JP6424450B2 - Substrate for imprint mold, method of manufacturing the same, and imprint mold - Google Patents

Description

  The present invention relates to an imprint mold substrate, a method of manufacturing the same, and an imprint mold using the imprint mold substrate.

  The nanoimprint technology as a microfabrication technology uses a mold member (imprint mold) in which a fine concavo-convex pattern is formed on the surface of a substrate, and transfers the fine concavo-convex pattern to a workpiece such as an imprint resin. This is a pattern forming technique for transferring a fine uneven pattern at an equal magnification (see Patent Document 1). In particular, with the progress of further miniaturization of a wiring pattern or the like in a semiconductor device, nanoimprint technology is increasingly attracting attention in the manufacturing process of the semiconductor device and the like.

  In such a nanoimprint technology, a strong force is required to peel off the imprint mold from a state in which the imprint mold and the imprint resin as the workpiece are in close contact with each other. Therefore, there is a possibility that destruction of the fine concavo-convex pattern transferred to the imprint resin, destruction of the imprint mold, and the like may occur at the time of peeling off the imprint mold.

  In order to solve such a problem, an imprint having a concave portion formed on the surface opposite to the surface on which the fine concavo-convex pattern is conventionally formed so that the dent is deepened from the outer edge of the substrate toward the central portion of the substrate A mold has been proposed (see Patent Document 2).

U.S. Patent No. 5,772,905 JP, 2009-170,773, A

  In the imprint mold disclosed in Patent Document 2, the imprint mold is separated from the imprint resin by having a recess on the surface opposite to the surface on which the fine asperity pattern is formed. Can be curved and release is possible with less force.

  However, the technology for processing the above-mentioned recess for enabling the imprint mold to be curved is a very advanced technology. When it is going to form the concave part which can curve an imprint mold to such an extent that desired peeling performance is obtained by machining using a cutting tool etc., control of the thickness of the bottom of the concave part concerned, surface finish etc. , The processing difficulty is very high. Therefore, it takes time to manufacture an imprint mold having an intended recess shape, which may cause a yield problem. In addition, expensive equipment investment is required to manufacture an imprint mold having the recess.

  In view of the above problems, the present invention has an object of providing a substrate for an imprint mold having concave portions with desired precision, a method of manufacturing the same, and an imprint mold manufactured using the substrate.

In order to solve the above problems, the present invention provides a thin plate portion having a main surface on which a fine asperity pattern can be formed, and a hollow cylindrical support portion supporting an opposing surface facing the main surface of the thin plate portion; And a joint portion interposed between the thin plate portion and the support portion and joining the thin plate portion and the support portion such that an opening end of the hollow cylindrical support portion is closed by the opposing surface; joint comprises said thin plate portion and the support portion and bonded to bondable resin material, a part of the contact portion between the joint portions in each of the thin portions及beauty front Symbol support, the gas A permeable gas permeable structure is provided, and the gas permeable structure provided in the thin plate portion and the gas permeable structure provided in the support portion sandwich the bonding portion therebetween. imprint mode, characterized in that oppositely Providing de substrate (invention 1).

  The supporting portion is joined to the opposing surface side of the thin plate portion via the joining portion, and the opening end of the supporting portion is closed by the opposing surface of the thin plate portion, so that the hollow portion of the supporting portion and the thin plate portion A concave portion is formed on the side opposite to the surface on which the fine asperity pattern of the print mold substrate can be formed. The hollow portion of the support portion constituting the side wall of the recess can be easily and precisely formed. Moreover, the opposing surface of the thin plate part which comprises the bottom face of a recessed part can be easily comprised as a surface which has high flatness. Therefore, according to the said invention (invention 1), the board | substrate for imprint molds which has a recessed part of the precision made desired can be provided.

  In addition, when the bonding portion for bonding the thin plate portion and the supporting portion in the substrate for imprint mold is one including a resin material (for example, a cured product of the pressure-sensitive adhesive composition), the substrate for imprint mold is manufactured. In the process (the process of bonding the thin plate portion and the support portion to form the bonding portion), the gas is not left in the bonding portion, or the gas is not sandwiched in the interface between the bonding portion and the thin plate portion and / or the support portion. Is required. Due to the presence of such a gas, air bubbles (voids) are easily generated in the joint portion or in the interface between the joint portion and the thin plate portion and / or the support portion, whereby the substrate for imprint mold or the imprint produced therefrom The strength of the mold and the flatness of the main surface of the thin plate portion may be adversely affected. In particular, when a solvent-containing adhesive composition is used as a pressure-sensitive adhesive composition for forming a joint, and the solvent remains in the joint, bubbles (voids) may be easily generated in the joint. On the other hand, an extremely thin joint is required as a joint interposed between the thin plate portion and the support portion. When the bonding portion formed by curing the pressure-sensitive adhesive composition is thick, internal stress is easily generated in the thin plate portion and the supporting portion at the time of curing of the pressure-sensitive adhesive composition (at the bonding time of the thin plate portion and the supporting portion) This is because the flatness of the main surface (the surface on which the fine asperity pattern is formed) may be adversely affected. On the other hand, if the bonding portion is formed extremely thin, the exposed area of the pressure-sensitive adhesive composition interposed between the thin plate portion and the support portion becomes extremely small, and when the pressure-sensitive adhesive composition containing a solvent is used, the solvent The problem may arise that it is difficult to volatilize and completely remove it. However, in the above invention (invention 1), in the process of manufacturing the substrate for an imprint mold, the gas permeable structure having gas permeability can be provided at the contact portion of the thin plate portion and / or the support portion with the bonding portion. A gas sandwiched at the interface between the joint portion and the thin plate portion and / or the support portion, and a volatilized solvent when the pressure-sensitive adhesive composition contains a solvent, effectively removed through the gas permeable structure It can be done. Therefore, according to the above invention (invention 1), air bubbles (voids) are not easily generated in the joint including the resin material, or at the interface between the joint and the thin plate and / or the support, so that it has sufficient strength. It is possible to obtain an imprint mold substrate having high flatness of parts.

In the above invention (invention 1), the part of the contact portion between the joint portions in each of the thin portions及beauty front Symbol support portion, having a gas permeability, the structure having voids is provided Is preferred (invention 2).
In the said invention (invention 1 and 2), the resin material which has a siloxane bond or an imide bond can be used as said resin material contained in the said junction part (invention 3).

  Further, the present invention provides an imprint mold having a fine concavo-convex pattern formed on the main surface of the thin plate portion of the substrate for an imprint mold according to the invention (inventions 1 to 3). (Invention 4).

Furthermore, according to the present invention, a thin cylindrical portion having a main surface, and a hollow cylindrical support portion supporting an opposing surface facing the main surface of the thin plate portion, and interposed between the thin portion and the support portion. A method of manufacturing a substrate for an imprint mold, comprising: a bonding portion for bonding them, the thin plate portion and the supporting portion being closed by closing an opening end of the supporting portion with an opposing surface of the thin plate portion. Forming a pressure-sensitive adhesive composition layer on the thin plate portion and / or the overlapping portion of the support portion when stacked, and forming the bonding portion by curing the pressure-sensitive adhesive composition layer and a step of bonding the thin plate portion and the support portion via the junction part of the part in contact with the joint portions in each of the thin portions及beauty front Symbol support portion, gas permeable a gas-permeable structure have a, et al provided in the thin plate section Characterized by bonding the thin plate portion and the support portion and the gas permeable structure and said gas permeable structure is provided on the support portion so as to face each other between the junction The present invention provides a method of manufacturing a substrate for imprint molds (invention 5).

  According to the present invention, it is possible to provide a substrate for an imprint mold having recesses with desired precision, a method of manufacturing the same, and an imprint mold manufactured using the substrate.

