Method of producing a nanohole on a structure by removal of projections and anodic oxidation

The present invention provides a method of producing a structure, which is capable of easily obtaining a structure of the nanometer scale by using an anodic oxidation method. A method of producing a structure with a hole includes: forming first projected structures regularly arranged on a substrate; forming a first anodic oxidating layer on the substrate having the first projected structures, thereby forming first recessed structures at center portions of cells formed by the projected structures on the anodic oxidating layer; removing the first projected structures to form holes; and subjecting the first anodic oxidating layer to anodic oxidation to form holes at positions of the first recessed structures.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method of producing a structure having projected and recessed structures having an interval of the nanometer scale.

2. Description of the Related Art

As a technique of producing a fine structure on the surface of an object, methods such as photolithography, electron beam exposure, X-ray exposure, and nanoimprint lithography have been known conventionally.

In addition to the above-mentioned methods, there is a method of forming a structure by a bottom-up method using an aluminum anodic oxidation method or a molecular self-organized structure.

Furthermore, a method of producing a pillar-type replica structure using a hole-type nanostructure formed by an anodic oxidation method as a mold has also been proposed. Japanese Patent Application Laid-Open No. 6-32675, Jpn. J. Appl. 36, 7791, 1997, and J. VAc. Sci. Technol. B. 19(2), 569, 2 propose methods in which a hole-type nanostructure is used as a mold, the hole is filled with a material such as resin or metal, and the mold is removed to obtain a pillar structure. Thus, a structure having a minute size and a high aspect ratio, which cannot be obtained by a production method using a semiconductor process, can be produced.

According to the direct patterning technique such as the above-mentioned electron beam lithography and ion beam lithography, a longer period of time is required for forming a pattern as a structure becomes finer. Therefore, for a product mass-produced at low cost, as a mainstream, a mask for X-ray or UV-ray exposure or for an imprint mold is produced precisely by a direct patterning technique, and patterning is performed in a short period of time at a time by photolithography or nanoimprint lithography.

However, there is a limit to the size of a structure that can be formed by any of the above-mentioned methods.

At present, even in an electron beam exposure capable of producing a finest structure, although a single dot of φ10 nm can be formed, it is difficult to arrange the dots with a pitch of 20 nm or less in a large area.

Furthermore, although the above-mentioned conventional method of forming a structure by the bottom-up method using a self-organization method by anodic oxidation of aluminum or a molecular self-organized structure is suitable for forming a regularly repetitive structure in a large area, it is difficult to form an arbitrary structure.

SUMMARY OF THE INVENTION

In view of the above-mentioned problem, an object of the present invention is to provide a method of producing a structure, which is capable of easily obtaining a structure of the nanometer scale, using an anodic oxidation method.

According to a first aspect of the present invention, there is provided a method of producing a structure to solve the above-mentioned problems, including: forming projected structures regularly arranged on a substrate; forming an anodic oxidating layer on the substrate having the projected structures, thereby forming recessed structures at center portions of cells formed by the projected structures on the anodic oxidating layer; removing the projected structures to form holes; and subjecting the anodic oxidating layer to anodic oxidation to form holes at positions of the recessed structures.

According to another aspect of the present invention, there is provided a method of producing a structure to solve the above-mentioned problems, including: forming projected structures regularly arranged on a substrate; forming an anodic oxidating layer on the substrate having the projected structures, thereby forming recessed structures at center portions of cells formed by the projected structures on the anodic oxidating layer; subjecting the anodic oxidating layer to anodic oxidation to form holes at positions of the recessed structures; and removing the projected structures to form holes.

According to still another aspect of the present invention, there is provided a method of producing a structure to solve the above-mentioned problems, including: filling the holes of the structure produced by the method described above with a filling material; and separating the filling material from the structure, thereby obtaining a reversed structure of which the recessed and projected portions respectively correspond to the projected and recessed portions of the structure produced by the method described above.

According to the present invention, there can be obtained a method of producing a structure capable of easily obtaining a structure of the nanometer scale by using an anodic oxidation method.

DESCRIPTION OF THE EMBODIMENTS

A first method of producing a structure solving the above-mentioned problem includes the following: forming projected structures regularly arranged on a substrate; and forming an anodic oxidating layer on the substrate having the projected structures, thereby forming recessed structures at center portions of cells formed by the projected structures on the anodic oxidating layer. Furthermore, the method includes: removing the projected structures to form holes; and subjecting the anodic oxidating layer to anodic oxidation to form holes at positions of the recessed structures.

