WO2010090088A1 - 基材作製方法、ナノインプリントリソグラフィ方法及び型複製方法 - Google Patents
基材作製方法、ナノインプリントリソグラフィ方法及び型複製方法 Download PDFInfo
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- WO2010090088A1 WO2010090088A1 PCT/JP2010/050887 JP2010050887W WO2010090088A1 WO 2010090088 A1 WO2010090088 A1 WO 2010090088A1 JP 2010050887 W JP2010050887 W JP 2010050887W WO 2010090088 A1 WO2010090088 A1 WO 2010090088A1
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- transfer
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Definitions
- the present invention relates to a substrate production method for transferring a transfer mold structure to a substrate, a nanoimprint lithography method using the substrate production method, and a mold replication method.
- Nanoimprint lithography is a lithography that impresses and transfers a fine structure of a mold, and is said to have a resolution of about 10 nm while being a simple and inexpensive method (see Non-Patent Document 1).
- FIG. 15 shows a conventional general nanoimprint lithography process.
- an ultraviolet curable resin 103 is applied to the substrate 102 by a spin coating method or the like (a).
- the resin layer 103 is irradiated with ultraviolet rays while pressing the resin layer 103 with a mold 101 having a fine structure 101a composed of a fine concavo-convex structure or the like (b), and then the mold is released and cured.
- 103 is separated from the mold 101 (c).
- the residual film 104 of the resin layer 103 on the base material 102 is removed by ashing (d), and then the base material 102 is removed by performing etching processing on the base material 102 (e).
- the resin layer 103 is completely removed, and the base material 102 having the microstructure 105 corresponding to the microstructure 101a of the mold 101 is produced (f).
- a nanoimprint method using an ultraviolet curable resin is generally referred to as an optical nanoimprint method or a UV (ultraviolet) nanoimprint method.
- a method may be used in which a thermoplastic resin is used as the resin and the microstructure 101a of the mold 101 is transferred by heating and pressing, and this is called a thermal nanoimprint method.
- Patent Document 1 discloses an imprint apparatus, an imprint method, and a chip manufacturing method in which a workpiece is partially supported by a support portion and pressed in order to reduce the influence at the time of imprint caused by bending of the workpiece. A method is disclosed.
- Patent Document 2 discloses a method of applying a pressure between a mold and a substrate by applying a static gas pressure to a pressure cavity formed by a sealing gasket between the mold and a holder and applying a sealing gasket between the mold and a holder in order to uniformly apply a load. Is disclosed.
- Patent Document 3 discloses a method of applying a polymer coat to a mold, transferring the polymer coat from the mold to a substrate at an appropriate temperature and pressure, and forming an imprint substrate having a desired micro / nano structure thereon.
- the transfer to the substrate is performed in a heated hydraulic press at a desired pressure and temperature (Claim 16), for example, at a temperature of about 90 ° C. and a pressure of about 5 MPa (Claim 30).
- the problem shown in FIG. 16 occurs when trying to transfer a fine structure with a relatively large area. That is, the flatness ( ⁇ m order) of the mold 101 and the base material 102, the deflection of the mold 101 and the base material 102 when held ( ⁇ m order), and the relative positional relationship (tilt) between the mold 101 and the base material 102 ) Are larger than the fine structure (nm order), and as shown in FIG. 16, there are areas A and B where the fine structure can be transferred in the resin layer 103, resulting in in-plane non-uniformity of transfer. End up. Even if the film is transferred, an in-plane distribution is generated in the thickness of the remaining film 104. If the subsequent steps (d), (e), and (f) in FIG. A defect such as a variation in depth occurs in the unevenness 105.
- the flatness (PV) of a silicon wafer generally used as a base material is about 5 ⁇ m (measurement area diameter 50 mm), and the flatness of a quartz wafer generally used as a mold is about the same. . Therefore, when a general base material and mold are used, when transferring a fine structure on the order of nm, problems such as in-plane non-uniformity of transfer and in-plane distribution of residual film thickness as shown in FIG. Is likely to occur.
- the method of partially supporting and pressing a workpiece in Patent Document 1 to reduce the influence of deflection during holding is basically for the purpose of manufacturing a semiconductor chip, and the chip size is about 20 mm square. It is. Further, it does not improve the influence of the flatness of the mold or the substrate.
- the press pressure due to gas pressure in Patent Document 2 improves the uniformity of the press pressure due to the influence of deflection when held and the poor relative positional relationship between the mold and the base material. No pressure is generated to compensate.
- the present invention is capable of transferring the mold structure to the entire surface of the base material regardless of the flatness of the mold or the base material. It is an object of the present invention to provide a substrate production method capable of realizing in-plane distribution uniformity, a nanoimprint lithography method and a mold replication method using the substrate production method.
- the substrate preparation method forms a cured layer made of a material to be transferred on a transfer mold, and a surface of the material to be transferred is formed on the surface of the cured material to be transferred.
- the transfer material layer is transferred by separating the transfer material layer and the base material having the surfaces that can be closely contacted by physical interaction, and integrating the transfer material and the transfer mold. It is characterized by producing the base material made.
- this base material preparation method by superimposing the base material on the cured transfer material layer on the transfer mold, the transfer material layer surface and the substrate surface are adsorbed to each other by physical interaction.
- the transferred material layer and the substrate can be brought into close contact with each other without interposing an adhesive or the like between the transfer material layer and the substrate. Since the closely adhered transfer target material layer and the base material can be separated from the transfer mold, the base material on which the transfer target material layer is transferred can be obtained.
- a cured transfer material layer is formed on the transfer mold, and the cured transfer material layer and the substrate are integrally separated from the transfer mold, so regardless of the flatness of the transfer mold and the substrate, The mold structure can be transferred onto the entire surface of the substrate.
- the in-plane of the transfer is caused by the deflection when holding the transfer mold or the substrate or the positional relationship (tilt, etc.) between the transfer mold and the substrate. It is possible to prevent the occurrence of non-uniformity and in-plane distribution of the remaining film thickness of the transfer material layer. Thereby, the base material which transferred the mold structure accurately can be produced at low cost.
- the base material and the transferred material layer are in a normal temperature normal pressure state or a normal temperature reduced pressure state, regardless of the flatness of the flat surfaces of the base material and the transferred material layer. Adsorb to each other.
- the transfer mold has a fine structure, and the fine structure is transferred to the other surface opposite to the surface of the transfer material layer that is in close contact with the base material.
- Examples of the fine structure include a periodic uneven structure.
- the transfer material includes at least one material selected from an ultraviolet curable resin, a thermosetting resin, a thermoplastic resin, a photoresist, an electron beam resist, and SOG (spin on glass). preferable.
- the transfer material layer can be formed by applying the transfer material to the transfer mold and then curing the transfer material.
- the transfer material is preferably applied by any one of a spin coating method, a spray coating method, a dip coating method, and a bar coating method.
- the coating method is selected mainly depending on the film thickness.
- spin coating or spray coating is suitable. The law is suitable.
- the dip coating method is suitable.
- the applied transfer material is subjected to a curing process by at least one of ultraviolet curing, thermal curing, and solvent volatilization.
- a plurality of curing methods may be combined. For example, when an ultraviolet curable resin or a thermosetting resin is diluted with a solvent, the solvent is volatilized by heat treatment, and then an ultraviolet curing treatment or a thermosetting treatment is performed. .
- the transfer material layer may be formed on the transfer mold by any one of vapor deposition, vapor deposition polymerization, CVD, and sputtering.
- the transfer mold is preferably composed of at least one of silicon, quartz, SOG, resin, and metal.