FIG. 1 is a cut end view showing a schematic configuration of a substrate for an imprint mold according to an embodiment of the present invention. FIG. 2 is a perspective view showing a schematic configuration of a thin plate portion of a substrate for an imprint mold according to an embodiment of the present invention. FIG. 3 is a plan view showing a schematic configuration of the facing surface of the thin plate portion of the imprint mold substrate according to the embodiment of the present invention. FIG. 4 is a cut end view schematically showing another configuration example of a substrate for an imprint mold according to an embodiment of the present invention. FIG. 5 is a perspective view showing a schematic configuration of a support portion of an imprint mold substrate according to an embodiment of the present invention. FIG. 6 is a partially enlarged cut end view schematically showing another configuration example in the vicinity of the bonding portion of the imprint mold substrate according to the embodiment of the present invention. FIG. 7 is a process flow diagram showing in cross-sectional view each process of a method of manufacturing a substrate for an imprint mold according to an embodiment of the present invention. FIG. 8 is a cut end view showing a schematic configuration of an imprint mold according to an embodiment of the present invention. FIG. 9 is a plan view showing a schematic configuration of an imprint mold according to an embodiment of the present invention. FIG. 10 is a process flow diagram showing each process of a method of manufacturing an imprint mold according to an embodiment of the present invention in a cut end view. FIG. 11 is a process flow diagram showing in cross-sectional view each process of the method for reclaiming a substrate for imprint mold in one embodiment of the present invention.

Embodiments of the present invention will be described with reference to the drawings.
[Substrate for imprint mold]
FIG. 1 is a cut end view showing a schematic configuration of an imprint mold substrate according to the present embodiment, and FIG. 2 is a perspective view showing a schematic configuration of a thin plate portion of the imprint mold substrate according to the present embodiment. FIG. 3 is a plan view showing a schematic configuration of the facing surface of the thin plate portion of the imprint mold substrate according to the present embodiment, and FIG. 4 is another configuration of the imprint mold substrate according to the present embodiment. It is a cutting end view showing an example roughly, and Drawing 5 is a perspective view showing a schematic structure of a supporter of a substrate for imprint mold concerning this embodiment.

  As shown in FIG. 1, a substrate 1 for an imprint mold according to the present embodiment includes a thin plate portion 2 having a main surface 2A on which a fine asperity pattern of the imprint mold can be formed, and a main surface 2A of the thin plate portion 2. A hollow cylindrical support portion 3 supporting the opposing surface 2B, and a joint portion 4 including a resin material, interposed between the thin plate portion 2 and the support portion 3 and joining them are provided. In addition, in this embodiment, although the thing formed by hardening the adhesive composition containing a solvent and the said resin material is mentioned as an example and demonstrated as the junction part 4, this invention is limited to such an aspect. Instead, the bonding portion 4 may be formed by curing a solvent-free pressure-sensitive adhesive composition.

  The thin plate portion 2 is joined to the support portion 3 via the joint portion 4 so as to close the opening end 31 (see FIG. 5) of the hollow cylindrical support portion 3. As described above, the imprint mold base 1 according to the present embodiment is configured by the hollow portion 30 (see FIG. 5) of the support portion 3 and the opposing surface 2B of the thin plate portion 2 closing the opening end 31. It has a recess 6. Therefore, the opposing surface 2B of the thin plate portion 2 is configured as a flat surface to the extent required on the bottom surface of the recess 6 of the imprint mold substrate 1.

  Examples of the thin plate portion 2 include glass substrates such as quartz glass substrates, soda glass substrates, fluorite substrates, calcium fluoride substrates, magnesium fluoride substrates, acrylic glass substrates, borosilicate glass substrates, etc .; polycarbonate substrates, polypropylene substrates, polyethylene A single-layer substrate made of a substrate, a resin substrate such as a polyolefin substrate, or the like, or a transparent substrate such as a multilayer substrate formed by laminating two or more substrates arbitrarily selected from the above substrates can be used.

  In the present embodiment, “transparent” means a light having a wavelength capable of curing the photocurable resin as the imprint resin, for example, a light beam having a wavelength of 200 to 400 nm (in this embodiment, a thin plate portion When irradiated from one side of 2), it means that light reaches the opposite side to the irradiated side. Since the purpose is to cure the photocurable resin, transparency is 60% or more, preferably 90% or more, and particularly preferably 96% or more, as a suitable standard, in terms of transmittance.

  In the present embodiment, the shape (planar shape) of the thin plate portion 2 is a substantially rectangular shape, but is not limited to such a shape, and an application of an imprint mold manufactured from the imprint mold substrate 1 It may have an arbitrary shape according to etc., for example, a substantially circular shape or the like. Further, the size of the thin plate portion 2 (the size in plan view) is not particularly limited either, and may be set to a size according to the application of the imprint mold manufactured from the substrate 1 for imprint mold .

  Furthermore, the thickness T2 of the thin plate portion 2 may be appropriately set according to the material of the thin plate portion 2, the application of the imprint mold manufactured from the substrate 1 for imprint mold, etc. When it is configured, it may be set to about 0.3 to 1.5 mm. The imprint mold 10 (see FIG. 8) manufactured from the imprint mold substrate 1 according to the present embodiment is formed by closing the opening end 31 of the hollow portion 30 of the support portion 3 with the thin plate portion 2 By having the concave portion 6, at the time of the imprinting process, particularly at the time of peeling of the imprint mold 10, at least a region of the thin plate portion 2 in which the fine concavo-convex pattern is formed can be curved. The effect of facilitating peeling is exhibited. Therefore, if the thickness T2 of the thin plate portion 2 is too thin or too thick, it may be difficult to bend as intended when peeling off the imprint mold 10. If the thickness T2 of the thin plate portion 2 is too thin, the strength of the imprint mold 10 may be reduced.

  In the imprint mold substrate 1 according to the present embodiment, a surface (abuts against the bonding portion 4) in the vicinity of the outer edge portion which is a region coming into contact with the bonding portion 4 among the facing surface 2B facing the main surface 2A The surface 2 </ b> C is provided with a structure (gas permeable structure) 21 having gas permeability. At the time of production of the substrate 1 for imprint mold according to the present embodiment (at the time of bonding of the thin plate portion 2 and the support portion 3), it is necessary to volatilize and remove the solvent from the adhesive composition containing the solvent. If the solvent is not sufficiently evaporated, the solvent remains in the bonding portion 4 and causes air bubbles. In addition, since the solvent remains, the heat resistance and the chemical resistance of the imprint mold substrate 1 and the imprint mold 10 produced therefrom may be deteriorated. At this time, as in the present embodiment, the gas permeable structure 22 is provided on the surface 2C in the vicinity of the outer edge portion of the thin plate portion 2, so that the solvent volatilized from the pressure-sensitive adhesive composition becomes the gas permeable structure 22. It is discharged to the outside of the joint 4 through. As a result, the solvent does not remain in the bonding portion 4 formed by curing the pressure-sensitive adhesive composition.

  The gas permeable structure 22 is not particularly limited as long as the solvent can evaporate from the pressure-sensitive adhesive composition. For example, when the thin plate portion 2 is formed of a quartz glass substrate, the gas permeable structure 22 may be a fine pillar structure or a minute structure formed on the entire surface 2C of the facing surface 2B of the thin plate portion 2 or in the vicinity of the outer edge portion. Examples thereof include a slit structure, a glass bonded to the surface 2C in the vicinity of the outer edge portion, a porous film formed of SOG or the like, and the like. If it is not necessary for the gas permeable structure 22 located at the junction between the thin plate portion 2 and the support portion 3 to transmit light, for example, a porous silicon layer which does not transmit light of a shorter wavelength than infrared light is anodized. The porous silicon layer may be formed on the surface 2C near the outer edge by a method etc., and this porous silicon layer may be used as the gas permeable structure 22 or from a resin material or the like in which gas easily dissolves like PDMS (polydimethylsiloxane). May be formed on the surface 2C near the outer edge, and this layer may be used as the gas permeable structure 22.

