JP5940283B2 - Pellicle - Google Patents

Description

  The present invention relates to a pellicle frame used for a pellicle used as a dust prevention when manufacturing a semiconductor device, a printed circuit board, a liquid crystal display, or the like, a manufacturing method thereof, and a pellicle.

  In the manufacture of semiconductors such as LSI and VLSI and the manufacture of liquid crystal displays and the like, a pattern is produced by irradiating a semiconductor wafer or liquid crystal master plate with light. A photomask or reticle (hereinafter referred to as a photomask for short) used at this time If the dust adheres to the (description), this dust will absorb light or bend the light, so the transferred pattern will be deformed, the edges will be sticky, and the ground will be black. There was a problem that dimensions, quality, appearance, etc. were impaired.

  For this reason, these operations are usually performed in a clean room, but it is still difficult to keep the photomask clean. Therefore, exposure is performed after a pellicle is attached to the surface of the photomask to prevent dust. In this case, the foreign matter does not adhere directly to the surface of the photomask but adheres to the pellicle. Therefore, if the focus is set on the pattern of the photomask during lithography, the foreign matter on the pellicle becomes irrelevant to the transfer.

  The pellicle is generally a transparent pellicle film made of nitrocellulose, cellulose acetate, fluororesin, or the like that transmits light well, and is attached or adhered to the upper end surface of a pellicle frame made of aluminum, stainless steel, polyethylene, or the like. is there. In addition, the lower end surface of the pellicle frame has a pressure-sensitive adhesive layer made of polybutene resin, polyvinyl acetate resin, acrylic resin, silicone resin, etc. for mounting on a photomask, and a release layer (separator) for the purpose of protecting the pressure-sensitive adhesive layer. Is provided.

  In order to support a thin pellicle film with a pellicle frame without slack, the pellicle frame must be adhered to the pellicle frame under an appropriate amount of tension. However, in a rectangular pellicle made of a conventional material, the pellicle frame after the pellicle film is attached is bent somewhat inward due to the tension of the pellicle film, and the pellicle film is easily loosened. For this phenomenon, for example, large pellicles used in the manufacture of printed circuit boards and liquid crystal displays, such as those with large pellicle frame lengths and small ones for semiconductor manufacturing, use low rigidity frames due to material and dimensional constraints. It appears prominently in the pellicle.

  On the other hand, there is a demand for a photomask to secure as wide an exposure area as possible for cost reduction. For this reason, there is a problem that if the size of the pellicle frame is reduced in order to make the deflection to the inside as small as possible, the available exposure area decreases. Furthermore, there is a demand for a cost reduction effect by widening the inner exposure area with a narrower pellicle frame while suppressing the amount of bending as much as possible.

  As a means for solving such bending of the pellicle frame, for example, in Patent Document 1, at least a pair of sides of the frame body, an arc-shaped portion having a central convex portion on an outer side, an arc-shaped portion having an outer concave shape on both sides thereof, and an outer side thereof Discloses a pellicle frame having a linear portion. According to this method, the amount of deflection can be controlled to a certain value or less by performing an appropriate design.

  However, it is possible to maintain the linear shape of the frame by adjusting the tension and balance at any frame width, but when trying to make the frame width as narrow as possible, the rigidity is ensured even if the linear shape is obtained. As a result, there is a problem that handling cannot be performed, or the pellicle film is wrinkled or slackened with a slight external force. The effect cannot be obtained.

  Since the frame height is determined from the optical design of the exposure machine, as means for essentially increasing the rigidity of the pellicle frame while narrowing the frame width, there is means for using a material having a high elastic coefficient. As such means, for example, Patent Document 2 describes a pellicle frame in which an aluminum alloy frame body is embedded with iron or titanium containing stainless steel having a larger elastic coefficient than the frame body. However, iron-based alloys such as steel and stainless steel are feared to be extremely heavy, and titanium alloys have a problem that workability (machinability) is very poor, and they are almost used in practice. Absent. As an alternative to this, when using carbon fiber composite materials that are currently used in the aircraft field and are known as high-rigidity materials, the rigidity can be greatly improved over the various metal materials described above. It is expected that there is no problem of workability. However, since carbon fibers are used, there has been a serious concern that foreign matters such as fiber dust resulting from the carbon fibers are mixed.

  Further, when carbon fiber composite materials are used, there is a problem that both the raw material cost and the processing cost are remarkably increased as compared with generally used aluminum alloys and the like. Due to these problems, carbon fiber composite materials have not been used in pellicle frames.

