JP2005353926A - Cleaning method and manufacturing method of substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of cleaning a substrate by peeling from the substrate unnecessary resin adhering onto and left behind on the substrate. <P>SOLUTION: A new ultraviolet curing resin 10 is applied on the substrate (h). The common substrate 7 is stuck on the resulting substrate such that a silane coupling processed surface is brought into close contact with the ultraviolet curing substrate 10, and is irradiated with ultraviolet rays. Consequently, although the new ultraviolet curing resin 10 is cured by the irradiation of the ultraviolet rays, this is, at this time, integrated with ultraviolet ray curing resin 3 left behind on the molded substrate after etching (i). Thereafter, the common substrate 7 is peeled from the quartz substrate 1. The surface of the common substrate 7 has undergone silane coupling processing so that it has been very powerfully bonded to the new ultraviolet curing resin 10. It is therefore possible to remove all the ultraviolet ray curing resin 3 from the surface of the quartz substrate 1 by peeling the quartz substrate 1 and the common substrate 7 (j). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for removing unnecessary resin remaining on the surface of a substrate from the substrate and cleaning the substrate, and a method for manufacturing a substrate having a fine pattern formed on the surface.

  There is a need to produce a fine shape on a substrate such as a quartz substrate or a silicon substrate. So far, photolithography has mainly played a role. In this method, a resist is applied to the substrate, and the pattern is exposed and transferred onto the resist by various exposure apparatuses to expose the resist. Thereafter, the resist is developed, and the remaining resist is used as a mask to etch the pattern onto the substrate. The method of engraving the shape is generally used.

  However, since a very expensive apparatus is required to expose a fine structure of 100 nm or less, the apparatus depreciation cost greatly affects the product cost. Therefore, mass production methods of substrates having a fine structure by different methods have been developed. In particular, an imprint method in which a fine uneven shape is transferred by being pressed against an object has been studied in various fields.

  There are two types of imprint methods. First, a resist or thermosetting resin is thinly and evenly applied onto a substrate such as Si or quartz, and a pre-made fine shape mold is pressed against the resist or thermosetting resin. A thermal nanoimprint method that transfers the fine shape of the mold by deforming the shape of the curable resin with heat and pressure. The second method is to apply a UV curable resin on a substrate such as Si or quartz and create it in advance. This is a photo-nanoimprint method in which a mold having a fine shape is pressed and then cured by irradiating the photo-curable resin with light. In either case, after the pattern of the mold is transferred to a resist, a thermosetting resin, or a photocurable resin, the shape of the mold can be transferred to the substrate by etching using these as a mask.

  Hereinafter, the optical nanoimprint method will be described in detail. Apply a thin and uniform photo-curing resin on a substrate such as Si or quartz, press a mold with a fine pattern that has been prepared in advance to prevent air from entering, and press uniformly to form the mold without any spots. Transfer. Thereafter, the photocurable resin is irradiated with light having a wavelength at which the photocurable resin is cured to cure the photocurable resin, and then the mold is peeled off. Up to this point, optical nanoimprinting is used, but in order to utilize this for applications such as semiconductor processes, this molded substrate is etched, etc., and the fine pattern is engraved in a substrate such as Si or quartz. .

  For example, when the molded substrate is etched, the thin film-like resin residue in the concave portions of the resin irregularities is first removed by ashing or the like. Thereafter, the resin is removed by etching, and the portion where the base substrate is visible is selectively engraved. After the target amount of etching is completed, the remaining resin is removed to complete shape creation on Si, quartz, or the like.

  However, there has been no suitable method for removing the resin remaining on the substrate surface after the etching of the substrate is completed. Resins mainly used in this optical nanoimprint method are UV curable resins, but they are excellent in solvent resistance, and chemicals that can completely remove the resin after curing in a short time Is not found.

  The present invention has been made in view of such circumstances, and a method of peeling off unnecessary resin remaining on the substrate from the substrate to clean the substrate, and this method during the manufacturing process. It is an object of the present invention to provide a method for manufacturing a substrate having the same.