The gas permeability coefficient in the gas permeable structure 22 of the thin plate portion 2 is preferably 1 × 10 ^-16 cm ³ · cm / cm ² · s · Pa or more, particularly preferably 1 × 10 ^-13 cm ³ · cm / It is cm ² · s · Pa or more. In addition, the gas permeation coefficient in the gas-permeable structure 22 can be easily calculated | required using a pressure sensor or a gas chromatography, and "JISK6275-1" can be referred as an extreme example. According to the said standard, a test cell which can be divided into a high pressure side cell and a low pressure side cell by a test piece is prepared, and a test gas is introduced into the high pressure side cell at atmospheric pressure or under pressure. It can be asked. This is because the test gas dissolves into the inside of the test piece due to the pressure difference generated between the low pressure side cell, and then diffuses by the test gas concentration gradient inside the test piece and dissipates from the test piece interface to the low pressure side cell. Thus, the amount of gas passing through the test piece can be determined by a pressure sensor (pressure sensor method) that measures the pressure increase in the low-pressure cell or gas chromatography (gas chromatography method) that measures an increase in the amount of test gas.

  In the present embodiment, the gas permeable structure 22 may be provided on the entire surface 2C in the vicinity of the outer edge portion of the facing surface 2B of the thin plate portion 2 or the gas permeable structure may be partially formed on the surface 2C. 22 may be provided. For example, as shown in FIGS. 3A and 3B, of the surface 2C in the vicinity of the outer edge portion of the facing surface 2B of the thin plate portion 2, the gas permeable structure 22 in contact with each of the four sides of the thin plate portion 2 A gas permeable structure 22 may be provided which is continuous further inward beyond the inner edge portion 23 of the surface 2C. That is, a part of the gas permeable structure 22 may be provided so as to be exposed on the outer surface of the imprint mold substrate 1 through the hollow portion 30 of the support portion 3. Thus, when the gas permeable structure 22 is provided in a partial region of the surface 2C, a part of the region provided with the gas permeable structure 22 is on the outer surface of the imprint mold substrate 1 It is required to be exposed and to be continuous between the outer surface of the imprint mold substrate 1 and the bonding portion 4 through the gas permeable structure 22. Since the gas permeable structure 22 functions as a flow path of the solvent volatilized from the pressure-sensitive adhesive composition, the gap between the outer surface of the imprint mold substrate 1 and the bonding portion 4 is continuous via the gas permeable structure 22. Otherwise, the gas permeable structure 22 does not function as a solvent flow path, causing a problem that the solvent can not be sufficiently removed from the pressure-sensitive adhesive composition.

  When gas permeable structure 22 is provided in each of a plurality of independent regions in surface 2C in the vicinity of the outer edge of opposing surface 2B of thin plate portion 2, the distance between adjacent two regions is the adhesive composition It may be appropriately set to such an extent that the solvent volatilized from the substance can be sufficiently discharged to the outside of the bonding portion 4 through the gas permeable structure 22.

  In addition, the ratio of the gas permeable structure 22 to the total area in plan view of the surface 2C in the vicinity of the outer edge portion of the facing surface 2B of the thin plate portion 2 is preferably larger. However, in view of the possibility of gas generation from all of the surfaces (surfaces of the bonding portion 4) contributing to the bonding between the thin plate portion 2 and the support portion 3, the gas permeable structure 22 has a surface 2C near the outer edge portion. Preferably, they are present as uniformly as possible in the plane of. Therefore, the ratio of the gas permeable structure 22 to the total area is preferably 30% or more, and more preferably 50% or more. Furthermore, the distribution of the density at which the gas-permeable structure 22 is present in the plane of the surface 2C near the outer edge is preferably less than 50%, and more preferably less than 30%. Although depending on the content of the solvent in the pressure-sensitive adhesive composition, the physical properties of the solvent, etc., the solvent is sufficiently evaporated from the pressure-sensitive adhesive composition when the ratio is less than 30% or the density distribution is 50% or more. There is a possibility that the gas can not be discharged or exhausted out of the joint 4. As described later, when the gas permeable structure 32 is provided on the main surface 3A of the support portion 3, the ratio of the gas permeable structure 22 of the thin plate portion 2 is less than 30% or the density distribution is 50% Even if it is the above, the thin plate portion 2 corresponds to the total area of the total area of the surface 2C of the thin plate portion 2 in plan view and the total area of the main surface 3A of the support portion 3 (total contact area with the bonding portion 4). The total area of the area of the gas permeable structure 22 and the area of the gas permeable structure 32 of the support 3 may be 30% or more, preferably 50% or more. On the other hand, density distribution should just be able to guarantee the whole in-plane by complementing with thin plate part 2 and support part 3 mentioned below, and it is sufficient to join surface (surface 2C of thin plate part 2 and main surfaces of support part 3) The total in-plane distribution of the gas-permeable structures 22 and 32 of the thin plate portion 2 and the support portion 3 may be less than 50%, preferably less than 30%.

  In the present embodiment, the thin plate portion 2 may have a so-called mesa structure having a convex structure portion 21 on the main surface 2A side as shown in FIG. 4 (A). Further, as shown in FIG. 4B, the main surface 2A of the thin plate portion 2 is a chromium-based material such as Cr, a nitride of Cr; silicon, an alloy containing silicon, a silicon oxide, a silicon nitride, etc. A hard mask layer 5 made of a silicon-based material or the like may be formed.

  As shown in FIGS. 1 and 5, the support portion 3 has a hollow rectangular tube shape whose outer shape is substantially square in a plan view, and a substantially circular hollow portion 30 is formed substantially at the center in a plan view . The main surface 3A of the support portion 3 is joined to the opposite surface 2B of the thin plate portion 2 through the joint portion 4 so that the opening end 31 of the support portion 3 is closed by the thin plate portion 2 (opposite surface 2B) Thus, the bottomed and substantially cylindrical recess 6 is formed.

  The material which comprises the support part 3 is not specifically limited, The material which comprises the thin-plate part 2 may be the same material, and a different material may be sufficient as it. When the support portion 3 is formed of a material different from the material constituting the thin plate portion 2, the material constituting the support portion 3 is, for example, a silicon-based material; a metal material; quartz glass, soda glass, fluorite, Glass materials such as calcium fluoride, magnesium fluoride, acrylic glass and borosilicate glass; resin materials such as polycarbonate, polypropylene, polyethylene and other polyolefins, and ceramic materials such as low expansion ceramics.

  The size of the outer shape of the support portion 3 in plan view may be substantially the same as the size of the thin plate portion 2 or may be larger than that of the thin plate portion 2. When the sizes are substantially the same, there is no difference in level when viewed from the thin plate portion 2 side. For example, when the thin plate portion 2 and the support portion 3 are joined, chamfering of the end face portion or the like is required. Is easy to implement. On the other hand, when the support portion 3 is larger than the thin plate portion 2, for example, when separating the support portion 3 and the thin plate portion 2, as a region capable of holding the support portion 3, the location where the difference in size occurs is held. It becomes possible. In addition, positional deviation at the time of bonding is also acceptable.