In this case, the order of the step of removing the projected structures to form holes and the step of subjecting the anodic oxidating layer to anodic oxidation to form holes at positions of recessed structures may be arbitrary.

The first method of the present invention will be described with reference toFIGS. 1A to 1EandFIGS. 2A to 2E.FIGS. 1A to 1Eare cross-sectional views illustrating the steps in one embodiment of a method of producing a structure of the present invention.FIGS. 2A to 2Eare plan views illustrating the steps in one embodiment of the method of producing a structure of the present invention

As shown inFIGS. 1A and 2A, first projected structures2in a triangular lattice arrangement with a period A are formed on a substrate1using photolithography, electron beam lithography, or etching. The first projected structures2are formed of resin, metal, or the like. Next, a first anodic oxidating layer3is laminated on the first projected structures1using sputtering, vapor deposition, or the like, and first recessed structures4and second projected structures5are formed on the surface of the first anodic oxidating layer using sputtering, vapor deposition, or the like (FIG. 1B). The anodic oxidating layer3may be made of, for example, aluminum or an aluminum alloy. The first recessed structures4are positioned at centers of cells14formed between the arranged first projected structures2, i.e., at centers of the second projected structures5(FIG. 2B). At this time, it is desirable to use the forming condition that the first recessed structures4become deeper with respect to the second projected structures5. Next, vertex portions of the first projected structures2buried in the first anodic oxidating layer3are exposed (FIG. 1CandFIG. 2C). Next, the first projected structures are removed by wet etching or dry etching, whereby the second recessed structures6are formed (FIG. ED andFIG. 2D). At this time, the first recessed structures4need to remain.

Assuming that the period of the arrangement of the first recessed structures4and the second recessed structures6is B, when the first projected structures2are in a triangular lattice arrangement, B[nm]=A[nm]/31/2, and when the first projected structures2are in a tetragonal lattice arrangement, B[nm]=A[nm]/21/2. Next, using the first recessed structures4as starting points of forming nanoholes (a hole structure of the nanometer scale will be referred to as “nanohole” in the present invention), the first anodic oxidating layer3is subjected to anodic oxidation. For example, when the first projected structures2are in a triangular lattice arrangement, the substrate is immersed in an acidic solution as an anode and is supplied with an anodic oxidation voltage [V]=A[nm]/31/2×2.5−1, and the anodic oxidating layer3is subjected to oxidation and etching reaction, whereby a nanohole structure is formed (FIG. 1EandFIG. 2E). Because the second recessed structures6have already been recessed structures, nanoholes are not formed, and nanoholes are formed from the first recessed structures4.

In the case where the conductive substrate1is exposed in the bottom portions of the second recessed structures6, an anodic oxidating current is concentrated, so it is necessary to form a base layer to be an oxidation insulating film on the substrate1by anodic oxidation.

After the step of exposing the vertex portions of the first projected structures2(FIG. 1C), the first anodic oxidating layer3may be subjected to anodic oxidation using the first recessed structures4as starting points of forming nanoholes. In this case, the first projected structures2are removed by wet etching or dry etching after the anodic oxidation, whereby a structure as shown inFIG. 1Ecan be produced.

Next, another embodiment of the first method of the present invention will be described with reference toFIGS. 6A to 6E.

This method is similar to the above-mentioned method up to the step inFIG. 1B, so the subsequent steps will be described.

AfterFIG. 6B, the first anodic oxidating layer3is subjected to anodic oxidation using the first recessed structures4as starting points of forming nanoholes (FIG. 6C). The anodic oxidation method is the same as that described above.

Next, vertex portions of the first projected structures2buried in the first anodic oxidating layer3are exposed (FIG. 6D).

Next, the first projected structures2are removed by wet etching or dry etching, whereby the second recessed structures6are formed (FIG. 1E).

According to the above-mentioned method, a structure having a nanohole of the present invention can also be produced.

A second method of the present invention will be described. The second method of the present invention will be described with reference toFIGS. 3A to 3F.FIGS. 3A to 3Fare cross-sectional views illustrating the steps in another embodiment of the method of producing a structure of the present invention.