  A first means for solving the problem is a method of removing unnecessary resin remaining on the substrate from the substrate and cleaning the substrate, and a new resin is formed on the substrate surface. A method for cleaning a substrate surface, comprising: a step of removing the unnecessary resin by coating the resin, integrating the unnecessary resin, and removing the new resin. ).

  In this means, a new resin is applied to the substrate surface, integrated with an unnecessary resin, and the new resin is peeled off to peel off the unnecessary resin. In this case, the new resin is preferably the same resin as the unnecessary resin. Since the adhesive force between the integrated unnecessary resin and the new resin is stronger than the adhesive force between the unnecessary resin and the substrate, the unnecessary resin can be easily removed by this means.

  The second means for solving the above problem is that after applying an ultraviolet curable resin on a substrate and bringing a mold having a surface on which a desired fine pattern is formed into close contact with the ultraviolet curable resin surface, The ultraviolet curable resin is irradiated with ultraviolet rays and cured, and the mold is peeled off to transfer the fine pattern to the ultraviolet curable resin, and the substrate having the transferred fine pattern as a mask is used as the substrate. A method of manufacturing a substrate having a fine pattern formed on a surface thereof, comprising a step of engraving the fine pattern on the substrate by etching, wherein the fine pattern is engraved on the substrate by etching the substrate. After that, a new resin is applied to the substrate surface and cured, and integrated with the ultraviolet curable resin remaining on the substrate after the etching, and then integrated. A method for manufacturing a substrate characterized by (claim 2) further comprising the step of separating the resin from the substrate.

  Also in this means, the ultraviolet curable resin remaining on the substrate after etching can be easily removed from the substrate for the same reason as described in the first means. Note that when the substrate is etched, the thin resin film in the portion to be engraved with the substrate may be removed by ashing or the like, or both the substrate and the resin film may be etched.

  A third means for solving the above-mentioned problem is the second means, wherein the friendship substrate has a stronger adhesion to the new resin than the substrate before the new resin is cured. Is attached to the surface of the new resin (claim 3).

  In this means, by applying a force that peels off the substrate and the friend board, it is possible to easily peel the integrated ultraviolet curable resin together with the friend board from the substrate.

  A fourth means for solving the problem is any one of the means of the first means to the third means, wherein an adhesion control layer is formed between the substrate and the ultraviolet curable resin. It is characterized by having the process to do (Claim 4).

  Among materials that are desired to be used as a substrate, there are materials that have poor adhesion to ultraviolet curable resins. In such a case, the adhesion control layer is formed between the substrate and the ultraviolet curable resin by the method of this means. For example, after forming an adhesion control layer on the surface of the substrate, an ultraviolet curable resin layer may be formed thereon.

  A fifth means for solving the above-mentioned problems is the fourth means, characterized in that the adhesion control layer is obtained by applying a diluted silane coupling agent solution and drying it. (Claim 4).

  Silane coupling treatment has the effect of improving the adhesion between quartz, glass, metal, and ultraviolet curable resin, and is suitable as an adhesion control layer.

  A sixth means for solving the problem is the fifth means, wherein the amount of dilution of the silane coupling agent solution is determined according to the type of the new resin, the substrate, and the friend board. It is characterized by changing (claim 6).

  In this means, the adhesion between the substrate and the ultraviolet curable resin can be adjusted to an optimum value.

  A seventh means for solving the problem is any one of the first means to the sixth means, wherein the new resin is an ultraviolet curable resin (claim). Item 7).

  According to the present invention, there is provided a method for removing unnecessary resin remaining on a substrate from the substrate and cleaning the substrate, and a method for manufacturing a substrate having the method in a manufacturing process. Can do.

  Hereinafter, an example of an embodiment of the present invention will be described with reference to the drawings. The pattern formed on the substrate in this embodiment is a fine line and space pattern. For example, the line width of the convex part is 100 nm, the height is 100 nm, and the space part (concave part) is 200 nm in width. This pattern is uniformly formed in a 1 mm square area.

  The die is a Si plate, and a pattern is formed on a substrate having a thickness of 2 mm and a size of 3 inches using an EB exposure apparatus. If the mold is used as it is, peeling from the resin cannot be performed satisfactorily. Therefore, a Ni film of about 1 nm is formed on the surface to form a peeling auxiliary film.

