaching temperature can be determined, for example, according to the vapor pressure and boiling point of the solvent contained in the resin solution. Also, the heating time until reaching the reaching temperature is preferably, for example, 10 to 50 hours according to the size of the molded product. Examples of the sheet-like breathable member include a sheet made of a water-repellent fiber such as a mesh filter. By cutting out the sheet-like breathable member and processing it into a frame shape, or by combining a plurality of processed sheet-like breathable members into a strip shape, a breathable member having a shape surrounding the thermosetting resin material can be obtained.

[0049] In addition, by producing a resin molded body having an arbitrary shape in the molding process, the grinding process described later may be omitted or simplified. For example, when producing a pellicle frame as a member for an exposure apparatus, by producing a resin molded body having a frame shape in the molding process, the grinding process described later may be omitted or simplified. In other words, it is also possible to manufacture a member for an exposure apparatus by producing a resin molded body having an arbitrary shape such as a frame shape in the molding process and not performing the grinding process, or by producing a resin molded body having an arbitrary shape such as a frame shape in the molding process, the amount of processing in the grinding process may be reduced.

[0050] [Carbonization process] From the viewpoint of enhancing the chemical stability of the resin molded body, preferably, before the above-mentioned firing step, an infusibilization step is provided in which the resin molded body is heated to a temperature of 150 °C or higher so that the resin molded body is infusibilized. The resin molded body obtained by molding a thermosetting resin material becomes a cured resin molded body by undergoing an infusibilization step, in which the resin component is cured. The heating in the infusibilization step varies depending on the type of resin and the like, but is preferably performed so that the reaching temperature is 170 °C or higher, more preferably 200 °C or higher. There is no particular limitation on the atmosphere during heating, and for example, heating can be performed under an air atmosphere. Examples of the apparatus used for infusibilization include a natural convection dryer, a forced convection dryer, a hot plate, and the like.

[0051] [Coating step] An application step of applying an antistatic agent may be provided to the infusibilized resin molded body before the above-mentioned firing step. By providing the application step, it becomes easier to prevent impurities from being mixed in or pores from being formed in the member for the exposure apparatus due to the adhesion of trace metal components contained in the environment. Examples of the antistatic agent include ionic surfactants and nonionic surfactants. Examples of the above-mentioned ionic surfactant include cationic surfactants, anionic surfactants, amphoteric surfactants, and the like.

[0052] [Firing step] In the firing step, a glassy carbon body (a raw body for a member for an exposure apparatus) is obtained by firing the resin molded body, preferably the resin molded body after the infusibilization treatment, at a high temperature. The firing step is preferably performed under an inert atmosphere such as nitrogen or argon, or under a vacuum of about 10 -3 ~10 -1 Torr. The firing process preferably includes a first heating process of heating at 900 to 1,100 °C and a second heating process of heating at a temperature higher than the first heating process. In the second heating process, heating is performed up to a temperature exceeding 1,100 °C and not exceeding 3,000 °C, and the crystal properties of the vitreous carbon can be controlled by adjusting the heating temperature and the holding time.

[0053] In the second heating process, heating may be performed while flowing a purification gas such as chlorine gas to purify the vitreous carbon. Examples of the purification gas include fluorine gas, chlorine gas, dichlorodifluoromethane, dichlorofluoromethane, carbon tetrachloride, and the like. In the first heating process, the firing temperature is preferably 900 to 1,100 °C, more preferably 930 to 1,050 °C, and still more preferably 950 to 1,000 °C at the reached temperature from the viewpoints of the uniformity of the obtained vitreous carbon body and prevention of cracking and fissuring. In the second heating process, the firing temperature is preferably 1,100 to 3,000 °C, more preferably 1,150 to 2,500 °C, and still more preferably 1,200 to 2,000 °C from the viewpoints of carbon structure and control of its physical properties. The apparatus for firing is not particularly limited as long as it can achieve the above firing temperature in the above atmosphere, and various apparatuses can be used. For example, an electric furnace, a lead hammer furnace, a vacuum furnace, etc. can be used.