JP 2006-56544 A JP 2006-284927 A

  The present invention has been made in order to solve the above-mentioned problems, and can be reduced in weight by using a composite material in which carbon fiber is impregnated with a resin, and the bending due to the tension of the pellicle film and the bending in handling are small and high. A rigid pellicle frame with reduced raw material costs and production costs, a manufacturing method thereof, and a pellicle with a pellicle film attached to the pellicle frame, which has a large exposure area and reduced raw material costs and production costs. The purpose is to provide.

Was made in order to achieve the above object, the pellicle frame according to claim 1 of the appended claims, the pellicle film is not covered nervous, corner becomes both arcuately inner wall and an outer wall and a polygonal-shaped frame has a composite member containing an epoxy resin while being oriented carbon fibers in a longitudinal direction of each side constituting the frame body, curing of the resin laminated with orbiting in the polygonal shape The surface of the frame body that is integrated and polished and / or cut and smoothed is coated with a resin film containing carbon black and selected from acrylic resins, silicone resins, and fluororesins . It is characterized by that.

  The pellicle frame according to claim 2 is the pellicle frame according to claim 1, wherein the composite member is laminated by the lap of a single member connected in series, or each of the multiple members each circulates at least once. It is characterized by being laminated by the above-mentioned circulation.

  A pellicle frame according to a third aspect is the one according to the first or second aspect, wherein the composite member is a sheet-like material in which a plurality of oriented carbon fibers are impregnated with the resin. It is characterized by being.

The pellicle frame according to claim 4 is the one according to any one of claims 1 to 3, wherein the long fibers of the carbon fibers on the inner wall and the outer wall of each side are both oriented in one direction. and said that you are.

A pellicle frame according to a fifth aspect of the present invention is the pellicle frame according to any one of the first to fourth aspects, wherein the corner portion has the arc shape with a minimum bending radius of 3 mm .

According to a method for manufacturing a pellicle frame according to claim 6, a core material smaller than a desired inner dimension of a polygonal frame body in which both the inner wall side and the outer wall side of the corner portion are arc-shaped , Wrapping a sheet-like composite member impregnated with an epoxy resin into carbon fibers oriented in the width direction at a width wider than the height and at least a width over the circumference of the frame body, from a desired outer dimension of the frame body A base material forming step in which the epoxy resin is heated and cured to form a base material, and the base material is cut to a desired inner size, outer size, and height of the frame body, and then polished and / or cut. And a frame body forming step of forming a film of a resin selected from an acrylic resin, a silicone resin, and a fluororesin, containing carbon black on the surface of the frame body. It is characterized by that.

  The method for manufacturing a pellicle frame according to claim 7 is the method according to claim 6, wherein a core material smaller than a desired inner dimension of the frame body is at least twice as high as a desired height of the frame body. A sheet-like composite member obtained by impregnating a carbon fiber oriented in the transverse width direction with a longitudinal width and at least a width over one circumference of the frame body, wound, and laminated to be larger than the outer dimension of the frame body The base material forming step is characterized in that the base material is formed by dividing into a plurality of parts in a direction parallel to the side of the frame body by cutting after heat curing.

A pellicle according to an eighth aspect is characterized in that a pellicle film is tension-covered and attached to the pellicle frame according to any one of the first to fifth aspects.

  The pellicle frame of the present invention is formed of a composite member obtained by impregnating carbon fibers with a resin, and is lightweight and has high rigidity. In this pellicle frame, the carbon fiber of the composite member constituting the pellicle frame is oriented in the longitudinal direction of each side, so that the mechanical strength of the fiber can be maximized, and in the bending and handling due to the tension of the pellicle film It can exhibit extremely high rigidity against bending. In addition to the orientation direction of the carbon fiber, there is no or little fiber seam, so it is possible to prevent the strength from being lowered by the seam, and it is possible to obtain higher rigidity, and it is difficult to crack and propagate, and it has high reliability. Sex can be obtained. Therefore, each side can be formed narrower than a conventionally used pellicle frame, and a large inner exposure area can be secured.

  Further, the surface of the pellicle frame is smoothed by a process such as polishing or cutting so that the dimensional accuracy is high. Further, since the surface is coated with a resin, the cut surface of the carbon fiber due to the processing of the pellicle frame is not exposed, so that the carbon fiber is prevented from falling off and dusting, and deterioration due to ultraviolet rays can be prevented.

  According to the method for manufacturing a pellicle frame of the present invention, a pellicle frame having a desired size is formed from a slightly larger base material by machining, so that defects on the surface can be removed, and a normal metal with high dimensional accuracy can be obtained. A product comparable to the processed product can be obtained.