  In addition, the size of the hollow portion 30 (the opening end 31 closed by the thin plate portion 2) in a plan view is a size that can include at least a region where the fine asperity pattern is formed on the main surface 2A of the thin plate portion 2 It is. In plan view, the hollow portion 30 has a size capable of containing the fine concavo-convex pattern, so that at the time of the imprinting process using the imprint mold manufactured from the substrate 1 for the imprint mold, particularly at the time of peeling off the imprint mold. The effect of curving at least a region where the fine concavo-convex pattern is formed and facilitating peeling from the imprint resin can be exhibited.

  The thickness T3 of the support portion 3 may be appropriately set according to the design value of the depth of the concave portion 6 of the imprint mold 10 manufactured from the imprint mold substrate 1 according to the present embodiment. It may be set to about 10 mm.

  In the imprint mold substrate 1 according to the present embodiment, a structure (gas permeable structure) having gas permeability like the thin plate portion 2 on the main surface 3A (surface contacting the bonding portion 4) of the support portion 3 ) 32 is provided. Thereby, the solvent volatilized from the pressure-sensitive adhesive composition is discharged out of the joint 4 through the gas permeable structure 32.

  The gas permeable structure 32 is not particularly limited as long as the solvent can evaporate from the pressure-sensitive adhesive composition. For example, in the case where the support 3 is formed of a quartz glass substrate, the gas permeable structure 32 may be a micro pillar structure or a micro slit structure formed on the main surface 3A of the support 3 or the main surface 3A. A porous film etc. which were formed by glass bonded together, SOG, etc. are mentioned. In addition, when the support portion 3 is made of a silicon-based material, the gas permeable structure 32 is the porous silicon layer formed on the main surface 3A of the support portion 3 by the anodization method or the like. A fine pillar structure, a fine slit structure, etc. are mentioned. As in the case of the silicon-based material, if it is not necessary for the gas permeable structure 32 located at the junction of the thin plate portion 2 and the support portion 3 to transmit light, for example, like PDMS (polydimethylsiloxane) A layer made of a resin material or the like in which gas is easily dissolved may be formed on the main surface 3A, and this layer may be used as the gas permeable structure 32.

The gas permeability coefficient of the gas permeable structure 32 of the support portion 3 may be the same as that of the gas permeable structure 21 of the thin plate portion 2, preferably 1 × 10 ⁻¹⁶ cm ³ · cm / cm ² · s · Pa The above, particularly preferably 1 × 10 ⁻¹³ cm ³ · cm / cm ² · s · Pa or more. In addition, the gas permeation coefficient in the gas permeable structure 32 can be easily calculated | required using a pressure sensor or gas chromatography, and can refer "JISK6275-1" as the example of the. According to the said standard, a test cell which can be divided into a high pressure side cell and a low pressure side cell by a test piece is prepared, and a test gas is introduced into the high pressure side cell at atmospheric pressure or under pressure. It can be asked. This is because the test gas dissolves into the inside of the test piece due to the pressure difference generated between the low pressure side cell, and then diffuses by the test gas concentration gradient inside the test piece and dissipates from the test piece interface to the low pressure side cell. Thus, the amount of gas passing through the test piece can be determined by a pressure sensor (pressure sensor method) that measures the pressure increase in the low-pressure cell or gas chromatography (gas chromatography method) that measures an increase in the amount of test gas.

  In the present embodiment, the gas permeable structure 32 may be provided on the entire surface of the main surface 3A of the support portion 3, or the gas permeable structure 32 may be provided on a part of the main surface 3A. It is also good. Thus, when the gas permeable structure 32 is provided in a partial region of the main surface 3A, a part of the region where the gas permeable structure 32 is provided is the outer surface of the imprint mold substrate 1 It is necessary that the outer surface of the imprint mold substrate 1 and the bonding portion 4 be continuous through the gas permeable structure 32. Since the gas permeable structure 32 functions as a flow path of the solvent volatilized from the pressure-sensitive adhesive composition, the gap between the outer surface of the imprint mold substrate 1 and the bonding portion 4 is continuous via the gas permeable structure 32. Otherwise, the gas permeable structure 32 does not function as a solvent flow path, causing a problem that the solvent can not be sufficiently removed from the pressure-sensitive adhesive composition.

  In the case where the gas permeable structure 32 is provided in each of the plurality of independent regions in the main surface 3A of the support portion 3, the space between the two adjacent regions corresponds to the solvent volatilized from the pressure-sensitive adhesive composition. It may be appropriately set to such an extent that the gas can be sufficiently discharged out of the bonding portion 4 through the gas permeable structure 32.

  The ratio of the gas permeable structure 32 to the total area of the main surface 3A of the support portion 3 in plan view is preferably as large as that of the thin plate portion 2. However, in view of the possibility of gas generation from all of the surfaces (surfaces of the bonding portion 4) contributing to the bonding between the thin plate portion 2 and the support portion 3, the gas permeable structure 32 has a surface in the main surface 3A. It is preferable to exist as uniformly as possible. Therefore, the ratio of the gas permeable structure 32 to the total area is preferably 30% or more, and more preferably 50% or more. Furthermore, the distribution of the density at which the gas-permeable structure 32 is present in the plane of the main surface 3A is preferably less than 50%, and more preferably less than 30%. Depending on the content of the solvent in the pressure-sensitive adhesive composition, the physical properties of the solvent, etc., the solvent is sufficiently evaporated from the pressure-sensitive adhesive composition when the ratio is less than 30% or the density distribution is 50% or more. There is a possibility that the gas can not be discharged out of the joint 4. As described above, when the gas permeable structure 22 is provided on the surface 2C of the thin plate portion 2, the ratio of the gas permeable structure 32 of the support portion 3 is less than 30% or the density distribution is 50% Even if it is the above, the thin plate portion 2 corresponds to the total area of the total area of the surface 2C of the thin plate portion 2 in plan view and the total area of the main surface 3A of the support portion 3 (total contact area with the bonding portion 4). The total area of the area of the gas permeable structure 22 and the area of the gas permeable structure 32 of the support 3 may be 30% or more, preferably 50% or more. On the other hand, the density distribution should be able to ensure the entire in-plane by complementing the thin plate portion 2 and the support portion 3, and the bonding surface (the surface 2 C of the thin plate portion 2 and the main surface 3 A of the support portion 3) On the other hand, the total in-plane distribution of the gas-permeable structures 22 and 32 of the thin plate portion 2 and the support portion 3 may be less than 50%, preferably less than 30%.

  The bonding portion 4 is a pressure-sensitive adhesive composition capable of bonding the thin plate portion 2 and the support portion 3 and is formed of a pressure-sensitive adhesive layer formed by curing a pressure-sensitive adhesive composition containing a solvent. The pressure-sensitive adhesive composition most preferably contains a resin material having a siloxane bond or an imide bond, and preferably contains a resin material having a silsesquioxane skeleton or a resin material such as an aromatic polyimide. Particularly suitable resin materials include pyrodogensil sesquioxane (HSQ), polyimide and the like. Since these resin materials are excellent in heat resistance, chemical resistance, etc., if it is the joint part 4 made to harden these, it can be considered as the substrate 1 for imprint molds which is excellent in heat resistance and chemical resistance. Moreover, you may use the material which has sufficient tolerance depending on the chemical | medical agent to be used like resin containing a fluorine, a phenol resin, an epoxy resin, etc. It is possible to withstand the heat generated by light irradiation in the imprinting process using the imprint mold manufactured from the substrate 1 and the action of the chemical in the cleaning of the imprint mold. In particular, in the imprint mold substrate 1 according to the present embodiment, since the solvent does not remain in the bonding portion 4, the substrate can be made more excellent in chemical resistance. In addition, in view of adhesiveness, the above-mentioned pressure-sensitive adhesive composition may contain a resin material having an acryl group, an epoxy group, and the like. With such a resin material, it is possible to obtain stable bonding strength by temporarily bonding by UV irradiation and appropriately heating. The solvent contained in the pressure-sensitive adhesive composition may be appropriately selected according to the type of the resin material, but heating at normal temperature or appropriately (low temperature heating, for example, 400 ° C. or less, preferably 200 ° C. or less) It is preferable to use a solvent which is easy to volatilize when heated). For example, as the above solvents, alkanes, ketones, toluene, xylene, benzene, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, 2-butanone, 2-propanol, cyclohexane, methyl 3-methoxypro Peonate, acetic acid diethylene glycol monoethyl ether, N-vinyl-2-pyrrolidone, N-methyl-2-pyrrolidone, glycol ester, methyl isobutyl ketone and the like can be used.