[0054] From the viewpoints of preventing cracking and fissuring and preventing impurity mixing into the obtained vitreous carbon body, preferably, after obtaining the resin molded body in the above molding process, the firing process is performed after further passing through an infusibilization process and a coating process.

[0055] The vitreous carbon body obtained through molding and firing using the above thermosetting resin material as a raw material has a crosslinked structure characteristic of vitreous carbon. When this crosslinked structure is developed, the uniformity of the structure becomes high, and dust generation due to particle detachment like graphite is less likely to occur. As a result, it becomes easier to suppress the generation of particles. The fact that it is vitreous carbon can be confirmed by the presence or absence of the above-described D band and G band in the Raman spectrum obtained by Raman spectroscopic analysis. As a method for developing a crosslinked structure and enhancing the uniformity of the structure, the heating rate of the heat treatment in the above molding process or infusibilization process can be appropriately set, or a breathable member can be used in the above molding process to make the structure of the resin molded body uniform, or the heating rate and the reaching temperature in the above firing process can be appropriately set.

[0056] [Polishing process] In the polishing process, by performing lapping and polishing, a base body for a member of an exposure apparatus with good flatness can be obtained. Furthermore, by adjusting the particle size of the abrasive grains, it can be finished to an arbitrary surface roughness. The polishing process may be carried out in two stages, and may include a primary polishing process of processing the surface of the vitreous carbon body that becomes the pellicle film installation surface or the mask bonding surface to a predetermined thickness, and a secondary polishing process of further processing so as to be below a predetermined surface roughness.

[0057] The primary polishing process can be carried out, for example, by using SiC abrasive grains or B4C abrasive grains with a particle size of #1000 to #2000 and polishing to a depth of 0.3 to 3.0 mm with a polishing apparatus such as a lap disc. The secondary polishing process can be carried out, for example, by performing mirror finishing using alumina-based mirror finishing abrasive grains or diamond-based mirror finishing abrasive grains. In the secondary polishing process, since the abrasive grains used are for mirror finishing and are very fine, the depth of damage to the surface of the vitreous carbon body due to polishing and the thickness (depth of modification) of the modified layer formed on the surface of the vitreous carbon body due to polishing can be reduced.

[0058] By going through the above-described polishing process, for example, when the member for the exposure apparatus is a pellicle frame, the above pellicle film installation surface and mask bonding surface can be used as the polishing surface, and the flatness of the pellicle film installation surface and mask bonding surface can be improved.

[0059] [Grinding Process] In the grinding process, the glassy carbon body is ground. For example, when the member for the exposure apparatus is a pellicle frame, the glassy carbon body is ground into a frame shape, or a through hole or a countersunk portion is formed in the glassy carbon body. In the grinding process, the corner portion may be processed into an R shape, such as the corner portion 10d of the pellicle frame 10 shown in FIG. 1(a). Any tool can be used for grinding. For example, a machining center equipped with a high-hardness grinding tool can be used. In the case of a member for holding an object to be exposed, such as a transfer arm, the contact surface that contacts the wafer can be tapered.

[0060] 4. Member for Composite Exposure Apparatus The member for a composite exposure apparatus according to an embodiment of the present invention includes the member for the exposure apparatus and a component made of a material different from that of the member for the exposure apparatus. Further, the composite pellicle frame according to an embodiment of the present invention includes the pellicle frame and a component made of a material different from that of the pellicle frame. Examples of the material different from the member for the exposure apparatus and the material different from the pellicle frame, which constitute each of the above components, include aluminum, resin, and stainless steel.

[0061] There is no particular limitation on the shape of each of the above components, and any shape can be used. For example, it can have the same shape as the member for the exposure apparatus in plan view. In the case of a composite pellicle frame, for example, the shape of the component can have the same frame shape as the pellicle frame. The component is provided, for example, on at least one of the pellicle film installation surface and the mask bonding surface of the pellicle frame, via an adhesive layer or an adhesive layer, when the member for the exposure apparatus is a pellicle frame. By providing the above components, the member for the composite exposure apparatus can more easily enhance the strength and rigidity compared to the member for the exposure apparatus, and the composite pellicle frame can more easily enhance the strength and rigidity compared to the pellicle frame.