  Materials that can be used for the substrate are semiconductors such as quartz and Si, oxides, metals, and the like. In this embodiment mode, quartz is used.

  The substrate has a disk shape with a thickness of 1 mm, an outer dimension of 100 mm in diameter, and a surface polished to 1 nm or less with Ra.

  The actual manufacturing process is shown in FIGS. As shown in FIG. 1, an ultraviolet curable resin 3 is uniformly coated on a quartz substrate 1 using a spin coater 2 (a). after that. The pattern surface of the mold 4 is brought into close contact with the ultraviolet curable resin 3 surface (b). At this time, air is prevented from entering between the pattern surface and the ultraviolet curable resin 3 surface. For example, there are methods such as performing in a vacuum chamber or molding in a special gas.

  Thereafter, by applying an appropriate pressure to the mold 4 uniformly, the mold 4, the ultraviolet curable resin 3, and the quartz substrate 1 are brought into close contact with each other. Under the convex part of the mold 4, there is a thin ultraviolet curable resin 3 layer, but it can be made very thin by increasing the pressing pressure or decreasing the resin viscosity. However, in principle, it cannot be made zero. In this state, ultraviolet rays are irradiated to cure the ultraviolet curable resin 3 (c).

  After curing, the mold 4 is carefully peeled off to obtain a molded transfer substrate 5. After that, ashing is performed to remove the thin resin layer under the convex portion of the mold 4 (the thin resin portion of the concave portion of the ultraviolet curable resin 3 when viewed from the molding transfer substrate side). As the ashing condition, a condition that the thin resin portion is completely removed in a prior experiment is obtained and used.

When the quartz substrate 1 is etched after the ashing, the ultraviolet curable resin 3 is removed and the exposed surface of the quartz substrate 1 is etched to form a concavo-convex pattern on the quartz substrate 1. The ultraviolet curable resin 3 remains on the convex portion 1 (e)
On the other hand, the friend board 7 is prepared according to the process as shown in FIG. This is obtained by applying a silane coupling agent 9 on the surface of the glass substrate 8 and baking it. The silane coupling agent 9 is a treatment agent for strongly bonding the ultraviolet curable resin 3 and the glass substrate 8.

  A thin silane coupling agent 9 is applied onto the surface of the glass substrate 8 using the spin coater 2 (f). Thereafter, when the silane coupling agent 9 is dried, the friend substrate 7 having the silane coupling agent 9 formed on the glass substrate 8 is completed (g).

  Next, in accordance with the process as shown in FIG. 3, using the friend substrate 7, the ultraviolet curable resin 3 remaining on the convex portion of the quartz substrate 1 in FIG. A new ultraviolet curable resin 10 is applied on a substrate as shown in FIG. 1E using a spin coater (h).

  Furthermore, the above-mentioned friend substrate 7 is laminated so that the silane coupling treatment surface is in close contact with the ultraviolet curable resin 10 and irradiated with ultraviolet rays. Thereby, the new ultraviolet curable resin 10 is cured by the ultraviolet irradiation, but at this time, it is integrated with the three layers of the ultraviolet curable resin remaining on the etched molded substrate (i).

  Some types of the ultraviolet curable resin 10 are not integrated with the ultraviolet curable resin 3, but here, a resin known to be integrated is used. Most preferably, the ultraviolet curable resin 3 and the ultraviolet curable resin 10 are the same resin.

  Thereafter, the friend substrate 7 is peeled off from the quartz substrate 1. Since the surface of the friend board 7 has been subjected to silane coupling treatment, it is very strongly bonded to the new ultraviolet curable resin 10. Further, the ultraviolet curable resin 10 and the ultraviolet curable resin 3 are also bonded very strongly by being integrated. However, the quartz substrate 1 and the ultraviolet curable resin 3 are not strongly bonded. That is, since the quartz substrate 1 is not subjected to any surface treatment, the adhesion force is the adhesion force between quartz and the ultraviolet curable resin 3 itself. Therefore, all the ultraviolet curable resin 3 can be removed from the surface of the quartz substrate 1 by peeling off the quartz substrate 1 and the friend substrate 7 (j).