The second method of producing a structure includes the following: forming a base metal layer on a substrate, and forming a second anodic oxidating layer on the base metal layer. Furthermore, the method includes: subjecting the second anodic oxidating layer to anodic oxidation to form regularly arranged holes and oxidating the base metal layer by the anodic oxidation, thereby allowing a metal oxide to project from the holes to form projected structures arranged regularly; removing a remaining portion of the second anodic oxidating layer; forming a first anodic oxidating layer on the regularly arranged projected structures, thereby forming recessed structures of the first anodic oxidating layer at centers of cells formed between the arranged projected structures; removing the projected structures to form holes; and subjecting the first anodic oxidating layer to anodic oxidation to form holes at positions of the recessed structures.

For example, a base metal layer9is formed on the substrate1, and a second anodic oxidating layer8is formed thereon (FIG. 3A). Herein, the base metal layer9may be made of a material that forms an oxide by anodic oxidation of the second anodic oxidating layer8and that contains, as a main component, at least one element selected from W, Nb, Mo, Ta, Ti, Zr, and Hf. The main component refers to that having a largest weight fraction among the elements contained in a certain material.

Next, the substrate is immersed in an acidic solution as an anode, whereby a nanohole structure is formed in the second anodic oxidating layer8. The anodic oxidation voltage supplied at this time may be [V]=A[nm]×2.5−1, assuming that the period of regularly arranged nanoholes to be formed is A. As a method of regulating nanoholes, a self regulating condition of alumina nanoholes, the use of starting points of nanoholes on the surface of the second anodic oxidating layer8, and the like are proposed. Anodic oxidation is continued even after the bottom portions of nanoholes to be formed reach the base metal layer9, or a voltage is supplied again after the solution is changed to another kind of solution in which the oxidation is promoted more than the dissolution of the base metal layer9. As a result, the volume of the base metal layer9increases, and the base metal layer9is formed as the first projected structure2in the nanoholes formed in the second anodic oxidating layer8(FIG. 3B). Next, etching is performed in an atmosphere of gas or liquid in which the second anodic oxidating layer8is dissolved and the first projected structures2are not affected, whereby the second anodic oxidating layer8is removed (FIG. 3C).

Next, in the same way as in the first method of the present invention, using sputtering, vapor deposition, or the like, the first anodic oxidating layer3is laminated on the first projected structures2, and the first recessed structures4are formed on the surface of the first anodic oxidating layer (FIG. 3D). Herein, in the case where the first projected structures made of the base metal layer have a high aspect or the period A is large relative to the diameter of the first projected structures, the first projected structures2are likely to be exposed from the vertex portions of the second projected structures5. Therefore, the step of exposing the first projected structures2as in the first method of the present invention is not required, and etching is performed in an atmosphere of gas or liquid in which the first projected structures2are removed without affecting the first anodic oxidating layer3, whereby second recessed structures6can be formed (FIG. 3E). Finally, when anodic oxidation is performed at an anodic oxidation voltage B [nm]×2.5−1[v] in the same way as in the first method, recessed structures with a period B are produced (FIG. 3F).

The steps afterFIG. 3Dcan also be performed as follows.

Another embodiment of the second method of the present invention will be described with reference toFIGS. 7A to 7F.

This method is similar to the above-mentioned method up to the step inFIG. 3D, so the subsequent steps will be described.

AfterFIG. 7D, using the first recessed structures4as starting points of forming nanoholes, the first anodic oxidating layer3is subjected to anodic oxidation (FIG. 7E). The method of anodic oxidation is the same as that as described above.

Finally, by removing the first projected structures, a structure having a nanohole according to the present invention can be produced (FIG. 7F).

As described above, after forming the first recessed structures and the second projected structures in the first and second methods of the present invention as described above, anodic oxidation may be performed at an anodic oxidation voltage [V]=B[nm]×2.5−1, and thereafter, the first projected structures may be removed. In this case, it is not preferable that the first projected structures are made of an insulator, because nanoholes are formed from the periphery of the first projected structures. It is not preferable that the first projected structures are made of a conductor and are in conduction with metal, because current is concentrated during anodic oxidation. That is, it is preferable that the first projected structures are made of a material having an appropriate resistance, a metal which forms an oxide with an anodic oxidation voltage, or the like.