Example

[0062] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.

[0063] Regarding the physical property values of the glassy carbon body used for manufacturing the pellicle frame of the following example and the measurement and evaluation of the physical property values of the pellicle frame of the following example, the following procedures were performed.

[0064] <Density> The mass and volume of the glassy carbon body serving as the original body for the member for the exposure apparatus were measured, and the value obtained by dividing the former by the latter was calculated and taken as the density of the glassy carbon constituting the member for the exposure apparatus.

[0065] <Shore hardness (HS)> On one end face of the above glassy carbon body, measurements were made at five arbitrary different locations using a Shore hardness tester D-type manufactured by Imai Seiki Co., Ltd., and the average value was taken as the Shore hardness (HS) of the glassy carbon.

[0066] <Coefficient of linear expansion> The measurement of the coefficient of linear expansion was carried out using a thermomechanical analyzer TMA8310 (Rigaku). As the reference sample, SiO2 with a diameter of φ5×10 mm was used. The measurement sample was prepared by grinding the original body for the member for the exposure apparatus into a φ5×10 mm size. The measurement conditions were heating at 10°C / min up to 200°C under a nitrogen flow. The coefficient of linear expansion was calculated from the change in the height of the test piece.

[0067] <Ash content> The original body for the member for the exposure apparatus was crushed into a powder so that it could be easily ashed, then placed in a platinum crucible, and the weight of the sample before treatment was measured. It was ashed at 800°C in oxygen in a muffle furnace. After confirming that no carbon content remained, the weight of the residue was measured as the ash content, and the amount of ash contained in the original body for the member for the exposure apparatus was calculated.

[0068] <Raman peak intensity ratio> Using a microscopic laser Raman spectrometer (Lab RAM manufactured by HORIBA Scientific) with a 532 nm Nd:YVO4 laser, Raman spectroscopic measurements were performed on the main surface of each sample, and in the obtained spectroscopic spectrum, the peak intensity I of the D band in the range of 1,300 to 1,400 cm -1 of the range, and the peak intensity I of the G band in the range of 1,550 to 1,650 cm D were used to calculate the peak intensity ratio I -1 / I G . D / I G was calculated.

[0069] <Exposure acceleration test> An exposure acceleration test was carried out on the original body for exposure apparatus members using an ArF excimer laser. The test was carried out under the conditions of a 193 nm ArF laser, an output of 3 mJ / cm 3 , and a total exposure amount of 1 kJ. The surface of the original body for exposure apparatus members before and after the test was observed with an optical microscope to examine the presence or absence of surface changes before and after exposure.

[0070] <Ion elution test> The original body for exposure apparatus members was immersed in deionized water and left at 90 °C for 2 hours. Then, using ion chromatography, the desorbed ions eluted in the above deionized water were quantified.

[0071] <Flatness of the original body for exposure apparatus members> The flatness of the original body for exposure apparatus members was measured by the following procedure. The height of the straight line part between each corner part of the original body for exposure apparatus members and the adjacent pair of corner parts was measured at a pitch of 5 mm, a least-squares plane (virtual plane) was calculated, and among the distances of each measurement point, the value calculated by subtracting the point farthest from the least-squares plane on the lower side (lowest point) from the point farthest from the least-squares plane on the upper side (highest point) was taken as the flatness of the original body for exposure apparatus members.