  According to the method for manufacturing a pellicle frame of the present invention, since the pellicle frame is formed from a base material having a size capable of forming a plurality of pellicle frames at a time, the material can be minimized, and the base material can be formed. The number of processing steps for the material is significantly reduced, and the raw material cost and the production cost can be greatly reduced as compared with the processing for each product.

  The pellicle of the present invention can secure a large exposure area by a high-rigidity pellicle frame, and contributes to cost reduction of manufacturing a semiconductor, a liquid crystal display, and the like. Moreover, there is no fear of dust generation during use, and extremely high reliability can be shown.

It is a perspective view of a pellicle frame to which the present invention is applied. It is the sectional view on the AA line of the pellicle frame to which the present invention is applied, the sectional view on the BB line, and its partially expanded sectional view. It is a plane schematic diagram of a pellicle frame to which the present invention is applied. It is a plane schematic diagram of another pellicle frame to which the present invention is applied. It is a figure showing the relationship which cuts a pellicle frame from the base material of the pellicle frame to which this invention is applied. It is a schematic diagram which shows the manufacturing method of the pellicle frame to which this invention is applied. It is a schematic diagram which shows another manufacturing method of the pellicle frame to which this invention is applied. 1 is a perspective view of a pellicle to which the present invention is applied.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

  The pellicle frame of the present invention will be described in detail with reference to FIG.

  The pellicle frame 1 is a quadrangular frame having long sides and short sides, and four corners thereof are arcuate on both the inner wall side and the outer wall side. A vent hole 2 for ventilating the inside and outside of the pellicle frame 1 and a recess hole 3 for use in handling are provided at predetermined locations on the wall surfaces of the long side and the short side, respectively. ing. In addition, a mask adhesive layer step 4 for forming the mask adhesive layer is provided on the lower end surface where the mask adhesive layer is provided. The step 4 for the mask adhesive layer does not necessarily have to be a step, and a chamfer or other steps, a dent, a groove, or the like may be further provided on the ridge as necessary.

  The pellicle frame 1 is composed of a composite member (hereinafter referred to as a prepreg) which is a carbon fiber sheet impregnated with a resin, and the prepreg 5 is laminated in a quadrangular shape to cure the resin in the prepreg 5. It is formed by integrating. This sheet-like prepreg 5 includes a cross-sectional view taken along line AA in FIG. 2A and a cross-sectional view taken along line BB in FIG. As shown in FIG. 2B, which is a partially enlarged cross-sectional view of the prepreg 5 in the cross-sectional view, each side has a prepreg 5a, 5b, 5c,... Yes. The entire surface of the pellicle frame 1 formed by laminating the prepreg 5 is covered with a resin coating 9.

  Each prepreg 5 is a sheet-like composite member in which a large number of long carbon fibers 15 are oriented in only one direction and impregnated with resin. Are arranged in a longitudinal direction with respect to each side of the frame, that is, in a parallel direction, so that the inner wall and the outer wall of each of the four sides are in a certain direction. Examples of the resin impregnated in the prepreg 5 include an epoxy resin. Especially, since the heating temperature can be increased when forming the resin coating 9 on the surface of the pellicle frame 1 and it is effective in reducing the amount of gas generated, it is preferable to select one having high heat resistance. The prepreg 5 is assumed to have a continuous length that extends at least around the pellicle frame 1. Among them, a sheet-like and long prepreg 5 that can form the pellicle frame 1 while rotating around by a single prepreg 5 that is a single member connected in series from the start to the end of winding is preferable.

  As shown in FIG. 3, the pellicle frame 1 is a continuous sheet-like prepreg 5 that is continuously wound so that the carbon fibers 15 of the prepreg 5 are parallel to the sides of the pellicle frame 1. Preferably, the structure is 3, a schematic plan view of the pellicle frame 1 formed by a preferable winding method of the prepreg 5 is shown in FIG. 3A, and the winding method is shown in FIG. 3B. In FIG. 3A, there are steps at the start of winding 6 and the end of winding 7, but since the prepreg 5 is substantially an extremely thin sheet, the steps can be ignored.

  By forming seamlessly from the winding start 6 to the winding end 7 with a single sheet-like prepreg 5, it is possible to prevent a decrease in strength due to the seam of the prepreg 5, extremely high reliability, and continuously Since work can be performed, workability is improved and production can be performed at low cost. However, since the length of the prepreg 5 is not infinite, whether the pellicle frame 1 is finished without a seam depends on the size and the stack thickness of the pellicle frame 1 to be manufactured, but there may be several seams in the middle. For example, the prepreg 5 having a length that can be circulated a plurality of times is circulated and laminated, and the winding start 6 of the prepreg 5 having a length that can be circulated a plurality of times is connected to the winding end 7 without gaps, and the wrapping is performed. The pellicle frame 1 may be formed by laminating the layers, or the pellicle frame 1 may be formed by laminating a prepreg 5 having a length that can circulate once and laminating a plurality of members.