  As a result, a line-and-space pattern whose depth is determined by the etching amount is created on the quartz substrate 1 in a shape reverse to that of the pattern formed on the mold 4.

  In the embodiment described above, quartz is used for the substrate. However, even when an object other than quartz or glass is used for the substrate, a resin layer can be similarly formed thereon by providing an adhesion control layer.

  For example, an inversion pattern of a pattern formed on a mold can be formed on an aluminum substrate in the same process as described above using aluminum as the substrate. However, in general, the adhesion between the aluminum substrate and the resin is not good. Therefore, the resin does not peel from the mold as it is, and the resin cannot be molded on the aluminum substrate.

  Therefore, silane coupling treatment is performed before applying the resin on the aluminum substrate. Silane is a surface treatment agent for bonding organic and inorganic substances. Usually, it is diluted to about 3% on the surface of glass, etc., and then applied, baked, and firmly adhered to the surface of glass and the like by chemical bonds. Create a state.

  However, it is also effective to improve the wettability with the resin, etc., by coating on a metal that does not bind OH groups. Accordingly, the adhesion to the resin is improved by performing a silane coupling treatment on the metal. In particular, if a release film such as Ni is formed on the surface of the mold, the resin can be molded on the substrate only by improving the adhesion between the substrate and the resin.

  On the contrary, since the silane coupling treatment is too strong, peeling may be difficult at the time of subsequent friendship. In such a case, the adhesion can be adjusted by increasing the dilution of the silane coupling agent.

  The above explanation is made by taking as an example the case of removing the ultraviolet curable resin remaining on the substrate in the process of engraving the pattern on the substrate. However, the resin removing method according to the method of the present invention is performed in other steps. Can also be used.

It is a figure for demonstrating the manufacturing method of the board | substrate which is embodiment of this invention. It is a figure for demonstrating the manufacturing method of a friend board | substrate. It is a figure for demonstrating the manufacturing method of the board | substrate which is embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Quartz substrate, 2 ... Spin coater, 3 ... Ultraviolet curable resin, 4 ... Mold, 5 ... Molding transfer substrate, 7 ... Friendship substrate, 8 ... Glass substrate, 9 ... Silane coupling agent, 10 ... Ultraviolet curable type resin

Claims (7)

A method of cleaning the substrate by removing unnecessary resin remaining on the substrate from the substrate, wherein a new resin is applied to the surface of the substrate and integrated with the unnecessary resin. And removing the unnecessary resin by peeling off the new resin. After applying a UV curable resin on the substrate, and having a mold having a surface on which a desired fine pattern is formed adhered to the UV curable resin surface, the UV curable resin is cured by irradiating with UV rays, The fine pattern is transferred to the ultraviolet curable resin by peeling the mold, and the substrate is etched using the resin having the transferred fine pattern as a mask, thereby forming the fine pattern on the substrate. A method of manufacturing a substrate having a fine pattern formed on a surface thereof, the method comprising: engraving the fine pattern on the substrate by etching the substrate, and then applying a new resin to the substrate surface. And curing with the ultraviolet curable resin remaining on the substrate after the etching, and then peeling the integrated resin from the substrate. Method of manufacturing a substrate, characterized by. The method of claim 2, further comprising: adhering a friend board having a stronger adhesion to the new resin to the surface of the new resin before the new resin is cured. The manufacturing method of the board | substrate of description. The method for manufacturing a substrate according to any one of claims 1 to 3, further comprising a step of forming an adhesion control layer between the substrate and the ultraviolet curable resin. The method for producing a substrate according to claim 4, wherein the adhesion control layer is obtained by applying a diluted silane coupling agent solution and drying the solution. 6. The method of manufacturing a substrate according to claim 5, wherein a dilution amount of the silane coupling agent solution is changed in accordance with types of the new resin, the substrate, and the friend board. The method for manufacturing a substrate according to any one of claims 1 to 6, wherein the new resin is an ultraviolet curable resin.

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