- the base material is preferably composed of at least one of quartz, glass, silicon, resin, and metal, and may be a composite material thereof.
- the base material, the material to be transferred, and the transfer mold so that the adhesive force between the base material and the transfer material layer is larger than the adhesive force between the transfer material layer and the transfer mold.
- the adhesion between the substrate and the transfer material layer is such that the adhesion between the substrate and the transfer material layer is larger than the adhesion between the transfer material layer and the transfer mold.
- the pretreatment is preferably any one of UV ozone treatment, primer treatment, oxygen ashing treatment, charging treatment, nitrogen plasma treatment and cleaning treatment.
- the separation is performed after performing at least one of standing for a predetermined time, heat treatment, electrostatic adsorption treatment and pressure treatment, and The adhesion between the transfer material layer can be increased.
- the nanoimprint lithography method according to the present invention is characterized in that lithography processing is performed on a substrate manufactured by the above-described substrate manufacturing method using a transfer material layer as a mask.
- the mold structure can be transferred to the entire surface of the substrate, regardless of the transfer mold and the planarity of the substrate, and the uniformity of the in-plane distribution of the transfer and the in-plane distribution of the remaining film thickness can be achieved. This can be realized and the accuracy of the material layer to be transferred is improved, so that accurate lithography processing is possible.
- Another nanoimprint lithography method transfers another transfer agent layer to another substrate using the transfer material layer of the substrate prepared by the above-described substrate preparation method, and Lithographic processing is performed using another transfer material layer as a mask.
- the mold structure can be transferred to the entire surface of the substrate, regardless of the transfer mold and the planarity of the substrate, and the uniformity of the in-plane distribution of the transfer and the in-plane distribution of the remaining film thickness can be achieved. This can be realized and the accuracy of the material layer to be transferred is improved, so that accurate lithography processing is possible.
- another transfer material layer can be replaced with a material suitable for lithography processing, and the lithography processing method can be stably executed.
- the mold duplication method according to the present invention is characterized in that a transfer mold is duplicated using a base material onto which a transfer agent layer has been transferred by the above-described base material preparation method.
- the mold structure can be transferred to the entire surface of the substrate side regardless of the flatness of the transfer mold or the substrate, and the uniformity of the in-plane distribution of the transfer and the in-plane distribution of the remaining film thickness can be achieved. This can be realized and the accuracy of the transfer material layer is improved, so that the transfer mold can be duplicated with high accuracy.
- the transfer mold is expensive and expensive, but an accurate replication mold can be manufactured at low cost.
- the base material onto which the transfer material layer has been transferred in the above-described mold duplication method can be a second-generation mold.
- the second transfer agent layer is transferred to the second substrate using the substrate to which the transfer material layer is transferred as the second transfer mold, and the third generation using the second substrate.
- a mold can be produced.
- transfer means that the transfer material layer is integrated with the base material and moves to the base material side, and a mold structure (fine structure) is formed on the surface of the transfer material layer. Used to mean both.
- flatness is a deviation from the geometric plane, and the degree of flatness (flatness: the difference in height between the maximum value (mountain) and the minimum value (valley) of surface distortion) and the flatness This means the type of sledge (how to warp and swell).
- the transfer of the mold structure is possible on the entire surface of the substrate side regardless of the transfer mold and the planarity of the substrate, the in-plane uniformity of transfer and the remaining film of the transfer material layer Uniformity of in-plane thickness distribution can be realized.
- FIG. 5 is a diagram for explaining each step (a) to (f) of the substrate manufacturing method according to the first embodiment.
- FIG. 2 is a side view (a) to (c) of a mold and a base material for illustrating each step (c), (d), and (f) of the base material manufacturing method of FIG. 1 in more detail. It is a side view which shows typically a mode that two base materials adsorb
- FIG. 10 is a diagram for explaining steps (a) to (f) of a third generation type manufacturing method (third example) using a transfer type SOG in the fourth embodiment.
- FIG. 10 is a diagram for explaining steps (a) to (f) of a third generation type manufacturing method (fourth example) using a transfer type SOG in the fourth embodiment.
- FIG. 10 is a diagram for explaining steps (a) to (h) of a third generation type manufacturing method (fifth example) using transfer type quartz in the fourth embodiment.
- 2 is a scanning electron micrograph showing the fine shape of the surface of a substrate onto which a transfer material is transferred in Example 1.
- FIG. 4 is a scanning electron micrograph showing the fine shape of the mold surface replicated from the transfer mold in Example 2.
- FIG. It is a diagram showing steps (a) to (f) of conventional nanoimprint lithography. It is a figure for demonstrating the problem which generate
- FIG. 10 is a diagram for
- FIG. 1 is a diagram for explaining each step (a) to (f) of the substrate manufacturing method according to the first embodiment.
- FIG. 2 is a side view (a) to (c) of a mold and a base material for illustrating each step (c), (d), and (f) of the base material manufacturing method of FIG. 1 in more detail.
- the substrate manufacturing method according to the present embodiment will be described with reference to FIGS. 1 and 2 and the drawings to be described later, the fine concavo-convex structure of the mold and the thickness and flatness of the mold / base material are exaggerated.
- a transfer mold 11 made of a silicon wafer and having a fine concavo-convex structure 10 is prepared, and an ultraviolet curable resin is used as a transfer material by spin coating on the surface of the transfer mold 11 having the fine concavo-convex structure 10. Is applied to form a resin layer 12 as a transfer material layer.
- the resin layer 12 is accurately formed to have a uniform thickness by spin coating.
- the transfer mold 11 can be obtained by producing a resist mask by, for example, electron beam drawing and forming fine irregularities on the silicon wafer by etching, but is not limited to this method.
- the resin layer 12 is entirely cured by irradiating the resin layer 12 with ultraviolet rays from an ultraviolet lamp 16. Thereby, the cured resin layer 12 on the transfer mold 11 can be formed to a uniform and accurate thickness.
- the resin layer 12 is cured by heat treatment instead of ultraviolet irradiation in the process of FIG.
- the resin layer 12 is cured by volatilizing the solvent by baking in the step of FIG.
- a thin film-like base material 13 made of quartz is set on the cured resin layer 12 on the transfer mold 11 and is adhered by overlapping. At this time, the resin layer 12 and the base material 13 adsorb to each other (self-adsorption) without interposing an adhesive or the like between the resin layer 12 and the base material 13.
- the heating temperature is preferably equal to or higher than the glass transition point of the resin used.
- the resin layer 12 can be transferred to the base material 13, and the fine irregularities of the transfer mold 11 are formed on the surface opposite to the contact surface between the resin layer 12 and the base material 13.
- a base material 15 having a resin layer 12 with a fine relief structure 17 formed by transferring the structure 10 can be produced.
- the fine uneven structure 17 of the resin layer 12 has a structure in which the uneven structure of the fine uneven structure 10 of the transfer mold 11 is inverted.
- the resin layer 12 applied by the spin coating method has a uniform and accurate thickness
- the resin layer 12 is cured in this state, and therefore, the resin layer 12 that has been transferred and cured by the fine concavo-convex structure 10 of the transfer mold 11. Can maintain thickness uniformity and accuracy.
- the resin layer 12 (transfer material layer) and the base material 13 can be brought into close contact with each other by being adsorbed (self-adsorbed) to each other regardless of the flatness of each plane, There is no limit to the size of the material.
- pressing is not required in the adhesion process, a large press essential to the normal nanoimprint method is not required.
- the self-adsorption speed is high, and the time required for adhesion between the 4-inch mold and the substrate is several seconds, and the adhesion process is not rate-limiting when considering the throughput, so there is no influence on productivity.