  In the case of manufacturing using a prepreg 5 having a length that can make one round, for example, as shown in FIG. 4, prepregs 5 a, 5 b, 5 c,. Each of the winding start 6a, 6b, 6c,... And the winding end 7a, 7b, 7c,... Is joined to form joints 8a, 8b, 8c,. A pellicle frame 1 is formed. 4, a schematic plan view of the pellicle frame 1 formed by joining and laminating the prepregs 5 for one round is shown in FIG. 4A, and how to wind the pellicle frame 1 is shown in FIG. 4B.

  It is preferable that the joints 8a, 8b, 8c,... That are the joints of the prepreg 5 do not hit the corners of the pellicle frame 1. Further, it is preferable that the layers 8a, 8b, 8c,... Are stacked in consideration of not overlapping each other. As a result, the influence of the joint portions 8a, 8b, 8c,... Can be made extremely small to an extent that can be ignored, and the strength reduction caused by the joint portions 8a, 8b, 8c,.

  Thus, the prepreg end surfaces of the upper and lower wall surfaces of the pellicle frame 1 on which the prepreg 5 is wound and laminated, and the surface of the pellicle frame 1 in which necessary holes are cut are exposed to the exposed carbon fibers and carbon fibers. In order to prevent deterioration due to ultraviolet rays used for exposure of a resin such as epoxy impregnated in the sheet, it is preferable that the sheet is covered with a resin film 9. Since the entire surface of the pellicle frame 1 is completely covered with the resin coating 9, dust generation due to the carbon fibers can be prevented.

  The resin coating 9 is preferably such that its material is not easily deteriorated by the ultraviolet rays used for exposure. As the color tone of the resin coating 9, since the prepreg 5 as a base is black, it is possible to use a dark color other than black (for example, dark blue) or transparent, but if it is black, the scattered light is further reduced. Is particularly preferable. The resin film itself may have a color, and a pigment, carbon black, or the like may be mixed into the resin film. The resin film 9 is preferably an acrylic resin, more preferably a silicone resin, and still more preferably a fluororesin. These resins have high resistance to ultraviolet rays and easily form a film having high peel strength. In the case of a fluororesin, the resistance to ultraviolet rays is particularly excellent, but since the ultraviolet ray transmittance is also high, it is preferable to combine pigments and the like that have low ultraviolet ray permeability. At the same time, since the insulating property is high and it is easy to be charged, it is preferable to select a highly conductive material.

  The pellicle frame 1 is a polygonal frame, and the shape thereof is not particularly limited. As a specific example, a quadrangle with rounded corners is illustrated, but a rectangular shape in which all four corners are right angles Other shapes similar to this, for example, a rectangle, a square, an octagon, and the like may be used.

  The pellicle frame 1 of the present invention is highly effective for a large pellicle having a side length exceeding 500 mm, which is used in liquid crystal manufacturing applications. However, the size of the pellicle that is the target of the pellicle frame 1 is not limited. The pellicle frame 1 of the present invention can be applied to all pellicles in which the rigidity of the pellicle frame has not been sufficiently ensured with respect to the size (side length) and the tension of the pellicle film.

  As a pellicle frame 1 that is practical for various sizes and has high dimensional accuracy, a prepreg 5 is laminated and heat-cured so that the inner dimension is smaller, the outer dimension is larger, and the height is higher than the desired pellicle frame 1. The base material of the pellicle frame 1 is preferably machined to a desired dimension by machine cutting. FIG. 5 is a view showing the relationship of cutting the pellicle frame 1 from the base material 10 that is slightly larger than the desired pellicle frame 1 on which the prepreg 5 is laminated. Of the base material 10, a desired pellicle frame 1 is indicated by a two-dot broken line.

  The inner and outer dimensions of the base material 10 may be determined in consideration of the cutting allowance, but should be increased by about 0.2 to 3 mm, more preferably 0.5 to 1 mm on one side with respect to the pellicle frame 1 to be manufactured. Is preferred. Even if the thickness of the prepreg 5 is thick, it is around 0.2 mm. Therefore, it is necessary to circulate nearly 5 turns to make a cutting allowance of 1 mm. It is clear that the smaller the cutting allowance, the more advantageous in terms of cost. It is. However, distortion may occur at the time of heat curing, and the longer the side length, the more error occurs in the machining. Therefore, the cutting allowance as described above is necessary.