[0072] [Production Example 1] As the thermosetting resin material, a methanol solution of a resol-type phenol-formaldehyde resin was used. Two fluororesin nonwoven fabrics, which are sheet-like breathable members, were prepared, and an aluminum mold with a polytetrafluoroethylene (PTFE) coat for forming the side surface was placed between these upper and lower nonwoven fabrics. The thermosetting resin material was placed in the mold and cast-molded to produce a square flat resin molded body with a length of 250 mm × width of 250 mm × thickness of 5 mm. The above cast molding was performed by gradually raising the temperature from room temperature to 90°C over 20 hours in an oven. Then, after removing the upper and lower nonwoven fabrics and the mold, the resin molded body was cured and further insolubilized to obtain a cured resin molded body by raising the temperature and heating from 90°C to 200°C over 30 hours in an oven. Using a vacuum furnace, the above cured resin molded body was heat-treated in a vacuum atmosphere of 0.01 Torr. As a first heating step, the temperature was gradually raised from room temperature to 1,000°C for heat treatment. Further, as a second heating step, the temperature was gradually raised from 1,000°C to 1,750°C for heat treatment to obtain a rectangular plate-shaped glassy carbon body made of glassy carbon with a length of about 200 mm × width of about 200 mm × thickness of about 4 mm.

[0073] Table 1 shows the measurement results of the above physical properties of the above glassy carbon body. For reference, Table 1 also shows the density, Shore hardness (HS), and linear expansion coefficient of aluminum (A5052) as Reference Example 1 and polyethylene (HDPE) as Reference Example 2. Note that the Shore hardness of Reference Example 1 is a value measured by the same method as in Example 1. The density and linear expansion coefficient of Reference Examples 1 to 3 are described as general values described in dictionaries and various documents.

[0074]

Table 1

[0075] As shown in Table 1, the glassy carbon body of Production Example 1 produced through the above respective steps has a Raman peak intensity ratio I D / I GThe value is 1.86, which is 1 or more, and the Raman D-band full width at half maximum is 75.5 cm -1 and is in the range of 50 to 130 cm -1 From this, it can be seen that disorder is formed in the crystal structure of carbon, and the uniformity of the structure is high due to the development of the crosslinked structure. And as is clear from the comparison with aluminum, the glassy carbon body of Production Example 1 has a high Shore hardness and a low linear expansion coefficient, and also has a low linear expansion coefficient compared with polyethylene and alumina. It can be seen that it is composed of glassy carbon suitable for the member for exposure apparatus. Also, as is clear from the comparison between Production Example 1 and Reference Example 1, it can be understood that the glassy carbon body of Production Example 1 has a lower density than aluminum and can greatly reduce the weight of the member for exposure apparatus. Also, as is clear from the comparison between Production Example 1 and Reference Example 3, since the glassy carbon body of Production Example 1 has a smaller linear expansion coefficient and a lower density than the ceramic, when used as a member for holding an object to be exposed such as a stage part, a mirror part, or a transfer arm, it can be understood that the positional accuracy can be improved.

[0076] Also, as shown in Table 1, as a result of the exposure acceleration test, no change was observed on the surface of the original body for the member for exposure apparatus of Production Example 1 even after exposure, and it can be seen that the original body for the member for exposure apparatus containing glassy carbon has high light resistance. Furthermore, as shown in Table 1, as a result of the ion elution test, SO4 2- is 5 ppb or less, and NH4 + is 15 ppb or less, and it can be seen that the elution of components from the original body for the member for exposure apparatus of Production Example 1 is extremely small.

[0077] [Example 1] Using the glassy carbon body produced in Production Example 1, the pellicle frame of Example 1 was produced by performing polishing and grinding processes in the following procedure. The installation surface of the pellicle film and the mask bonding surface of the glassy carbon body were polished with #1000 SiC abrasive grains as the primary processing using a lapping machine to a thickness of 0.5 mm or more. As the secondary processing, the surfaces of the pellicle film installation surface and the mask bonding surface were mirror-finished with alumina-based mirror-finishing abrasive grains and finished to a thickness of 3 mm. The glassy carbon body with mirror-finished upper and lower surfaces thus obtained was machined using a machining center equipped with a diamond tool to finish the outer shape (L1 and L2 in Fig. 1(b)) to 150 mm × 110 mm and the width of the frame portion (W in Fig. 1(b)) to 2 mm. For each straight portion of the frame portion, when viewed in plan, at positions sandwiching the center between one end and the other end from the center of the straight portion, from the central portion in the thickness direction (direction D in Fig. 1(b)) of the side surface on the outer shape side toward the width direction (direction W in Fig. 1(b)) of each frame portion, a countersink hole with a diameter of 1.5 mm and a depth of 1 mm was provided. Thus, a pellicle frame was produced.