- FIG. 3 is a side view schematically showing how two substrates adsorb to each other in order to explain the self-adsorption action of the resin layer 12 and the substrate 13 of FIGS.
- the surfaces of the base material and the transfer material layer to be self-adsorbed are flat, and the average surface roughness is 1 nm or less in terms of the center line average roughness Ra as the flatness. Is preferred.
- Ra is the surface roughness of the surface of the transfer material, and does not include the uneven component derived from the fine structure.
- the self-adsorption step in FIG. 1 (d) may be performed under atmospheric pressure (normal pressure), but by performing under vacuum, air bubbles are not caught between the transfer material layer and the substrate. Since it contributes to the improvement of adhesiveness more, it is more preferable to carry out in a vacuum (reduced pressure) state.
- the surfaces of the transfer material layer and the substrate to be self-adsorbed in FIG. 1 have such rigidity that they can be deformed by intermolecular force.
- FIG. 4 is a view for explaining the principle of transferring the resin layer to the base material in the base material manufacturing method of FIGS.
- FIG. 5 is a diagram for explaining the adhesion forces Fa and Fb between the silicon (mold), the resin, and the base material before the pretreatment is performed.
- FIG. 6 is a diagram for explaining preprocessing (first example) according to the present embodiment.
- FIG. 7 is a diagram for explaining the preprocessing (second example).
- FIG. 8 is a view for explaining combinations (third example) of materials according to the present embodiment.
- the process necessary for transferring the resin layer (transfer material layer) to the substrate is a process of applying the transfer material layer 12 to the transfer mold 11 and curing it as shown in FIG.
- FIG. 4B is a step of bonding to the base material 13 by self-adsorption, and a step of releasing the mold as shown in FIG. 4C.
- the mold material is silicon (Si)
- the transfer material is acrylic resin
- the base material is glass
- the adhesion force Fa can be obtained at any interface by simply bonding together.
- Fb are due to the interaction between the —OH group and —CH 3, and Fa ⁇ Fb, and thus cannot be stably transferred.
- Fa> Fb is realized as in the following first to third examples.
- the resin surface is subjected to UV ozone treatment as a pretreatment.
- the —OH group is oriented on the resin surface, and the adhesive force Fa is increased by the electrostatic interaction with the —OH group of the glass substrate, so that Fa> Fb.
- the heating step, the pressing step, and leaving for a predetermined time after this step the intermolecular distance of —OH and —OH can be further reduced, and the adhesion force Fa can be further increased.
- the transfer material is acrylic resin
- the base material is glass as in FIG. Is subjected to primer treatment.
- the adhesion force Fa is increased and Fa> Fb is satisfied. It is considered that since both surfaces become —CH 3 , the conformity between molecules becomes good, the intermolecular distance becomes small, and a large intermolecular force works. Note that the intermolecular distance between —CH 3 and —CH 3 can be further reduced and the adhesion force Fa can be further increased by leaving the heating step, the pressing step, and leaving for a predetermined time after this step.
- the transfer material is SOG (spin-on glass)
- the substrate is glass
- the —OH group on the SOG surface and the glass substrate Since the adhesion force Fa is increased by the electrostatic interaction with the OH group, Fa> Fb is satisfied even without pretreatment.
- the intermolecular distance of —OH and —OH can be further reduced and the adhesion can be further increased by leaving the heating step, pressing step, and leaving for a predetermined time after the adhesion step. Further, by appropriately combining the materials of the transfer mold, the transfer material, and the base material, the adhesion force Fa between the base material and the transfer material layer can be made larger than Fb.
- the release material layer and the transfer mold can be stably released.
- the adhesion between the resin surface and the inorganic material surface is increased by performing any one of UV ozone treatment, excimer lamp treatment, oxygen ashing treatment, alkali washing and alcohol washing as the surface activation treatment.
- adhesion to the resin surface can be increased by performing film formation on glass using an acrylic silane coupling agent as a primer treatment for the inorganic material.
- the adhesiveness between the base material and the material to be transferred can be further strengthened by performing a combination of the material of the base material and the material to be transferred without particularly performing pretreatment. it can.
- the third embodiment is a nanoimprint lithography method performed using the substrate manufacturing method according to the first or second embodiment.
- FIG. 9 is a diagram for explaining each step (a) to (i) of the nanoimprint lithography method according to the third embodiment.
- 9A to 9F correspond to the steps of the substrate manufacturing method shown in FIGS. 1A to 1F and are the same as those in FIG. It is preferable to increase the adhesion between the substrate and the resin layer (transfer material layer) in the same manner as in FIGS.
- the base material 15 having the resin layer 12 in close contact with the base material 13 is obtained.
- the resin layer 12 of the base material 15 is formed by inverting the fine concavo-convex structure 10 of the transfer mold 11.
- the fine concavo-convex structure 17 is provided.
- ashing is performed on the resin layer 12 having the fine concavo-convex structure 17 on the base material 13 to remove the remaining film 14 in the concave portions of the fine concavo-convex structure 17.
- the removal of the remaining film 14 exposes the bottom surface of the concave portion of the base material 13 as indicated by the broken line in the figure, and lowers the convex portion of the fine uneven structure 17 of the resin layer 12.
- the base material 13 is processed by etching the base material 13 using the resin layer 12 of FIG. 9 (g) as a mask. Although it remains, the base material 20 which formed the fine concavo-convex structure 19 corresponding to the fine concavo-convex structure 17 in the base material 13 as shown in FIG.
- the substrate 15 having the fine concavo-convex structure 17 made of a resin obtained by inverting the fine concavo-convex structure 10 of the transfer mold 11 as described above the fine concavo-convex structure 19 obtained by inverting the fine concavo-convex structure 10 of the transfer mold 11 is formed.
- the base material 20 formed on the base material 13 can be obtained.
- the surface of the resin layer 12 Prior to the self-adsorption process of FIG. 9 (d), the surface of the resin layer 12 is subjected to oxygen ashing or the like to activate the surface of the resin layer 12 and reduce the thickness of the resin layer 12. May be. This increases the adhesion between the resin layer 12 and the glass substrate 13 in the self-adsorption step of FIG. 9D, and reduces the thickness of the resin layer 12 to reduce the thickness of the resin layer 12 of FIG. The time required for the remaining film removal step can be shortened.
- the fine concavo-convex structure 10 of the transfer mold 11 can be transferred to the entire surface on the base 13 side regardless of the flatness of the transfer mold 11 and the base 13, and the in-plane uniformity of transfer.
- the uniformity of the in-plane distribution of the thickness of the remaining film 14 can be realized, the accuracy of the transfer material layer 12 is improved, and the accuracy of the fine uneven structure 19 formed on the substrate 13 is improved.
- the remaining film 14 of the resin layer 12 is uniform throughout the surface, the remaining film 14 is uniformly and uniformly removed by the ashing process of FIG. For this reason, since the base material 13 is uniformly and uniformly processed in the etching process of FIG. 9H, the accuracy of the fine concavo-convex structure 19 formed on the base material 13 is improved.
- the fourth embodiment is a method for obtaining a transfer-type replica using the substrate manufacturing method according to the first or second embodiment.
- the first to fifth examples according to this embodiment will be described.
- the second generation mold of the transfer mold is produced in the same process as in FIGS. 9 (a) to (i). That is, the transfer mold 11 of FIG. 9A is the first generation, and the substrate 20 obtained in FIG. 9I by using, for example, quartz as the substrate 13 is a second generation mold made of quartz.