  By machine cutting from the base material 10 to the desired pellicle frame 1, the stacking error and distortion at the time of heat curing are almost corrected by cutting. Therefore, the dimensional accuracy after processing is similar to that of a general metal pellicle frame. The equivalent is obtained. Further, since the amount of the prepreg 5 used is only slightly larger than the shape of the pellicle frame 1, the amount of waste is extremely small, and the production cost can be greatly reduced as compared with the method of cutting out from a single plate. In addition, even when each side is made with a bar-shaped member, and the shape of the pellicle frame is produced by splicing this, the amount of prepreg 5 can be reduced, but man-hours for splicing each bar-shaped member are required. Furthermore, there is a concern about the strength of the seam. For this reason, the method of the present invention is superior in terms of both production cost and strength.

  Further, in this machine cutting process, it is difficult to precisely match the direction of the carbon fibers 15 included in the prepreg 5 and the direction of the side formed thereby when cutting out from the base material 10. The carbon fiber 15 of the laminated prepreg 5 and the side of the pellicle frame 1 may not be strictly parallel. In addition, the carbon fiber 15 that has been continuous at the stage of the base material 10 may be cut by machine cutting when the carbon fiber 15 is close to the surface. However, in any case, since there is little practical influence and the intended effect can be obtained, it is included in the scope of the technical idea of the present invention.

  An embodiment of such a method for manufacturing the pellicle frame 1 is shown in FIG. 6 and will be described in detail.

  As shown in FIG. 6A, the cutting allowance is taken into consideration that the cutting margin is longer and shorter than the inner dimension of the desired pellicle frame 1 that is a rectangular frame and higher than the desired pellicle frame 1 height. The core material 12 designed as described above is prepared, and the long prepreg 5 cut in advance with a predetermined width is prepared so that the orientation of the carbon fiber 5 is in the longitudinal direction of the side of the frame to be formed. Wrap around without slack. The width of the prepreg 5 is at least a horizontal width over one circumference of the frame body to be formed and a vertical width wider than the height of the frame body to be formed. At this time, it is preferable that the carbon fiber 15 of the prepreg 5 and the side to be formed are parallel. In FIG. 6A, the arrow P indicates the orientation direction of the carbon fiber 15. Further, it is preferable to provide the core material 12 with a step 13 corresponding to the thickness of the prepreg 5 in order to finish the winding start 6 of the prepreg 5 cleanly. Therefore, the radius is preferably at least 3 mm or more. Furthermore, the corners of the core material 12 are preferably formed with a radius close to the shape of the corners of the pellicle frame 1 to be formed.

  The base material 10 of the pellicle frame shown in FIG. 6B is obtained by winding and laminating until the outer dimension of the pellicle frame 1 becomes larger by the cutting allowance. At this time, when a seam enters the prepreg 5 during the lamination, it is preferable to adjust so that the seam does not hit the corner and to join the next prepreg 5 without a gap. Moreover, it is preferable that the core material 12 has a mechanism that spreads outward by a force such as a spring so that tension can be applied to the outside after the prepreg 5 is laminated and during heat curing (not shown).

  The base material 10 is housed in a polyethylene bag (not shown) together with the core material 12, vacuumed to remove the air contained therein, and heated while being pressurized in an autoclave. The impregnated resin is cured. When the core material 12 is removed from the autoclave after cooling, the base material 10 that is slightly larger than the desired pellicle frame 1 as shown in FIG. 6C is obtained. The base material 10 is machined by a machining center or the like, polished, cut and smoothed to finish each surface to a predetermined size, and further a jig hole which is a vent hole 2 or a recessed hole 3 is processed. Thus, as shown in FIG. 6D, a pellicle frame 1 that is practical and has high dimensional accuracy can be manufactured.

  In the pellicle frame 1 of the present invention, when the vent hole 2 or the recessed hole 3 is processed, the hole processing is performed perpendicular to the laminated surface of the prepreg 5, so that there is little concern about the prepreg 5 being peeled or cracked during the hole processing. Has the advantage.

  Further, after the cutting process, the obtained pellicle frame 1 is washed, and if necessary, the surface thereof is coated with a resin coating 9 so that the carbon fibers broken by the cutting process are not exposed on the surface. By covering the surface of the pellicle frame 1 with the resin coating 9, the carbon fiber and the resin fall off when the pellicle is used, which occurs when the broken carbon fiber is exposed or a completely clean surface is not obtained by washing. This is more preferable because there is no risk of dust generation. In addition, in the resin such as epoxy constituting the prepreg 5, it is possible to prevent deterioration due to ultraviolet rays used for exposure and a decrease in strength due thereto.