  In the pressure-sensitive adhesive composition, the thin plate portion 2 and the support portion 3 are separated when the imprint mold produced from the substrate 1 for imprint mold according to the present embodiment is used for the imprinting process. There is no problem as long as the adhesive strength (adhesive strength to the thin plate portion 2 and the support portion 3 as adherends) is sufficient, and the thin plate portion is made of the imprint resin (photocurable resin) cured at the time of the imprinting process. It is sufficient if it can withstand a force twice or more, preferably five times or more, of the force required to peel 2 vertically. For example, in the case where the bonding portion 4 is formed of the pressure-sensitive adhesive layer, and the thin plate portion 2 and the support portion 3 are both formed of quartz, the thin plate portion 2 is vertically oriented from a cured imprint resin (photocurable resin). If the maximum value of the force required to peel off is 20 N, the above-mentioned pressure-sensitive adhesive layer adhered to quartz in the same area as the contact area between the cured imprint resin (photo-curable resin) and the thin plate portion 2 It is preferable that the maximum value of the force required to exfoliate is 40N or more. However, in the actual imprinting process, the thin plate portion 2 is curved when peeling off the imprint mold, so that in the joint portion 4, the resultant of the force in the vertical direction and the horizontal force due to the bending of the thin plate portion 2 Of the thin plate portion 2 in the vertical direction from the cured imprint resin (photocurable resin) in order to prevent repeated use in the imprinting process and peeling due to accidental external force other than the imprinting process. It is preferable to set it as 5 times or more (100 N or more) of the force required to.

  In the present embodiment, a peeling layer 7 may further be provided between the thin plate portion 2 and the joint portion 4 or between the support portion 3 and the joint portion 4 (see FIGS. 6A and 6B). ). In this case, the peeling layer 7 is preferably located between the support portion 3 and the bonding portion 4 (see FIG. 6B). By having the peeling layer 7, the thin plate portion 2 and the support portion 3 can be separated, and the support portion 3 can be reused. In particular, when the bonding portion 4 remains on the supporting portion 3 side when the thin plate portion 2 and the supporting portion 3 are separated, it is necessary to remove the bonding portion 4 when the supporting portion 3 is reused. By having the peeling layer 7 between the portion 3 and the bonding portion 4, the bonding portion 4 easily remains on the thin plate portion 2 side, and reuse of the support portion 3 can be made easier.

  The thickness T4 of the bonding portion 4 is preferably as thin as possible, but can be appropriately set in accordance with the material forming the bonding portion 4 and the thin plate portion 2. When the pressure-sensitive adhesive composition is used to form the joint portion 4, when the thickness T4 of the joint portion 4 is reduced, internal stress that may be generated in the thin plate portion 2 when the thin plate portion 2 and the support portion 3 are joined is reduced. Thus, the flatness of the main surface 2A of the thin plate portion 2 can be maintained. For example, the thickness T4 of the bonding portion 4 can be about 3 to 100 nm. The internal stress that may occur in the thin plate portion 2 depends on, for example, the contraction rate and expansion rate of the pressure-sensitive adhesive composition before and after bonding, and the thermal expansion coefficient. Therefore, when using a pressure-sensitive adhesive composition having a low coefficient of contraction or expansion or a thermal expansion coefficient close to that of the thin plate portion 2, the thickness T4 of the bonding portion 4 is within the above-mentioned numerical range It can be thicker than 3 to 100 nm). For example, when a material including a material having elasticity such as a resin is used as the pressure-sensitive adhesive composition for forming the bonding portion 4, it is possible to reduce the stress required for peeling when nanoimprinting is performed. Moreover, when using the imprint mold produced from the substrate 1 for an imprint mold according to the present embodiment in an application where the internal stress that can be generated in the thin plate portion 2 can be ignored, The thickness may be, for example, submicron or micron thickness T4.

  In addition, although a photocurable resin composition and a thermosetting or thermoplastic resin composition can also be used as an adhesive composition for forming the junction part 4, a thermosetting or thermoplastic resin composition can be used. It is desirable to use. The photocurable resin composition generally includes a main component which is a monomer component and a crosslinking agent (curing agent), but even if the main component is a resin material having the above bond (a siloxane bond, an imide bond, etc.), The heat resistance and chemical resistance of the bonding portion of the bonding portion 4 due to the crosslinking agent (hardening agent) may be low, and the heat resistance and chemical resistance of the bonding agent 4 as a whole may be inferior. However, as described above, in order to stabilize the bonding process, a material having photo-curing property and thermosetting property may be used in which temporary bonding is performed and then bonding strength is improved by heating.

  The imprint mold substrate 1 having the above-described configuration has a configuration in which the thin plate portion 2 and the support portion 3 are joined via the joint portion 4, thereby closing the hollow portion 30 of the support portion 3 and the opening end 31 thereof. The thin plate portion 2 (opposing surface 2B) forms a bottomed substantially cylindrical recess 6. The hollow portion 30 of the support portion 3 can be formed with high accuracy by an easy processing technique, and the opposing surface 2B of the thin plate portion 2 can be configured as a surface having a high degree of flatness. Such an imprint mold substrate 1 has a highly accurate recess 6. In addition, the gas permeable structures 22 and 32 are provided on the surfaces of the thin plate portion 2 and the support portion 3 in contact with the bonding portion 4 so that the solvent contained in the pressure-sensitive adhesive composition for forming the bonding portion 4 can be used. Can be effectively removed from the joint 4. Therefore, it is hard to produce a bubble (void) in the junction part 4, and it can be set as the board | substrate 1 for imprint molds which has sufficient intensity | strength.

[Method of Manufacturing Imprint Mold Substrate]
The imprint mold substrate 1 having the above-described configuration can be manufactured as follows. FIG. 7 is a process flow diagram schematically showing a manufacturing process of the imprint mold substrate 1 according to the present embodiment in a cross-sectional view.

  As shown in FIG. 7A, first, the thin plate portion 2 having the gas permeable structures 22 and 32 and the support portion 3 are prepared, and the above-mentioned pressure-sensitive adhesive composition (solvent (Pressure-sensitive adhesive composition) is applied to form a pressure-sensitive adhesive composition layer 40. A hard mask layer 5 (see FIG. 4B) may be formed in advance on the main surface 2A of the thin plate portion 2.

As a method of providing the gas permeable structure 22 on the surface 2C in the vicinity of the outer edge portion of the facing surface 2B of the thin plate portion 2, for example, when the gas permeable structure 22 is a pillar array structure or a fine slit structure, the thin plate portion 2 After forming a resist pattern corresponding to a pillar array or a slit on the surface 2C and the like in the vicinity of the outer edge portion of the facing surface 2B, a pillar array structure as the gas permeable structure 22 can be formed by etching. When the gas permeable structure 22 is a porous film, the separately prepared porous film is attached to the surface 2C in the vicinity of the outer edge portion of the facing surface 2B of the thin plate portion 2 to form a gas on the surface 2C. A permeable structure 22 can be provided.
The support portion 3 is obtained by preparing a base having a predetermined shape and forming the hollow portion 30 substantially at the center of the base. The method of forming the hollow portion 30 is not particularly limited. For example, the hollow portion 30 may be mechanically processed using a cutting tool or the like, or a resist pattern or the like having an opening corresponding to the hollow portion 30 may be formed. It may be etched.