- the second generation mold of the transfer mold is produced in the same process as in FIGS. 9 (a) to 9 (f). That is, the transfer die 11 in FIG. 9A is the first generation, and the base material 15 having the resin layer 12 on which the fine concavo-convex structure 17 is formed on the base material 13 is obtained in the mold release step in FIG. 9F.
- the base material 15 is a second-generation type made of resin.
- an SOG layer is formed using, for example, SOG as a transfer material in FIG. 9A, and the SOG layer on which the fine concavo-convex structure 17 is formed by releasing in FIG. 9F.
- the base material 15 which has on the base material 13 is obtained.
- This base material 15 is the second generation type by SOG.
- FIG. 10 is a diagram for explaining the steps (a) to (f) of the third generation type manufacturing method (third example) using the transfer type SOG in the present embodiment.
- the same process as in FIGS. 9A to 9F is followed to the mold release process. That is, as shown in FIG. 10A, the resin layer 12 in close contact with the substrate 13 is released from the transfer mold 11 as in FIG. 9F. The fine concavo-convex structure 10 of the transfer mold 11 is inverted and the fine concavo-convex structure 17 is transferred to the resin layer 12 on the substrate 13.
- the substrate 15 having the resin layer 12 is used as a second transfer mold, and SOG is applied as a second transfer material on the resin layer 12 by a spin coating method.
- An SOG layer 21 is formed as a transfer material layer.
- the second base material 22 made of glass is adhered to the SOG layer 21 by self-adsorption in the same manner as described above.
- the adhesiveness between the SOG layer 21 and the substrate 22 in FIG. 10D is increased by performing a heat treatment. Then, after the SOG layer 21 and the base material 22 are cooled to room temperature, the SOG layer 21 and the base material 22 are separated from the resin layer 12 as shown in FIG.
- the fine concavo-convex structure 23 in which the fine concavo-convex structure 17 of the resin layer 12 is inverted is transferred to the SOG layer 21 on the glass substrate 22, and the mold 24 having the fine concavo-convex structure 23.
- the mold 24 is a third generation mold because the fine concavo-convex structure is transferred in the order of the transfer mold 11 ⁇ the resin layer 12 ⁇ the SOG layer 21.
- the third generation mold 24 of the transfer mold 11 constituted by the SOG layer 21 on which the fine uneven structure 23 is formed and the glass substrate 22 can be obtained.
- FIG. 11 is a diagram for explaining the steps (a) to (f) of the third generation type manufacturing method (fourth example) by the transfer type SOG in the present embodiment.
- the base material 15 having the resin layer 12 is used as the second transfer mold, and the same steps as in FIG.
- An SOG layer is formed as the second transfer material layer. That is, the SOG layer 21 is formed on the resin layer 12 as shown in FIG.
- the second substrate 25 made of silicon is adhered to the SOG layer 21 by self-adsorption in the same manner as described above.
- the base material 13 is separated from the resin layer 12 and released.
- the resin layer 12 in FIG. 11D is removed by peeling, ashing, solvent treatment, or the like.
- the fine concavo-convex structure 26 in which the fine concavo-convex structure 17 of the resin layer 12 is inverted is transferred to the SOG layer 21, and the third generation mold 27 having the fine concavo-convex structure 26 is obtained. .
- the third generation die 27 of the transfer die 11 composed of the SOG layer 21 on which the fine concavo-convex structure 26 is formed and the silicon substrate 25.
- the base material 13 is made of resin
- the mold release step in FIG. 11 (c) is omitted
- the base material 13 and the resin layer 12 are integrated in the resin removal step in FIG. 11 (d). You may make it remove.
- FIG. 12 is a diagram for explaining the steps (a) to (h) of the third generation type manufacturing method (fifth example) using the transfer type quartz in the present embodiment.
- the base material 15 having the resin layer 12 is used as the second transfer mold, and FIGS. 10B and 11A are used.
- the SOG layer is formed as the second transfer material layer in the same process as in FIG. That is, the SOG layer 21 is formed on the resin layer 12 as shown in FIG.
- the surface of the SOG layer 21 formed on the resin layer 12 is thinned by performing an etching process, and the SOG layer 21 has a fine surface 21 a whose surface 21 a is fine. The thickness is reduced until it is close to the convex surface 17a of the concavo-convex structure 17.
- the second substrate 25 made of silicon is adhered to the surface 21a of the SOG layer 21 by self-adsorption in the same manner as described above.
- the base material 13 is separated from the resin layer 12 and released.
- the resin layer 12 in FIG. 12E is removed by peeling, ashing treatment, solvent treatment, or the like. Thereby, the convex part of the SOG layer 21 remains on the base material 25 as shown in FIG.
- the silicon base material 25 is processed by etching the silicon base material 25 shown in FIG. 12F using the SOG layer 21 as a mask, and the remaining portion of the SOG layer 21 remains.
- a third-generation die 29 in which a fine uneven structure 28 corresponding to the fine uneven structure 17 of the resin layer 12 is formed on the silicon base material 25 is obtained as shown in FIG.
- the third generation mold 29 of the transfer mold 11 in which the fine uneven structure 28 is formed on the substrate 25 can be obtained.
- the base material 13 is made of resin
- the mold release step of FIG. 12D is omitted
- the base material 13 and the resin layer 12 are integrated in the resin removal step of FIG. You may make it remove.
- the fine concavo-convex structure 28 is formed on the substrate 25, so the method of FIG. 12 can be executed as one of nanoimprint lithography methods.
- the fine concavo-convex structure 10 of the transfer mold 11 can be transferred to the entire surface on the substrate side regardless of the flatness of the transfer mold 11 and the substrate 13, and the in-plane uniformity of transfer and Since the uniformity of the in-plane distribution of the remaining film thickness can be realized and the accuracy of the transfer material layer is improved, the transfer mold can be replicated with high accuracy.
- the transfer mold first generation
- an accurate replication mold second generation, third generation
- An acrylic ultraviolet curable resin (PAK02 manufactured by Toyo Gosei Co., Ltd.) was applied as a transfer material to this transfer mold by a spin coat method (3000 rpm, 60 seconds). Thereafter, the ultraviolet curable resin was cured by irradiating ultraviolet rays having a peak wavelength of 365 nm for 1 minute in a nitrogen atmosphere.
- the surface of the transfer material was activated (-OH orientation) by subjecting the surface of the transfer material to UV ozone treatment (UV light source: low-pressure mercury lamp, treatment time: 2 minutes).
- FIG. 13 shows a scanning electron micrograph of the fine shape of the substrate surface onto which the transfer material is transferred in Example 1.
- Example 1 As a modified example of Example 1, as a transfer mold material, other glass such as quartz glass and Pyrex (registered trademark) glass, SOG (spin-on-glass), and a composite material thereof (with SOG coated on glass) are used. Even when it was used, transfer was possible as in Example 1.
- other glass such as quartz glass and Pyrex (registered trademark) glass, SOG (spin-on-glass), and a composite material thereof (with SOG coated on glass) are used. Even when it was used, transfer was possible as in Example 1.
- An acrylic ultraviolet curable resin (PAK02 manufactured by Toyo Gosei Co., Ltd.) was applied as a transfer material to this transfer mold by a spin coat method (3000 rpm, 60 seconds). Thereafter, the ultraviolet curable resin was cured by irradiating ultraviolet rays having a peak wavelength of 365 nm for 1 minute in a nitrogen atmosphere.
- a polyimide resin substrate (3 inches, thickness 0.6 mm, flatness PV 5 ⁇ m (effective diameter 50 mm)) was used as the substrate.