Next, a third production method of the present invention will be described. In the first method of the present invention, when the substrate1is made of aluminum or an aluminum alloy, which is a material for forming nanoholes by anodic oxidation, a structure having a higher aspect ratio can be formed. In anodic oxidation in the first method of the present invention, both the second recessed structures and the first recessed structures function as starting points, and nanoholes can be formed continuously in the substrate1(FIG. 4). Herein, when the composition of the first anodic oxidating layer3is different from that of the substrate1, even if anodic oxidation is performed under the same anodic oxidation condition, the diameter of nanoholes to be formed may vary.

The structure produced by the above-mentioned method of the present invention is filled with a different material, and then the filling material is separated, whereby a replica structure (reversed structure in which the projected and recessed portions of the structure produced by the above-mentioned method of the present invention are reversed) can also be produced. As to filling, various kinds of methods are considered. For example, in the case of filling a liquid resin, the resin is dropped onto hole openings in vacuum, or degassing processing is performed by centrifugal force. Furthermore, in the case of filling a metal or the like, sputtering or vapor deposition is performed.

In the first to third methods of the present invention, even in the case where the regular arrangement of the first projected structures is composed of a plurality of kinds of arrangements, the structure can be produced by a similar method. For example, there is a case where a triangular lattice arrangement with a period A and a tetragonal lattice region with the period A are arranged with a common part13(FIG. 5). At this time, it is preferable that the anodic oxidation voltage is A[nm]×2.5−1[V], and the structure can be formed in accordance with the arrangement without causing disorder of the holes in the common part.

EXAMPLES

Hereinafter, the present invention will be described by way of examples with reference to the drawings.

First, a substrate1is obtained by laminating titanium (Ti) with a thickness of 10 nm on silicon (Si). On the substrate1, first projected structures2, in which projected structures (diameter: 35 nm and height: 50 nm) are arranged in a triangular lattice arrangement with a period of 70 nm as shown inFIGS. 1A and 2A, is formed on the substrate with an electron beam resist by electron beam lithography. As the resist, ZEP520A produced by ZEON Co. or polymethyl methacrylate (PMMA) was used. Next, a first anodic oxidating layer3made of an aluminum-hafnium (AlHf, the atomic weight percentage of Hf: 6 atm %) alloy with a thickness of 40 nm is laminated on the electron beam resist. On the surface of the first anodic oxidating layer3, first recessed structures4and second projected structures5are formed (FIG. 1B). By adjusting sputtering conditions, the first recessed structures4are positioned at centers of gravity (center points) of unit cells of the second recessed structures5, and the bottom portions of the first recessed structures are positioned lower than the first projected structures (FIG. 2B). Next, the vertex portion of the electron resist buried in the AlHf alloy layer is exposed by dry etching in a mixed plasma of chlorine gas and oxygen gas (FIG. 1CandFIG. 2C). Subsequently, the electron beam resist is removed by dry etching in an oxygen gas plasma (FIG. 1DandFIG. 2D). At this time, care should be taken so that the first recessed structures4remain without fail. The period of the arrangement of the first recessed structures4and the second recessed structures6is about 40 nm. The substrate is immersed in a sulfuric acid aqueous solution (1 mol/L, 10° C.) as an anode, and anodic oxidation is performed at a voltage of 16.2 V. Oxidation and etching reaction are effected with both the first recessed structures4and the second recessed structures6being as starting points, whereby a nanohole structure is formed (FIG. 1EandFIG. 2E).

Because the second recessed structures have already been of recessed structures, a sulfuric acid aqueous solution enters therein. However, the titanium layer becomes an oxide by anodic oxidation and is difficult to be dissolved, so nanoholes are formed only in the first recessed structures.

Furthermore, tungsten (W) is deposited by sputtering so as to fill the nanohole structure, and a support substrate is attached thereto with an adhesive and is peeled off, whereby a replica projected structure with the projected and recessed portions as reversed can be obtained.