  Formation of the resin film 9 on the surface of the pellicle frame 1 is not particularly limited, and the manufactured pellicle frame 1 is sufficiently washed and dried, and the resin for forming the resin film 9 is dissolved in an appropriate concentration. A known coating technique such as spraying, dipping, or electrodeposition coating can be used in a state in which a pigment, carbon black, or the like dissolved in and dissolved in the solvent is dispersed in a solvent. These are best selected according to the type of resin used, and after the coating is formed, the entire pellicle frame is heat-treated to completely remove the solvent and remove low molecular weight contained in the coating. It is preferred to reduce the components. The heating temperature is preferably as high as possible, but is preferably determined comprehensively from the heat-resistant temperature of the prepreg 5, the heat-resistant temperature of the coating resin 9, the boiling point of the solvent used when coating the coating resin 9, and the like.

  Moreover, as another manufacturing method, the method of processing from the pipe-shaped base material 10 as shown in FIG. 7 is mentioned. As shown in FIG. 7A, a core having a long side and a short side that are smaller than the inner dimension of the desired pellicle frame 1 that is a rectangular frame and at least twice as high as the height of the desired pellicle frame 1 The material 12 is prepared, and the long prepreg 5 cut in advance with a predetermined width is wound without slack so that the carbon fiber direction is the longitudinal direction of the side of the frame to be formed. The width of the prepreg 5 is at least a horizontal width over the circumference of the frame to be formed, and at least twice as high as the height of the frame to be formed, more preferably 5 times or more. At this time, it is preferable that the carbon fiber of the prepreg 5 and the side to be formed are parallel. In Fig.6 (a), the arrow P shows the orientation direction of carbon fiber. Even in this case, the core member 12 is preferably provided with a step 13 corresponding to the thickness of the prepreg 5, and further preferably has a mechanism for applying tension to the outside (not shown).

  A pipe-shaped base material 10 as shown in FIG. 7B can be obtained by winding and laminating until the outer dimension of the pellicle frame 1 becomes larger by the cutting allowance and then heat-curing as described above. .

  As shown in FIG. 7C, the pipe-shaped base material 10 is cut into a ring shape with a grinder 16 in a direction parallel to the side of the pellicle frame 1 to be formed, so that the desired height of the pellicle frame 1 is obtained. Alternatively, the base material 10a having a height close to that is obtained. Similarly, a plurality of base materials 10a, 10b, 10c,... Can be obtained at a time as shown in FIG. Although the example which uses the grinder 16 was shown as a processing method to carry out circular cutting, it is not limited to this, For example, a water jet, a diamond cutter, laser cutting etc. can be used. Among these, a water jet is particularly preferable because it has less adverse effects on the cutting quality and the base material 10. The base materials 10a, 10b, 10c,... Obtained here can be individually machined and finished as pellicle frames 1 as in FIG. A plurality of pellicle frames 1 can be produced at a time, and the productivity can be greatly improved.

  FIG. 8 shows a schematic perspective view of a pellicle constructed using the pellicle frame 1 manufactured as described above. A pellicle film 22 is stretched through a pellicle film adhesive layer on a pasting surface 21 of one end face of the pellicle frame 1 on which the resin film 9 is formed on the surface of the prepreg 5, thereby forming a pellicle 20. As the material of the pellicle film 22, cellulose, a derivative thereof, a fluororesin, or the like can be used. A mask adhesive layer 23 is provided on the other end surface on the opposite side. As the mask pressure-sensitive adhesive forming the mask pressure-sensitive adhesive layer 23, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a hot melt pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, or the like can be used. In order to protect the mask adhesive layer 23, a separator 24 provided with a release agent layer on a thin resin film such as PET may be attached to the surface of the mask adhesive layer 23 as necessary. Further, if necessary, a vent hole 2 penetrating the side surface of the pellicle frame 1 is provided to eliminate the swelling and dent of the pellicle film 22 due to the pressure difference between the inside and outside of the pellicle, and dust enters the pellicle from outside the pellicle with ventilation. It is preferable to provide a filter 25 so as not to cause a failure. Moreover, you may provide the recessed hole 3, a groove | channel, etc. (not shown) in a required place for handling etc.