- the substrate and the transfer material surface were subjected to UV ozone treatment (UV light source: low-pressure mercury lamp, treatment time: 2 minutes) to activate the substrate and the transfer material surface (-OH orientation).
- the substrate and the transfer material were brought into close contact with each other by self-adsorption force (intermolecular force). Thereafter, heat treatment (120 ° C., 20 seconds) was performed to improve adhesion to the substrate. Thereafter, the material to be transferred was transferred to the substrate surface by cooling to room temperature and releasing the mold.
- Modification 2 As a modified example of Example 2, other glass such as quartz glass and Pyrex (registered trademark) glass, SOG (spin-on-glass), or a composite material (with SOG coated on glass) is used as a transfer type material. Even in the case of transfer, transfer was possible in the same manner as in Example 2.
- Example 3 As the transfer material, a resin (a material obtained by forming a fine shape on an acrylic ultraviolet curable resin on quartz) was used. An acrylic ultraviolet curable resin (PAK02 manufactured by Toyo Gosei Co., Ltd.) was applied as a transfer material to this transfer mold by a spin coating method (3000 rpm, 60 seconds). Thereafter, the ultraviolet curable resin was cured by irradiating ultraviolet rays having a peak wavelength of 365 nm for 1 minute in a nitrogen atmosphere. The surface of the transfer material was activated (-OH orientation) by subjecting the surface of the transfer material to UV ozone treatment (UV light source: low-pressure mercury lamp, treatment time: 2 minutes).
- UV ozone treatment UV light source: low-pressure mercury lamp, treatment time: 2 minutes.
- Quartz glass (3 inches, thickness 0.6 mm, flatness PV 2 ⁇ m (effective diameter 50 mm)) was bonded to this, and the entire surface was brought into close contact by self-adsorption force (intermolecular force). Thereafter, heat treatment (120 ° C., 20 seconds) was performed to improve adhesion to the substrate. Thereafter, the material to be transferred having a fine shape was transferred onto the surface of the substrate by cooling to room temperature and releasing the mold.
- the transfer material could be transferred in the same manner using an EB resist, a photoresist, a thermosetting resin, or a thermoplastic resin.
- the transfer was possible in the same manner when any of the excimer lamp treatment (2 minutes) or oxygen ashing (ICP etching apparatus 5 Pa, 150 W, 30 sccm, 1 minute) was used as the surface activation treatment.
- Adhesiveness could be further improved by performing nitrogen plasma treatment (ICP etching apparatus, 5 Pa, 150 W, 30 seconds cm, 1 minute) after the surface activation treatment.
- Example 4 As the transfer material, a resin (a material obtained by forming a fine shape on an acrylic ultraviolet curable resin on quartz) was used. An acrylic ultraviolet curable resin (PAK02 manufactured by Toyo Gosei Co., Ltd.) as a transfer material was applied to this transfer mold by a spin coating method (3000 rpm, 60 seconds). Thereafter, the ultraviolet curable resin was cured by irradiating ultraviolet rays having a peak wavelength of 365 nm for 1 minute in a nitrogen atmosphere. Polyimide resin (3 inches, thickness 0.6 mm, flatness PV 5 ⁇ m (effective diameter 50 mm)) was used as the substrate.
- PAK02 manufactured by Toyo Gosei Co., Ltd.
- the substrate and the surface of the material to be transferred were subjected to UV ozone treatment (UV light source: low-pressure mercury lamp, treatment time: 2 minutes) to activate the surface of the substrate and the material to be transferred (-OH orientation).
- UV ozone treatment UV light source: low-pressure mercury lamp, treatment time: 2 minutes
- the substrate and the transfer material were brought into close contact with each other by self-adsorption force (intermolecular force).
- heat treatment 120 ° C., 20 seconds
- the material to be transferred having a fine shape was transferred onto the surface of the substrate by cooling to room temperature and releasing the mold.
- Modification 4 As a modification of Example 4, the transfer type material could be transferred in the same manner even when an EB resist, a photoresist, a thermosetting resin, or a thermoplastic resin was used.
- the transfer material could be transferred in the same manner using an EB resist, a photoresist, a thermosetting resin, or a thermoplastic resin.
- Example 5 As the transfer material, a resin (a material obtained by forming a fine shape on an acrylic ultraviolet curable resin on quartz) was used. SOG (OCD T-12, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied as a transfer material to this transfer mold by spin coating (6000 rpm, 30 seconds). The surface of the transfer material was activated (-OH orientation) by subjecting the surface of the transfer material to UV ozone treatment (UV light source: low-pressure mercury lamp, treatment time: 2 minutes). Quartz glass (3 inches, thickness 0.6 mm, flatness PV 2 ⁇ m (effective diameter 50 mm)) was bonded to this, and the entire surface was brought into close contact by self-adsorption force (intermolecular force).
- SOG OCD T-12, manufactured by Tokyo Ohka Kogyo Co., Ltd.
- Example 5 As a modification of Example 5, the transfer type material could be transferred in the same manner even when an EB resist, a photoresist, a thermosetting resin, or a thermoplastic resin was used.
- Example 6 As the transfer material, a resin (a material obtained by forming a fine shape on an acrylic ultraviolet curable resin on quartz) was used. SOG (OCD T-12, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied as a transfer material to this transfer mold by spin coating (6000 rpm, 30 seconds). A polyimide resin substrate (3 inches, thickness 0.6 mm, flatness PV 5 ⁇ m (effective diameter 50 mm)) was used as the substrate material. The surface of the transfer material and the surface of the substrate were subjected to UV ozone treatment (UV light source: low-pressure mercury lamp, treatment time: 2 minutes) to activate the surface of the transfer material and the surface of the substrate (-OH orientation).
- UV ozone treatment UV light source: low-pressure mercury lamp, treatment time: 2 minutes
- the substrate and the transfer material were brought into close contact with each other by self-adsorption force (intermolecular force). Thereafter, heat treatment (120 ° C., 20 seconds) was performed to improve adhesion to the substrate. Thereafter, the material to be transferred having a fine shape was transferred onto the surface of the substrate by cooling to room temperature and releasing the mold.
- Example 6 As a modification of Example 6, the transfer type material could be transferred in the same manner even when an EB resist, a photoresist, a thermosetting resin, or a thermoplastic resin was used.
- SOG OCD T-12, manufactured by Tokyo Ohka Kogyo Co., Ltd.
- the substrate and the transfer material were brought into close contact with each other by self-adsorption force (intermolecular force). Thereafter, heat treatment (120 ° C., 20 seconds) was performed to improve adhesion to the substrate. Thereafter, the material to be transferred having a fine shape was transferred onto the surface of the substrate by cooling to room temperature and releasing the mold.
- Modification 7 As a modification of Example 7, the transfer type material could be transferred in the same manner even when an EB resist, a photoresist, a thermosetting resin, or a thermoplastic resin was used.
- a base material other glass such as Pyrex (registered trademark) glass, SOG, silicon or a composite material thereof (a glass coated with SOG) could be similarly transferred.
- Pyrex registered trademark
- SOG silicon
- a composite material thereof a glass coated with SOG
- Example 8 the transfer mold was duplicated by repeating the process twice.
- a resist mask was prepared on the transfer mold by electron beam drawing, and a fine shape was dug by dry etching. This fine shape is a hole array structure having a structure period of 620 nm, a hole diameter of 310 nm, and a structure depth of 200 nm.
- An acrylic ultraviolet curable resin (PAK02 manufactured by Toyo Gosei Co., Ltd.) was applied as a transfer material to this transfer mold by a spin coating method (3000 rpm, 60 seconds).