  As a method of providing the gas-permeable structure 32 on the main surface 3A of the support portion 3, for example, when the gas-permeable structure 32 is a porous silicon layer, the main surface 3A of the support portion 3 manufactured from a silicon wafer By performing electric field etching in an aqueous HF solution by an anodization method, the gas permeable structure 32 made of a porous silicon layer can be provided on the main surface 3A of the support portion 3. Moreover, when the said gas-permeable structure 32 is a fine pillar structure, a fine slit structure, a porous film etc., it can be provided by the method similar to the gas-permeable structure 22 in the thin plate part 2 mentioned above.

  As a method of apply | coating an adhesive composition on main surface 3A of the support part 3, arbitrary application methods, such as a spin coat method, an inkjet method, a dispenser method, are employable. In the present embodiment, since the viscosity of the pressure-sensitive adhesive composition can be adjusted by a solvent, it can be easily applied, and thinning of the pressure-sensitive adhesive composition layer 40 becomes easy. In addition, when providing the peeling layer 7 (refer FIG. 6 (B)) between the junction part 4 and the support part 3, the peeling layer 7 is formed on main surface 3A of the support part 3, and the said peeling layer 7 is formed. The pressure-sensitive adhesive composition may be applied. When the peeling layer 7 (see FIG. 6A) is provided between the bonding portion 4 and the thin plate portion 2, the pressure-sensitive adhesive composition is applied onto the main surface 3 A of the supporting portion 3. The peeling layer 7 may be formed on the surface 2C in contact with the bonding portion 4 in the facing surface 2B.

  Next, as shown in FIG. 7B, the opposing surface 2B of the thin plate portion 2 and the main surface of the supporting portion 3 are closed so as to close the opening end 31 of the supporting portion 3 with the thin plate portion 2 (facing surface 2B). 3A is bonded via the bonding portion 4 formed by curing the pressure-sensitive adhesive composition. Thereby, the imprint mold substrate 1 according to the present embodiment can be manufactured.

  When the pressure-sensitive adhesive composition is cured and the facing surface 2B of the thin plate portion 2 and the main surface 3A of the support portion 3 are bonded, the solvent is volatilized from the pressure-sensitive adhesive composition layer 40. Since the solvent volatilized in this way is released to the outer surface through the gas permeable structure 22 of the thin plate portion 2 and / or the gas permeable structure 32 of the support portion 3, a bonding portion formed by curing the pressure-sensitive adhesive composition No solvent remains in 4). Therefore, air bubbles (voids) are not easily generated in the bonding portion 4, and a substrate for an imprint mold having sufficient strength and high flatness of the thin plate portion 2 can be manufactured.

  In order to volatilize the solvent effectively from the pressure-sensitive adhesive composition layer 40, the environment for bonding the thin plate portion 2 and the support portion 3 is preferably an atmosphere having a low solvent concentration and a low partial pressure of the solvent. In addition, it is preferable to raise the temperature of the atmosphere. However, although volatilization of the solvent from the pressure-sensitive adhesive composition layer 40 is promoted by raising the ambient temperature, if the ambient temperature becomes too high, the solvent exceeds the gas permeability in the gas permeable structures 22 and 32, and the solvent is exceeded. Is volatilized, and air bubbles (voids) may be easily generated at the interface between the pressure-sensitive adhesive composition layer 40 (the bonding portion 4) and the gas-permeable structures 22, 32. Therefore, it is desirable that the atmosphere temperature be appropriately set according to the type of solvent contained in the pressure-sensitive adhesive composition, the solvent concentration / partial pressure in the atmosphere, and the like.

[Imprint mold]
Subsequently, an imprint mold that can be manufactured from the imprint mold substrate 1 according to the present embodiment described above will be described. FIG. 8 is a cut end view showing the imprint mold 10 in the present embodiment, and FIG. 9 is a plan view showing the imprint mold 10.

  As shown in FIG. 8, in the imprint mold 10 according to the present embodiment, a desired fine concavo-convex pattern 11 is formed on the main surface 2A of the thin plate portion 2 of the imprint mold substrate 1 according to the present embodiment. . The shape, size, aspect ratio, etc. of the fine concavo-convex pattern 11 may be appropriately set according to the application of the imprint mold 10.

  As shown in FIG. 9, in plan view of the imprint mold 10, the area PA where the fine concavo-convex pattern 11 is formed is included in the area HA defined by the outer shape of the hollow portion 30 of the support portion 3. Therefore, in the imprinting process using the imprint mold 10, at least the area PA in which the fine asperity pattern 11 is formed in the thin plate portion 2 of the imprint mold 10 can be curved. Can be easily peeled off from the imprint resin.

  In the imprint mold 10, the solvent contained in the pressure-sensitive adhesive composition for forming the bonding portion 4 does not remain in the bonding portion 4 for bonding the thin plate portion 2 and the support portion 3. Air bubbles (voids) are not easily generated in the portion 4 and the thin plate portion 2 having sufficient strength and high flatness is provided.

  Further, when the imprint mold 10 is discarded due to multiple uses, for example, when the imprint mold 10 is discarded, the imprint mold 10 is separated from the joining portion 4 joining the thin plate portion 2 and the support portion 3. , And at least the support 3 can be reused.

[Method of manufacturing imprint mold]
The imprint mold 10 can be manufactured, for example, as follows. FIG. 10 is a process flow diagram showing each step of the method for manufacturing an imprint mold in the present embodiment in a cross-sectional view.

  In the method of manufacturing the imprint mold 10 according to this embodiment, first, the substrate 1 for imprint mold in which the hard mask layer 5 such as a metal chromium film is provided on the main surface 2A of the thin plate portion 2 is prepared A resist pattern 60 corresponding to the pattern 11 is formed on the area PA where the fine concavo-convex pattern 11 of the main surface 2A is to be formed (see FIG. 10A).

  The thickness of the hard mask layer 5 is appropriately determined in consideration of the etching selectivity according to the material of the thin plate portion 2 of the imprint mold substrate 1, the aspect ratio of the fine concavo-convex pattern 11 in the imprint mold 10, etc. It can be set.

  The resist material constituting the resist pattern 60 is not particularly limited, and a conventionally known energy ray sensitive resist material (for example, electron beam sensitive resist material, ultraviolet sensitive resist material, etc.) may be used. it can.

  The method of forming the resist pattern 60 is not particularly limited. For example, the resist pattern 60 can be formed by an electron beam lithography method, a photolithography method, or the like.

  Subsequently, the hard mask layer 5 is etched by a dry etching method using the resist pattern 60 as a mask to form a hard mask pattern 51 (see FIG. 10B). Then, using the hard mask pattern 51 as a mask, the main surface 2A of the thin plate portion 2 of the imprint mold substrate 1 is etched to form a fine concavo-convex pattern 11 (see FIG. 10C).

  Finally, the hard mask pattern 51 is removed (see FIG. 10D). Thereby, the fine concavo-convex pattern 11 is formed on the main surface 2A of the thin plate portion 2, and the imprint mold 10 having the concave portion 6 with high precision can be manufactured.

  In the case of using the electron beam lithography method or the photolithography method when forming the resist pattern 60, the thin plate portion 2 has no deflection and is uniformly flat when viewed from the exposure light source side. preferable. Therefore, it is preferable that the thin plate portion 2 have a thickness corresponding to the size or be attached to the support portion 3 so as to have tension.