  With the above configuration, the pellicle 20 having a large exposure area can be obtained at a low cost, and the pellicle 20 having a large exposure area can be obtained at low cost. It becomes a high quality thing.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

(Example)
A pellicle frame 1 made of a composite member having a shape as shown in FIG. 1 was manufactured by mechanical cutting. The shape of the pellicle frame 1 is as follows: the outer dimensions of each corner are 904.5 × 750 mm, the inner dimension is a rectangle of 896.5 × 742 mm, the thickness is 5.8 mm, the shape of each corner is the inner R2, The outer side was R6. In addition, recesses 3 having a diameter of 2.5 mm and a depth of 2 mm were provided for handling at an interval of 860 mm on the long side, and recesses 3 of the same shape were provided on the short side at an interval of 730 mm. In addition, vent holes 2 having a diameter of 1.5 mm were provided in the vicinity of the center of both long sides, four on each side.

  The specific manufacturing process of such a pellicle frame 1 is as follows. The composite member used here was a sheet-like prepreg 5 (trade name; E8025C-25N manufactured by Nippon Graphite Fiber Co., Ltd.) in which carbon fibers oriented in one direction were impregnated with an epoxy resin. This prepreg 5 is cut at a width of 200 mm, and wound around the core material 12 so that the fiber direction is parallel to each side as shown in FIGS. A pipe-shaped base material 10 having an outer size of about 906.5 × 752 mm, an inner size of 894.5 × 740 mm, and a height of about 200 mm was obtained. The base material 10 was cut out at a height of 6.5 mm by water jet processing to obtain base materials 10a, 10b, 10c,. Then, each of the base materials 10a, 10b, 10c,... Was machined into the shape of the pellicle frame 1 having the above dimensions by a machining center.

  Next, the pellicle frame 1 was thoroughly washed with a surfactant and pure water, dried by heating at 80 ° C. for 3 hours, and then coated with a resin to form a resin film 9. For the resin, a fluororesin (trade name; Cytop CTX109A manufactured by Asahi Glass Co., Ltd.) is dissolved in a fluorine-based solvent (trade name: NOVEC7300, manufactured by Sumitomo 3M Co., Ltd.), and carbon black (trade name; HCF2650, Mitsubishi Chemical ( This was performed four times by a spray method using a solution in which the product was dispersed. Thereafter, the solvent was completely dried by heating to 130 ° C. in an oven. The film thickness of the fluororesin coating 9 was about 30 μm.

  Finally, the dimensions were inspected, and the outer and inner dimensions were all in the range of + 0 / −0.3 mm of the processing designated dimensions. In addition, the perpendicularity was a deviation of 0.5 mm with respect to the imaginary line drawn at 90 degrees with respect to the long side.

  The pellicle frame 1 was carried into a clean room, washed with a surfactant and pure water, dried, and then inspected for its appearance while being irradiated with a 400,000 lux halogen lamp in a dark room. As a result, the composite member was not exposed at all. In addition, defects such as surface scratches and uneven coating, and peeling of the resin film 9 due to cleaning were not observed.

  Next, using this pellicle frame 1, a pellicle 20 as shown in FIG. A silicone adhesive as the pellicle film adhesive layer is applied to the affixing surface 21 on one end face of the pellicle frame 1, and a silicone adhesive (trade name KR3700, manufactured by Shin-Etsu Chemical Co., Ltd.) is applied as the mask adhesive layer 23 to the other end face. It was applied with a pressure dispenser and cured (cured) by heating. Then, a separator 24 for protecting the mask adhesive layer manufactured by cutting a PET film having a thickness of 125 μm having a release agent applied onto the surface thereof into a shape substantially the same as that of the pellicle frame 1 is attached, and further, the vent hole 2 is covered. A PTFE filter 25 having a size of 3.6 × 9.5 mm and a thickness of 0.35 mm was attached.

  Separately from the pellicle frame 1, a fluoropolymer (trade name Cytop, manufactured by Asahi Glass Co., Ltd.) was formed on a 1200 × 850 × 10 mm thick rectangular quartz substrate by the slit coat method, and the solvent was dried. Later, the pellicle film 22 having a thickness of about 3 μm was obtained by bonding and peeling to an aluminum alloy temporary frame having the same shape as the outer shape of the substrate. The pellicle film 22 is bonded to the affixing surface 21 on one end face of the pellicle frame 1 finished as described above via a pellicle film adhesive layer, and then the unnecessary pellicle film 22 around the pellicle frame 1 is used as a cutter. The pellicle 20 was produced by cutting and removing.

  Then, the pellicle 20 was placed on a surface plate, and the amount of bending of each side of the pellicle frame 1 was measured. As a result, the amount of deflection to the inside of the central portion of the long side was 1.0 mm on one side, and the amount of deflection to the inside of the center portion of the short side was 0.6 mm on one side.