- the ultraviolet curable resin was cured by irradiating ultraviolet rays having a peak wavelength of 365 nm for 1 minute in a nitrogen atmosphere.
- the structure of the resin transferred onto the quartz is used as the second transfer mold, SOG (OCD T-12 manufactured by Tokyo Ohka Kogyo Co., Ltd.) is used as the second transfer material, and the second transfer mold is spin coated. (6000 rpm, 30 seconds).
- self-adsorption force intermolecular force
- Adhered 120 ° C., 20 seconds
- heat treatment 120 ° C., 20 seconds
- FIG. 14 shows a scanning electron micrograph of the fine shape of the mold surface duplicated from the transfer mold in Example 2.
- Example 9 is an application to nanoimprint lithography.
- a resist mask was prepared on the transfer mold by electron beam drawing, and a fine shape was dug by dry etching.
- the fine shape is a hole array structure having a structure period of 620 nm, a hole diameter of 310 nm, and a structure depth of 200 nm.
- An acrylic ultraviolet curable resin (PAK02 manufactured by Toyo Gosei Co., Ltd.) was applied as a transfer material to this transfer mold by a spin coating method (3000 rpm, 60 seconds).
- the ultraviolet curable resin was cured by irradiating ultraviolet rays having a peak wavelength of 365 nm for 1 minute in a nitrogen atmosphere.
- a transfer material was formed to a thickness of about 1 ⁇ m on the transfer mold.
- the surface of the transfer material was subjected to oxygen ashing treatment for 4 minutes, thereby reducing the thickness of the resin to 50 nm and activating the surface.
- heat treatment 120 ° C., 20 seconds
- the material to be transferred was transferred to the substrate surface by cooling to room temperature and releasing the mold.
- the transfer material on the quartz was again subjected to oxygen ashing for 10 seconds to remove the remaining film of the transfer material and expose the quartz.
- a fine shape was dug into quartz by performing dry etching (ICP etching apparatus, CHF3 gas, 1 minute) using quartz as a mask. This fine shape had a structure period of 620 nm, a pillar diameter of 310 nm, and a structure depth of 200 nm.
- Example 10 In the above examples and modifications, the substrate and the material to be transferred were bonded at room temperature and normal pressure. In this example, the basic conditions were the same as in Example 1, and bubbles were introduced in the bonding process. In order to eliminate the possibility of entanglement and improve the yield, bonding was performed at room temperature in a 10 Pa vacuum chamber, and the entire surface was brought into close contact by self-adsorption force (intermolecular force). Thereafter, heat treatment (120 ° C., 20 seconds) was performed to improve adhesion to the substrate under atmospheric pressure. Thereafter, the material to be transferred having a fine shape was transferred onto the surface of the substrate by cooling to room temperature and releasing the mold.
- bonding was performed at room temperature in a 10 Pa vacuum chamber, and the entire surface was brought into close contact by self-adsorption force (intermolecular force). Thereafter, heat treatment (120 ° C., 20 seconds) was performed to improve adhesion to the substrate under atmospheric pressure. Thereafter, the material to be transferred having a fine shape was transferred onto the surface
- Example 11 In this example, the basic conditions were the same as in Example 1, and the method for forming the transfer material was vapor deposition. A PMMA (polymethacrylate) film having a thickness of 200 nm was formed on the transfer mold as a transfer material layer by vacuum deposition. In other steps, the transfer material having a fine shape was transferred onto the surface of the substrate in the same manner as in Example 1.
- a PMMA (polymethacrylate) film having a thickness of 200 nm was formed on the transfer mold as a transfer material layer by vacuum deposition.
- the transfer material having a fine shape was transferred onto the surface of the substrate in the same manner as in Example 1.
- the transfer material layer may be formed on the transfer mold by vapor deposition, vapor deposition polymerization, CVD, or sputtering, but as the material of the transfer material, materials other than resin can be used.
- the transfer material layer is formed by vapor deposition, vapor deposition polymerization, CVD or sputtering, a dent may appear on the surface of the transfer material layer due to the influence of the fine structure of the transfer mold. There is no problem as long as the self-adsorption action between the transferred material layer and the substrate as described in 3 is within the range that can be exhibited.
- the curing process can be performed by solvent volatilization.
- Photoresist, electron beam resist, and SOG are cured by solvent volatilization.
- ZEP520A which is an electron beam resist
- a cured thin film can be obtained by volatilizing the solvent by heat treatment.
- OCD T-12 (Tokyo Ohka Kogyo Co., Ltd.), which is an inorganic SOG, is a propylene glycol dimethyl ether solution of a hydrosiloxane polymer.
- a cured thin film can be obtained by volatilizing the solvent.
- the solvent is easy to fly, so the solvent is volatilized and hardened immediately after application.
- the ultraviolet curable resin and the thermosetting resin are cured only by ultraviolet irradiation and heat treatment, respectively.
- an ultraviolet curable resin or a thermosetting resin is diluted with a solvent. In this case, after spin coating, the solvent is volatilized by heat treatment, and then ultraviolet curing treatment and thermosetting treatment are performed.
- PAK-01 which is an ultraviolet curable resin
- PAK-01 which is an ultraviolet curable resin
- acrylic resin a precursor of acrylic resin
- various dilution ratios are commercially available. These can be applied by spin coating, then the solvent is volatilized, and a cured thin film can be obtained by irradiating with ultraviolet rays.
- the heating process and the release process may be performed in a reduced pressure state in the vacuum chamber.
- a substrate to which a transfer mold structure is transferred can be prepared with high transfer accuracy, and a substrate on which various fine concavo-convex structures corresponding to the purpose can be manufactured at low cost.
- patterned media such as hard disks, discrete media, optical disks, microlens arrays, grating lenses, diffraction gratings, etc. can be manufactured with high precision, and nanoimprint lithography methods and transfer-type replication methods can be used. Can be executed with high accuracy.