[0078] The pellicle frame containing the glassy carbon of Example 1 obtained through the above polishing and grinding processes was able to achieve a flatness of less than 20 μm. Also, considering the density of aluminum (2.68 g / cm 3 ) and the linear expansion coefficient (about 24 × 10 -6 / K), compared with an aluminum pellicle frame having a similar shape, the mass can be reduced by about 40% or more, and the linear expansion when heated from room temperature to 200 °C can be suppressed to about 10% of the linear expansion of the above aluminum pellicle frame. Also, as a resin pellicle frame, compared with a polyethylene pellicle frame having a similar shape (linear expansion coefficient 110 - 130 × 10 -6 / K), it can be suppressed to about 2%.

Explanation of Signs

[0079] 10: Pellicle frame 10a: Pellicle film installation surface 10b: Mask bonding surface 10c: Opening

Claims

1. A member for an exposure apparatus comprising glassy carbon, the exposure apparatus member is in a frame shape having a straight portion, A member for an exposure apparatus, wherein at least one of two surfaces positioned in a thickness direction of the member for an exposure apparatus is a polished surface.

2. A component for an exposure apparatus as described in claim 1, wherein the component for an exposure apparatus is frame-shaped having a plurality of straight portions.

3. The density of the glassy carbon is 1.6 g / cm ３ 3. The member for an exposure apparatus according to claim 1 or 2, wherein:

4. 4. The member for an exposure apparatus according to claim 1, wherein the vitreous carbon has a Shore hardness (HS) of 100 or more.

5. The linear expansion coefficient of the glassy carbon is 4.0×10 －６ The member for an exposure apparatus according to any one of claims 1 to 4, wherein the surface roughness is 1 / K or less.

6. 6. The member for an exposure apparatus according to claim 1, wherein the mass fraction of ash in the glassy carbon is 50 ppm or less.

7. The glassy carbon has a Raman spectrum of 1,300 to 1,400 cm －１ The D band peak intensity I in the range Ｄ and 1,550 to 1,650 cm －１ The G-band peak intensity I in the range Ｇ Peak intensity ratio I Ｄ / I Ｇ is 1.0 to 2.5, and the half width of the D band is 50 to 130 cm －１ The member for an exposure apparatus according to any one of claims 1 to 6,

8. 8. A member for an exposure apparatus according to claim 1, wherein both of two surfaces positioned in a thickness direction of the member for an exposure apparatus are polished surfaces.

9. A method for producing an exposure apparatus member according to any one of claims 1 to 8, comprising the steps of: A molding step of molding a thermosetting resin material to produce a resin molded body; and a firing step of firing the resin molded body to obtain a glass-like carbon body.

10. The method further includes a step of heating the resin molded body to a temperature of 150° C. or higher to make the resin molded body infusible prior to the firing step, 10. The method for manufacturing an exposure apparatus member according to claim 9, wherein the infusible resin molded body is baked at 900 to 3,000° C. in the baking step.

11. The method for manufacturing a member for an exposure apparatus according to claim 9 or 10, further comprising at least one of a polishing process step of polishing the glass-like carbon body and a grinding process step of grinding the glass-like carbon body into an arbitrary shape.

12. 9. A composite member for an exposure apparatus, comprising: the member for an exposure apparatus according to claim 1; and a part made of a material different from that of the member for an exposure apparatus.

13. A pellicle frame comprising the member for an exposure apparatus according to any one of claims 1 to 8.

14. A composite pellicle frame comprising the pellicle frame according to claim 13 and a component made of a material different from that of the pellicle frame.

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