  The substrate 1 for an imprint mold according to the above-described embodiment, which is used in the method for manufacturing an imprint mold according to the embodiment, is included in a solvent (an adhesive composition for forming the junction 4 in the junction 4 As a result, since no solvent (solvent) is left, air bubbles are not easily generated in the joint portion 4, which has sufficient strength and high flatness of the thin plate portion 2. Therefore, according to the method for manufacturing an imprint mold in the present embodiment, the fine concavo-convex pattern 11 can be formed with high precision because the flatness of the thin plate portion 2 is high, and the imprint mold 10 having sufficient strength. Can be manufactured.

  Although the resist pattern 60 is formed by electron beam lithography, photolithography, etc. in the above method, the resist pattern 60 is formed by nanoimprint lithography using an imprint mold having a fine concavo-convex pattern corresponding to the resist pattern 60. A resist pattern 60 may be formed.

[Method for Reproducing Imprint Mold]
Subsequently, a method of regenerating the imprint mold 10 will be described. FIG. 11 is a process flow chart showing the respective steps of the method for reclaiming an imprint mold in the present embodiment by cross-sectional views.

  In the present embodiment, first, the thin plate portion 2 and the support portion 3 of the used imprint mold 10 are separated (see FIG. 11A). As a method of separating the thin plate portion 2 and the support portion 3, for example, the adhesive strength of the pressure-sensitive adhesive composition layer constituting the bonding portion 4 is reduced by irradiating the bonding portion 4 with infrared rays and heating the thin plate The method etc. which isolate | separate the part 2 and the support part 3 can be mentioned. At this time, if the peeling layer 7 is provided between the support portion 3 and the bonding portion 4 (see FIG. 4B), the bonding portion 4 is left on the thin plate portion 2 side, The support portion 3 can be easily separated.

  Next, as necessary, the bonding portion 4 remaining on the main surface 3A of the support portion 3 is removed or the main surface 3A is cleaned, and a new thin plate portion 2 ′ is prepared separately. The opposing surface 2B 'of the thin plate portion 2' and the main surface 3A of the support portion 3 are joined via the joint portion 4 'so that the opening end 31 is closed by the thin plate portion 2'. (See FIG. 11 (B)). Thereby, the used imprint mold 10 can be regenerated as the imprint mold substrate 1.

  In addition, a new thin plate portion 2 ′ is bonded separately to the surface facing the main surface 3A (the surface to which the thin plate portion 2 is bonded) of the support portion 3 of the used imprint mold 10, It may be regenerated as the substrate 1.

  A hard mask layer 5 formed of a metal chromium film or the like may be formed on the main surface 2A 'of the thin plate portion 2' (see FIG. 4B). As a method of bonding the thin plate portion 2 and the support portion 3 through the bonding portion 4, a method (see FIG. 7B) similar to the method described in the method of manufacturing the imprint mold substrate 1 is employed. can do.

  Then, the imprint mold 10 can be regenerated by manufacturing the imprint mold 10 by the method shown in FIG. 10 using the regenerated imprint mold substrate 1.

  As described above, according to the present embodiment, at least the support 3 can be reused, and the used imprint mold 10 can be regenerated.

  The embodiments described above are described to facilitate the understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents that fall within the technical scope of the present invention.

  In the above embodiment, although the thin plate portion 2 and the support portion 3 have been described by way of an example having the gas permeable structures 22 and 32, the present invention is not limited to such an embodiment, The aspect which one of the thin plate part 2 and the support part 3 has the gas-permeable structure 22 and 32 may be sufficient.

  In the above embodiment, the fine asperity pattern 11 is formed on the main surface 2A of the thin plate portion 2 of the imprint mold substrate 1 formed by bonding the thin plate portion 2 and the support portion 3 via the bonding portion 4. Although the imprint mold 10 is manufactured by this, the present invention is not limited to such an aspect. For example, the thin plate portion 2 in which the fine concavo-convex pattern 11 is formed on the main surface 2A, and the support portion 3 are prepared, and the thin plate portion 2 and the support portion 3 are The imprint mold 10 may be manufactured by bonding through the bonding portion 4 so as to be covered with the opposing surface 2B of the second embodiment.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

Example 1
A quartz substrate (152 mm × 152 mm, thickness T2 = 1.0 mm) as thin plate portion 2 and a support portion 3 (152 mm × 152 mm, thickness T3 = 5.35 mm, diameter of hollow portion 30) made of quartz glass = 60 mm), and on the main surface 3A of the support portion 3, an adhesive composition prepared by adjusting the viscosity of HSQ as a resin material with methyl isobutyl ketone (hereinafter MIBK) is opposed to the thin plate portion 2 by spin coating. It apply | coated to the surface 2B, and formed the adhesive composition layer 40. FIG. Gas permeable structures 22 and 32 made of a porous silicon oxide film are provided on the entire surface 2C in the vicinity of the outer edge of the opposing surface 2B of the thin plate portion 2 and the entire main surface 3A of the support portion 3 respectively. (See Figure 1 etc.). The porous silicon oxide film was obtained by forming a silicon film on each of the facing surface 2B of the thin plate portion 2 and the main surface 3A of the support portion 3, anodizing it, and oxidizing it. In addition, the current density at the time of anodization was set to 80 mA / cm ² , and a solution in which a 46 mass% hydrofluoric acid aqueous solution and ethanol were mixed at a volume ratio of 7: 3 was used as the formation solution. The thickness of the obtained porous silicon oxide film was about 1.5 μm.

  Further, the gas permeability coefficient of the gas permeable structures 22 and 32 is such that a porous silicon oxide film is produced on the same quartz glass as the support portion 3 except that the hollow portion 30 is not provided, and the porous silicon oxide film The gas permeation coefficient of was measured and evaluated as follows.

First, an O-ring having the same diameter as the hollow portion 30 is prepared, and the O-ring corresponds to the inner region corresponding to the hollow portion 30 of the porous silicon oxide film and the gas permeable structure 32 on the main surface 3A. It divided into the outside area. Then, the vaporized MIBK was supplied to the inner region, and the MIBK leaking from the outer region was detected by gas chromatography to determine the vapor gas permeation coefficient. As a result, the gas permeation coefficient was 1.3 × 10 ^-16 cm ³ · cm / cm ² · s · Pa.

Next, the adhesive composition layer 40 on the main surface 3 A of the support portion 3 is brought into contact with the surface 2 C in the vicinity of the outer edge portion of the opposing surface 2 B of the thin plate portion 2 to cure the adhesive composition. The thin plate portion 2 and the support portion 3 were joined such that the opening end 31 was closed by the thin plate portion 2 (the opposing surface 2B). At this time, in order to evaporate the solvent from the pressure-sensitive adhesive composition layer 40, heating was performed in an oven at 150 ° C. for 30 minutes. At this time, sufficient evacuation was performed so that the inside of the oven was not filled with the volatilized solvent, and dry N ₂ was sent into the oven. In addition, the adhesive composition attached to the portion corresponding to the hollow portion 30 in the facing surface 2B of the thin plate portion 2 in the spin coating of the pressure sensitive adhesive composition on the facing surface 2B of the thin plate portion 2 After bonding with the support portion 3, it was removed by etching. Thus, an imprint mold substrate 1 was produced. In the first embodiment, although the pressure-sensitive adhesive composition attached to the facing surface 2B of the thin plate portion 2 exposed from the hollow portion 30 is removed, when there is no difference in use as an imprint mold, The pressure-sensitive adhesive composition may not be removed.