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Abstract
Description
図1は第1の実施形態による基材作製方法の各工程(a)~(f)を説明するための図である。図2は図1の基材作製方法の各工程(c)(d)(f)をより詳しく説明するために示す型と基材の側面図(a)~(c)である。図1,図2を参照しながら、本実施形態による基材作製方法を説明する。なお、図1,図2及び後述の各図では、型の微細凹凸構造や型・基材の厚さや平面度等が誇張して描かれている。
第2の実施形態は、図1,図2において樹脂層12と基材13との間の吸着力を大きくするために前処理を行うか(図6,図7)または各材料を選択し組み合わせるもの(図8)である。
第3の実施形態は、第1または第2の実施形態による基材作製方法を用いて行うナノインプリントリソグラフィ方法である。図9は第3の実施形態によるナノインプリントリソグラフィ方法の各工程(a)~(i)を説明するための図である。
第4の実施形態は、第1または第2の実施形態による基材作製方法を用いて転写型の複製を得る方法である。本実施形態による第1例~第5例について説明する。
転写型材料はシリコンウエハ(4インチ、厚さ0.525mm、平面度PV=5μm(有効径50mm))を用いた。転写型に電子ビーム描画によってレジストマスクを作製し、ドライエッチングによって、周期的に微細な凹凸のある微細形状を掘り込んだ。この微細形状は構造周期620nm、ホール径310nm、構造深さ200nmのホールアレイ構造である。
実施例1の変形例として、転写型材料として石英ガラスやパイレックス(登録商標)ガラスなどその他のガラス、SOG(スピンオングラス)、また、その複合材料(ガラスの上にSOGが塗布されたもの)を用いた場合でも、実施例1と同様に転写できた。
転写型材料はシリコンウエハ(4インチ、厚さ0.525mm、平面度PV=5μm(有効径50mm))を用いた。転写型に電子ビーム描画によってレジストマスクを作製し、ドライエッチングによって微細形状を掘り込んだ。この微細形状は構造周期620nm、ホール径310nm、構造深さ200nmのホールアレイ構造である。
実施例2の変形例として、転写型材料として石英ガラスやパイレックス(登録商標)ガラスなどその他のガラス、SOG(スピンオングラス)、またその複合材料(ガラスの上にSOGが塗布されたもの)を用いた場合でも実施例2と同様に転写できた。
転写型材料は樹脂(石英上のアクリル系紫外線硬化性樹脂に微細形状を形成したもの)を用いた。この転写型に被転写材としてアクリル系紫外線硬化性樹脂(東洋合成工業製PAK02)をスピンコート法で塗布した(3000rpm、60秒)。その後、窒素雰囲気下で、ピーク波長365nmの紫外線を1分間照射することで紫外線硬化性樹脂を硬化させた。この被転写材表面にUVオゾン処理(UV光源:低圧水銀ランプ、処理時間:2分)を行うことで被転写材表面を活性化(-OH配向)した。これに石英ガラス(3インチ、厚さ0.6mm、平面度PV2μm(有効径50mm))を貼り合わせ、自己吸着力(分子間力)によって全面を密着させた。その後、基材への密着性向上のために加熱処理(120℃、20秒)を行った。その後、室温まで冷却し離型を行うことで基材表面に微細形状を持つ被転写材を転写できた。
実施例3の変形例として転写型材料はEBレジスト、フォトレジスト、熱硬化性樹脂、熱可塑性樹脂を用いた場合でも、実施例3と同様に転写できた。
転写型材料は樹脂(石英上のアクリル系紫外線硬化性樹脂に微細形状を形成したもの)を用いた。この転写型に被転写材としてアクリル系紫外線硬化性樹脂(東洋合成工業製PAK02)をスピンコート法で塗布した(3000rpm、60秒)。その後、窒素雰囲気下で、ピーク波長365nmの紫外線を1分間照射することで紫外線硬化性樹脂を硬化させた。基材としてポリイミド樹脂(3インチ、厚さ0.6mm、平面度PV5μm(有効径50mm))を用いた。この基材と被転写材表面にUVオゾン処理(UV光源:低圧水銀ランプ、処理時間:2分)を行うことで基材と被転写材表面を活性化(-OH配向)した。基材と被転写材を自己吸着力(分子間力)によって全面を密着させた。その後、基材への密着性向上のために加熱処理(120℃、20秒)を行った。その後、室温まで冷却し離型を行うことで基材表面に微細形状を持つ被転写材を転写できた。
実施例4の変形例として転写型材料はEBレジスト、フォトレジスト、熱硬化性樹脂、熱可塑性樹脂を用いた場合でも同様に転写できた。
転写型材料は樹脂(石英上のアクリル系紫外線硬化性樹脂に微細形状を形成したもの)を用いた。この転写型に被転写材としてSOG(東京応化工業製OCD T-12)をスピンコート法で塗布した(6000rpm、30秒)。この被転写材表面にUVオゾン処理(UV光源:低圧水銀ランプ、処理時間:2分)を行うことで被転写材表面を活性化(-OH配向)した。これに石英ガラス(3インチ、厚さ0.6mm、平面度PV2μm(有効径50mm))を貼り合わせ、自己吸着力(分子間力)によって全面を密着させた。その後、基材への密着性向上のために加熱処理(120℃、20秒)を行った。その後、室温まで冷却し離型を行うことで基材表面に微細形状を持つ被転写材を転写できた。なお、本実施例で使用したSOGはスピンコート処理後ただちに溶媒が揮発し硬化が完了する。溶媒が揮発し難いSOGを用いた場合はベイク処理を行うことで溶媒揮発を行って硬化させてもよい。
実施例5の変形例として転写型材料はEBレジスト、フォトレジスト、熱硬化性樹脂、熱可塑性樹脂を用いた場合でも同様に転写できた。
転写型材料は樹脂(石英上のアクリル系紫外線硬化性樹脂に微細形状を形成したもの)を用いた。この転写型に被転写材としてSOG(東京応化工業製OCD T-12)をスピンコート法で塗布した(6000rpm、30秒)。基材材料としてポリイミド樹脂基材(3インチ、厚さ0.6mm、平面度PV5μm(有効径50mm))を用いた。被転写材表面と基材表面にUVオゾン処理(UV光源:低圧水銀ランプ、処理時間:2分)を行うことで被転写材表面と基材表面を活性化(-OH配向)した。基材と被転写材を自己吸着力(分子間力)によって全面を密着させた。その後、基材への密着性向上のために加熱処理(120℃、20秒)を行った。その後、室温まで冷却し離型を行うことで基材表面に微細形状を持つ被転写材を転写できた。
実施例6の変形例として転写型材料はEBレジスト、フォトレジスト、熱硬化性樹脂、熱可塑性樹脂を用いた場合でも同様に転写できた。
転写型材料は樹脂(石英上のアクリル系紫外線硬化性樹脂に微細形状を形成したもの)を用いた。この転写型に被転写材としてSOG(東京応化工業製OCD T-12)をスピンコート法で塗布した(6000rpm、30秒)。基材材料として石英ガラス(3インチ、厚さ0.6mm、平面度PV=2μm(有効径50mm))を用いた。この基材材料表面と被転写材料表面にプライマー処理(信越化学KBM503、3000rpm、30秒スピンコート→100℃、1分間熱処理)を施した。基材と被転写材を自己吸着力(分子間力)によって全面を密着させた。その後、基材への密着性向上のために加熱処理(120℃、20秒)を行った。その後、室温まで冷却し離型を行うことで基材表面に微細形状を持つ被転写材を転写できた。
実施例7の変形例として転写型材料はEBレジスト、フォトレジスト、熱硬化性樹脂、熱可塑性樹脂を用いた場合でも同様に転写できた。
実施例8は、プロセスを2回繰り返すことで転写型を複製したものである。転写型材料はシリコンウエハ(4インチ、厚さ0.525mm、平面度PV=5μm(有効径50mm))を用いた。転写型に電子ビーム描画によってレジストマスクを作製し、ドライエッチングによって微細形状を掘り込んだ。この微細形状は構造周期620nm、ホール径310nm、構造深さ200nmのホールアレイ構造である。この転写型に被転写材としてアクリル系紫外線硬化性樹脂(東洋合成工業製PAK02)をスピンコート法で塗布した(3000rpm、60秒)。その後、窒素雰囲気下で、ピーク波長365nmの紫外線を1分間照射することで紫外線硬化性樹脂を硬化させた。この被転写材表面にUVオゾン処理(UV光源:低圧水銀ランプ、処理時間:2分)を行うことで被転写材表面を活性化(-OH配向)した。これに石英ガラス(3インチ、厚さ0.6mm、平面度PV=2μm(有効径50mm))を貼り合わせ、自己吸着力(分子間力)によって全面を密着させた。その後、基材への密着性向上のために加熱処理(120℃、20秒)を行った。その後、室温まで冷却し離型を行うことで基材表面に微細形状を持つ被転写材を転写した。