(Comparative example)
A pellicle frame having the same size and shape as in Example 1 was manufactured by machining. At this time, the base material used was a sheet-shaped prepreg (trade name; DIALEAD HMFJ3113 / 948A1, manufactured by Mitsubishi Plastics), in which a plain-woven carbon fiber was impregnated with an epoxy resin, and heat-cured. It is a plate material of 910 × 760 × thickness of about 6 mm. The plate material was machined into a pellicle frame shape with the above dimensions by a machining center, and resin coating was performed on the surface in the same process as in Example 1.

  Next, using this pellicle frame, a pellicle as shown in FIG. 8 is manufactured in the same process as in the first embodiment, the completed pellicle is placed on a surface plate, and the amount of deflection of each side of the pellicle frame is measured. did. As a result, the amount of bending inward of the central portion of the long side was 2.3 mm on one side, and the amount of bending inward of the central portion of the short side was 1.9 mm on one side. Moreover, this cost was about 9 times that of the above embodiment.

(Comparative Example 2)
Using aluminum alloy A5052, a pellicle frame having the same size and shape as in the above example was manufactured by machining, and the surface was black anodized. I tried to make a pellicle using this pellicle frame, but when the pellicle was erected vertically, the long side and the short side bent about 20 mm, and the shape of the rectangular frame could be maintained in the first place. There wasn't. Therefore, this cannot be used at all as a pellicle frame.

  The pellicle frame of the present invention can be used suitably for pellicles used in manufacturing processes of semiconductors, IC packages, printed circuit boards, liquid crystals, organic EL displays, etc., because a large area of exposure can be secured by greatly improving rigidity. .

  1 is a pellicle frame, 2 is a vent hole, 3 is a recess hole, 4 is a step for a mask adhesive layer, 5 is a prepreg, 6 is winding, 7 is winding end, 8 is a joint, 9 is a resin coating, 10 and 10a , 10b, 10c are base materials, 12 are core materials, 13 are steps, 15 is carbon fiber, 16 is a grinder, 20 is a pellicle, 21 is a bonding surface, 22 is a pellicle film, 23 is a mask adhesive layer, and 24 is a separator. , 25 is a filter.

Claims (8)

Pellicle film is not covered nervous, corner a polygonal shaped frame which is both arcuate in the inner wall and the outer wall side, oriented carbon fibers in a longitudinal direction of each side and forming a frame A composite member containing an epoxy resin is laminated while rotating in the polygonal shape and integrated by curing of the resin , and the surface of the frame body smoothed by polishing and / or cutting is made of carbon black. A pellicle frame characterized by being coated with a resin film selected from acrylic resin, silicone resin, and fluororesin .   2. The pellicle frame according to claim 1, wherein the composite members are stacked by the rotation of a single member connected in series, or are stacked by the rotation of a plurality of members each of which rotates at least once.   3. The pellicle frame according to claim 1, wherein the composite member has a sheet shape in which a large number of oriented carbon fibers are impregnated with the resin. The pellicle frame according to any one of claims 1 to 3, wherein the long fibers of the carbon fibers on the inner wall and the outer wall of each side are oriented in one direction . The pellicle frame according to any one of claims 1 to 4, wherein the corner portion has the arc shape with a minimum bending radius of 3 mm . In the core material smaller than the desired inner dimension of the polygonal frame body in which both the inner wall side and the outer wall side of the corner are arcuate, the vertical width wider than the desired height of the frame body and at least one circumference of the frame body A sheet-like composite member obtained by impregnating an epoxy resin with carbon fibers oriented in the width direction in a transverse width is wound, laminated to a size larger than a desired outer dimension of the frame, and the epoxy resin is heat-cured to form a base material A base material forming process, and
The base material is cut into the desired inner dimensions, outer dimensions and height of the frame body , polished and / or cut to smooth the frame body, and carbon black is applied to the surface of the frame body. A frame forming step of forming a film of a resin selected from acrylic resin, silicone resin, and fluororesin ,
A method for manufacturing a pellicle frame, comprising:   Resin the carbon fiber oriented in the width direction with a core material smaller than a desired inner size of the frame body, at least twice as long as the desired height of the frame body and at least a width over one circumference of the frame body The sheet-shaped composite member impregnated with is wound, laminated larger than the outer dimensions of the frame body, the resin is heat-cured, and then divided into a plurality of parts in a direction parallel to the sides of the frame body by cutting. The method for manufacturing a pellicle frame according to claim 6, further comprising the base material forming step as a base material.   A pellicle, wherein the pellicle film is tension-covered and affixed to the pellicle frame according to claim 1.

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