Example 2
An imprint mold substrate 1 was produced in the same manner as in Example 1 except that the gas permeable structure 32 was not formed on the main surface 3A of the support portion 3.

[Example 3]
An imprint mold substrate 1 was produced in the same manner as in Example 1 except that the gas permeable structure 22 was not formed on the surface 2C in the vicinity of the outer edge portion of the facing surface 2B of the thin plate portion 2.

Example 4
In a plurality of independent regions on the surface 2C near the outer edge of the opposing surface 2B of the thin plate portion 2, the area ratio is 32% with respect to the total area in plan view of the surface 2C A substrate 1 for an imprint mold was produced in the same manner as in Example 1 except that the gas permeable structure 22 was formed by protecting the surface to prevent contact.

[Example 5]
Example except that the gas permeable structure 32 is formed in a plurality of independent regions of the main surface 3A of the support portion 3 so that the area ratio is 36% of the total area of the main surface 3A in plan view In the same manner as in 1, an imprint mold substrate 1 was produced.

[Example 6]
The gas permeable structure 22 is formed to have an area ratio of 26% with respect to the total area of the area to be a joint in plan view of the surface 2C in the vicinity of the outer edge of the facing surface 2B of the thin plate 2 An imprint mold substrate 1 was produced in the same manner as in Example 1 except that the gas permeable structure 32 was formed so that the area ratio was 32% with respect to the total area of the main surface 3A in plan view.

Comparative Example 1
A substrate for an imprint mold is prepared in the same manner as in Example 1 except that the gas permeable structures 22 and 32 are not provided on the surface 2C in the vicinity of the outer edge portion of the facing surface 2B of the thin plate portion 2 Made.

[Test Example 1]
Using the substrates for imprint molds of Examples 1 to 6 and Comparative Example 1, evaluation tests for the presence or absence of air bubbles, heat resistance, and chemical resistance at the bonding portion 4 were performed as follows.

[Air bubble evaluation]
The presence or absence of air bubbles in the bonding portion 4 of the substrate for imprint molds of Examples 1 to 6 and Comparative Example 1 was evaluated by observing the bonding portion 4 from the main surface 2A side of the thin plate portion 2 using an optical microscope. The results are shown in Table 1.

[Heat resistance evaluation]
The support portion 3 of the imprint mold substrate of each of Examples 1 to 6 and Comparative Example 1 is fixed by a fixing jig, and a pressure of 10 N is applied from the main surface 2A side of the thin plate portion 2 toward the hollow portion 30 side. The mixture was heated at 600 ° C. for 30 minutes. Thereafter, the substrate for imprint mold was cooled, and after being cooled to room temperature, the pressurization was stopped. The amount of distortion (the amount of depression after heating and cooling) of the approximate center (the part corresponding to the hollow portion 30) of the thin plate portion 2 after the above cooling of the substrate for imprint mold is measured using TROPEL FLATMASTER FM200 (manufactured by Corning) It was measured. The results are shown in Table 1.

[Chemical resistance evaluation]
Immersed in MIBK for 3 hours while fixing the supporting portion 3 of the imprint mold substrate of Examples 1 to 6 and Comparative Example 1 with a fixing jig, and then, from the main surface 2A side of the thin plate portion 2, a hollow portion A pressure of 10 N was applied toward the 30 side for 3 hours. At the outer edge of the substrate for an imprint mold after pressing, it is observed using an optical microscope whether or not a void is generated when viewed from the main surface 2A side of the thin plate portion 2, and the length of the void (imprint An image was taken of the length of the air gap from the outer edge portion of the mold substrate with ECLIPS L300, and the distance was measured using ACT-2U (all manufactured by Nikon Corporation). The occurrence of this void means that the resin (HSQ) constituting the joint 4 is attacked by the drug, and it can be evaluated that the chemical resistance is inferior. The results are shown in Table 1.

  In the heat resistance evaluation of Table 1, the measured value of the distortion amount evaluated 100 nm or less as "no change." Further, in the chemical resistance evaluation, the gap length of 10 μm or less was evaluated as “no change”.

  As shown in Table 1, in the imprint mold substrates of Examples 1 to 6, no bubbles were present in the bonding portion 4, while in the imprint mold substrate of Comparative Example 1, the bonding portion 4 was not There were air bubbles in the

  Further, in the imprint mold substrates of Examples 1 to 6, both the heat resistance and the chemical resistance were good results, whereas in the imprint mold substrate of Comparative Example 1, the heat resistance and the chemical resistance were good. The result was inferior to sex.

  As apparent from the results of this evaluation test, by having the gas permeable structures 22 and 32 between the thin plate portion 2 and / or the support portion 3 and the joint portion 4, the pressure-sensitive adhesive composition containing a solvent Since the solvent can be volatilized and removed from the bonded portion 4, it has been confirmed that heat resistance and chemical resistance can be improved without having air bubbles in the bonded portion 4.

  The present invention is useful in the field of microfabrication technology in which a nanoimprint process is performed using an imprint mold to form a microrelief pattern on a semiconductor substrate or the like.

DESCRIPTION OF SYMBOLS 1 ... Substrate for imprint mold 2 ... Thin plate part 2 A ... Principal surface 2 B ... Opposite surface 22 ... Gas permeable structure 3 ... Support part 3 A ... Principal surface 31 ... Opening end 32 ... Gas permeable structure 4 ... Joint part 40 ... Adhesion Agent composition layer 6 ... concave portion 7 ... peeling layer 10 ... imprint mold 11 ... fine asperity pattern

Claims (5)

A thin plate portion having a main surface on which a fine asperity pattern can be formed;
A hollow cylindrical support portion supporting an opposing surface opposed to the main surface of the thin plate portion;
And a joint portion interposed between the thin plate portion and the support portion and joining the thin plate portion and the support portion so as to close an opening end of the hollow cylindrical support portion with the opposing surface;
The bonding portion includes a resin material capable of bonding and bonding the thin plate portion and the support portion,
The part of the contact portion between the joint portions in each of the thin portions及beauty front Symbol support part, the gas is provided capable gas permeable structure permeable, the gas permeability provided in the thin portion A substrate for an imprint mold characterized in that the elastic structure and the gas permeable structure provided in the support portion are opposed to each other with the bonding portion interposed therebetween . The part of the contact portion between the joint portions in each of the thin portions及beauty front Symbol support unit, according to claim 1, characterized in that it comprises a gas permeable, structure with voids is provided Substrate for imprint molds.   The said resin material is a resin material which has a siloxane bond or an imide bond, The board | substrate for imprint molds of Claim 1 or 2 characterized by the above-mentioned.   An imprint mold characterized in that a fine concavo-convex pattern is formed on the main surface of the thin plate portion of the substrate for an imprint mold according to any one of claims 1 to 3. A hollow cylindrical support portion supporting a thin plate portion having a main surface and an opposing surface facing the main surface of the thin plate portion, and a joint portion interposed between the thin plate portion and the support portion and joining them A method of manufacturing a substrate for an imprint mold comprising:
The thin plate portion and / or the overlapping portion of the support portion are adhesively bonded when the thin plate portion and the support portion are superimposed so that the opening end of the support portion is closed by the opposing surface of the thin plate portion. Forming an agent composition layer,
Curing the pressure-sensitive adhesive composition layer to form a bonding portion, and bonding the support portion and the thin plate portion via the bonding portion;
Part of the portion in contact with the joint portions in each of the thin portions及beauty front Symbol support portion, the gas will have a permeable gas permeable structure, wherein the gas permeable structure is provided on the thin plate section The substrate for imprint mold, wherein the support portion and the thin plate portion are joined such that the gas permeable structure provided in the support portion and the gas permeable structure are opposed to each other with the joint portion interposed therebetween. Manufacturing method.

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