実施例9はナノインプリントリソグラフィへの応用である。転写型材料はシリコンウエハ(4インチ、厚さ0.525mm、平面度PV=5μm(有効径50mm))を用いた。転写型に電子ビーム描画によってレジストマスクを作製し、ドライエッチングによって微細形状を掘り込んだ。微細形状は構造周期620nm、ホール径310nm、構造深さ200nmのホールアレイ構造である。この転写型に被転写材としてアクリル系紫外線硬化性樹脂(東洋合成工業製PAK02)をスピンコート法で塗布した(3000rpm、60秒)。その後、窒素雰囲気下で、ピーク波長365nmの紫外線を1分間照射することで紫外線硬化性樹脂を硬化させた。この手法で転写型上に被転写材が約1μm成膜された。この被転写材表面に酸素アッシング処理を4分間行うことで、樹脂の厚みを50nmと薄膜化するとともに表面を活性化させた。これに石英ガラス(3インチ、厚さ0.6mm、平面度PV=2μm(有効径50mm))を貼り合わせ、自己吸着力(分子間力)によって全面を密着させた。その後、基材への密着性向上のために加熱処理(120℃、20秒)を行った。その後、室温まで冷却し離型を行うことで基材表面に微細形状を持つ被転写材を転写した。
上記実施例1~9及び変形例1~7では接着性を増強する為に自己吸着後に加熱処理を行っているが、所定時間放置(12時間)することでも同様に転写できた。
上記実施例1~9及び変形例1~7では接着性を増強する為に自己吸着後に加熱処理を行っているが、加圧処理(4MPa、1分)することでも同様に転写できた。
上記実施例1~9及び変形例1~7では接着性を増強する為に自己吸着後に加熱処理を行っているが、静電処理(基板間に1000V印加、30秒)することでも同様に転写できた。
上記実施例1~9及び変形例1~10では自己吸着させる基材と被転写材層の互いの面は分子間力によって変形できる程度の剛性であることが好ましいが、互いの面がテンパックスガラス基板の場合、外形と厚さを変えて実験した結果、表1のような結果となった。基材と被転写材層の外径と厚さの組み合わせは、表1の吸着できる範囲(○で示す)であることが好ましい。
上記実施例及び変形例では常温常圧の状態で基材と被転写材との貼り合わせを行ったが、本実施例では基本的な条件を実施例1と同様にし、貼り合わせ工程において気泡をはらむ可能性をなくし、歩留まりを向上させるために10Paの真空チャンバ内において常温で貼り合わせ、自己吸着力(分子間力)によって全面を密着させた。その後、大気圧下で基材への密着性向上のために加熱処理(120℃、20秒)を行った。その後、室温まで冷却し離型を行うことで基材表面に微細形状を持つ被転写材を転写することができた。
本実施例では基本的な条件を実施例1と同様にし、転写材の形成方法を蒸着とした。転写型に被転写材層としてPMMA(ポリメタクリレート)を真空蒸着によって200nm成膜した。これ以外の工程は、実施例1と同様にして基材表面に微細形状を持つ被転写材を転写することができた。
11 転写型
12 樹脂層、被転写材層
13 基材
14 残膜
15 基材
17、19、23、26、28 微細凹凸構造
20 基材
21 SOG層、被転写材層
22、25 基材
Claims (20)
- 転写型に被転写材からなる硬化した層を形成し、
前記硬化した被転写材層表面に、前記被転写材層の表面と物理的相互作用によって密着可能な表面を有する基材を重ね合わせ、
密着により一体化させた被転写材層及び基材と、前記転写型と、を分離することで、前記被転写材層が転写された基材を作製することを特徴とする基材作製方法。 - 前記重ね合わせを常温常圧の状態で行うことを特徴とする請求項1に記載の基材作製方法。
- 前記重ね合わせを常温減圧の状態で行うことを特徴とする請求項1に記載の基材作製方法。
- 前記転写型は微細構造を有し、該微細構造を前記被転写材層の前記基材と密着する表面とは反対側の、もう一方の表面に転写することを特徴とする請求項1から3のいずれか1項に記載の基材作製方法。
- 前記被転写材は、紫外線硬化性樹脂、熱硬化性樹脂、熱可塑性樹脂、フォトレジスト、電子ビームレジスト及びスピンオンガラス(SOG)から選ばれる少なくとも1つの材料を含むことを特徴とする請求項1から4のいずれか1項に記載の基材作製方法。
- 前記転写型に前記被転写材を塗布した後に硬化させることで前記被転写材層を形成することを特徴とする請求項1から5のいずれか1項に記載の基材作製方法。
- 前記被転写材の塗布を、スピンコート法、スプレーコート法、ディップコート法及びバーコート法のうちのいずれかにより行うことを特徴とする請求項6に記載の基材作製方法。
- 前記塗布した被転写材について、紫外線硬化、熱硬化及び溶剤揮発のうちの少なくともいずれか1つにより硬化処理を行うことを特徴とする請求項6または7に記載の基材作製方法。
- 前記転写型に前記被転写材層を蒸着、蒸着重合、CVD及びスパッタリングのうちのいずれかにより形成することを特徴とする請求項1から5のいずれか1項に記載の基材作製方法。
- 前記転写型は、シリコン、石英、SOG、樹脂及び金属のうちの少なくとも1つから構成されることを特徴とする請求項1から9のいずれか1項に記載の基材作製方法。
- 前記基材は、石英、ガラス、シリコン、樹脂及び金属のうちの少なくとも1つから構成されることを特徴とする請求項1から10のいずれか1項に記載の基材作製方法。
- 前記基材と前記被転写材層との間の密着力が前記被転写材層と前記転写型との間の密着力よりも大きくなるように前記基材、前記被転写材及び前記転写型の各材料を組み合わせることを特徴とする請求項1から11のいずれか1項に記載の基材作製方法。
- 前記基材と前記被転写材層との間の密着力が前記被転写材層と前記転写型との間の密着力よりも大きくなるように前記基材及び前記被転写材層の密着する各表面の少なくとも一方に対し前記重ね合わせの前に前処理を行うことを特徴とする請求項1から12のいずれか1項に記載の基材作製方法。
- 前記前処理は、UVオゾン処理、プライマー処理、酸素アッシング処理、帯電処理、窒素プラズマ処理及び洗浄処理の内のいずれかであることを特徴とする請求項13に記載の基材作製方法。
- 前記基材と前記被転写材層との密着後に、所定時間放置、加熱処理、静電気吸着処理及び加圧処理のうちのいずれかを実行してから、前記分離を行うことを特徴とする請求項1から14のいずれか1項に記載の基材作製方法。
- 請求項1から15のいずれか1項に記載の基材作製方法により作製した基材について被転写材層をマスクとしてリソグラフィ加工を行うことを特徴とするナノインプリントリソグラフィ方法。
- 請求項1から15のいずれか1項に記載の基材作製方法により作製した基材の被転写材層を用いて別の基材に別の被転写剤層を転写し、前記別の基材について別の被転写材層をマスクとしてリソグラフィ加工を行うことを特徴とするナノインプリントリソグラフィ方法。
- 請求項1から15のいずれか1項に記載の基材作製方法により被転写剤層が転写された基材を用いて転写型を複製することを特徴とする型複製方法。
- 前記被転写材層が転写された基材を2代目型とすることを特徴とする請求項18に記載の型複製方法。
- 前記被転写材層が転写された基材を第2の転写型として用いて第2の基材に第2の被転写剤層を転写し、前記第2の基材を用いて3代目型を作製することを特徴とする請求項18に記載の型複製方法。
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JP2011066273A (ja) * | 2009-09-18 | 2011-03-31 | Konica Minolta Holdings Inc | 微細マスクパターンの形成方法、ナノインプリントリソグラフィ方法および微細構造体の製造方法 |
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