On a silicon substrate1, tungsten (W) is laminated to a thickness of 20 nm as a base metal layer9, and furthermore, the same aluminum-hafnium alloy as that of Example 1 is formed to a thickness of 200 nm as a second anodic oxidating layer8(FIG. 3A). On the surface of the aluminum-hafnium alloy layer, recessed structures in a triangular lattice arrangement with a pitch of 70 nm is formed by a focused ion beam (FIB) method. Next, a substrate is immersed in an oxalic acid aqueous solution (0.3 mol/L, 20° C.) as an anode, and a voltage of 28 V is applied to the aluminum-hafnium alloy layer, whereby anodic oxidating nanoholes are formed. The nanoholes are formed with the recessed structures formed by the FIB method being starting points, so a triangular lattice arrangement with a pitch of 70 nm is obtained. If the anodic oxidation is continued even after the bottom portions of the nanoholes reach the tungsten layer, the oxidation is promoted to increase the volume of tungsten, whereby tungsten grows in the nanoholes (FIG. 3B). At the time when the length of the tungsten oxide from the substrate reaches 200 nm, the anodic oxidation is terminated. Herein, in the case of increasing the diameter of the tungsten oxide, the following may be conducted. The anodic oxidation is suspended once at the time when the nanoholes reach the tungsten layer, the nanoholes are immersed in a phosphoric acid aqueous solution (5 wt %) to be dissolved to an arbitrary diameter, and anodic oxidation is performed again to grow tungsten oxide.

When the substrate is immersed in a phosphoric acid aqueous solution (5 wt %) for several hours to remove the aluminum-hafnium alloy layer, the tungsten oxide arranged regularly remains (FIG. 3C). In the same way as in Example 1, the aluminum-hafnium alloy layer with a thickness of 150 nm is laminated by sputtering, whereby first recessed structures4and second projected structures5are formed (FIG. 3D). The tungsten oxide can form a structure with a very high aspect ratio, compared with the resist structure obtained by lithography in Example 1, so even after the first anodic oxidating layer is laminated, the entire surface of tungsten oxide is not covered. Therefore, tungsten oxide can be removed without exposing the tip end portions of the second projected structures5. Tungsten oxide is removed by baking and immersion in a phosphoric acid aqueous solution (5 wt %) (FIG. 3E). Finally, the resultant structures are immersed in a sulfuric acid aqueous solution (1 mol/L, 10° C.) in the same way as in the first method, and anodic oxidation is performed at an anodic oxidation voltage of 16.2 [V], so a triangular lattice arrangement nanohole structure with a period of 40 nm is obtained.

In this case, it is also applicable to perform anodic oxidation at a voltage of 16.2 [V] without removing tungsten oxide followed by removal of tungsten oxide. Under the same condition as that of the above, first recessed structures and second projected structures are formed (FIG. 3D), and anodic oxidation at a voltage of 16.2 [V] is performed without removing tungsten oxide, whereby third recessed structures are formed with the first recessed structures being starting points. In conducting normal anodic oxidation, which is a self-regulating phenomenon, nanoholes are formed even at the position of the tungsten oxide. However, in this case, due to the presence of tungsten oxide, holes are not formed, oxidation is promoted at a rate in accordance with an applied voltage, and the formation of nanoholes from the first recessed structures is not inhibited. Next, when the tungsten oxide2is baked and immersed in a sulfuric acid aqueous solution (5 wt %) and is removed, a structure shown inFIG. 3Fis obtained.

The case where the substrate1is made of aluminum in Example 1 will be described. After the first projected structures are removed, the resultant structures are immersed in a sulfuric acid aqueous solution (1 mol/L, 10° C.), and a voltage of 16.2 [V] is applied to perform anodic oxidation. The first recessed structures and the second recessed structures function as starting points of forming nanoholes, whereby a structure is formed. Nanoholes can be formed continuously from the aluminum-hafnium alloy layer to the aluminum substrate. Under the above-mentioned anodic acid oxidation conditions, the diameter of the nanoholes formed in the aluminum-hafnium alloy is smaller than that of the nanoholes formed in the aluminum substrate; however, the regularity is not lost (FIG. 4). Furthermore, the formation of nanoholes proceeds further as the depth of the initial starting point is larger. Therefore, in the case where the depth of the second recessed structures6is larger than that of the first recessed structures4(FIG. 1D), nanoholes from the second recessed structures are formed earlier (FIG. 4). Herein, it is not preferable that there is too much difference in depth between the first recessed structures and the second recessed structures, because the verticality of nanoholes from the deep side with respect to the substrate is impaired.

According to the present invention, a structure of the nanometer scale can be obtained easily using a conventional anodic oxidation method of aluminum or the like, so the present invention can be used for a method of producing a structure on a nanometer scale.

This application claims the benefit of Japanese Patent Application Nos. 2006-228364, filed Aug. 24, 2006 and 2007-137225, filed May 23, 2007, which are hereby incorporated by reference herein in their entirety.