JP2011084068A - Method for manufacturing fine pattern duplicate, and duplicate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To simply manufacture a fine duplicate of a molecular level with contrast. <P>SOLUTION: The coating of a resin is carried out to a plate which has a convex-like pattern on the surface, a stamp comprising the resin is produced by exfoliating the resin from the plate, a hydrophobic molecule ink dispersing a hydrophobic molecule therein is made to adhere to the stamp, a fine pattern comprising a layer of the hydrophobic molecule is formed on a substrate using the stamp to which the molecule ink adhered, is immersed in the hydrophilic molecule ink making a hydrophilic molecule disperse around the substrate surface of the fine pattern, and thereby a fine pattern duplicate which gives chemical modification is manufactured. In this case, after forming the fine pattern, a substrate on which a fine pattern has been formed is immersed in water, hydrophobic molecules composing a fine pattern is made to hydrophobic bond together, and the hydrophobic molecules are made to aggregate together, then chemical modification by the hydrophilic molecule ink is given to the substrate surface around the fine pattern in water. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a fine pattern replica and a replica capable of developing a pattern at a molecular level in a manufacturing process of various functional devices, DNA chips and the like.

  In the field of molecular chemistry, F. L. Carter proposed the concept of a molecular device in 1982, and since then, research, development in this field has been actively conducted by companies, universities, research institutions, and the like. For example, if a function is given to each organic molecule and an aggregate of these organic molecules is formed, it is possible to form an ultra-high density semiconductor device that is not comparable to the degree of integration so far. . In recent years, DNA genome analysis and the like have been actively researched, and so-called biochips have attracted attention, but their application is also conceivable.

  On the other hand, photolithography, which has been conventionally performed as a method for replicating a fine pattern, involves the steps of replicating a substrate with a desired pattern by taking several steps for each sheet. There was a limit. In addition, since photolithography involves complicated processes such as exposure, development, and etching, it is not suitable for handling materials such as cells, DNA, enzymes, etc. that are weak in heat resistance, mechanical resistance, and the like. In addition, the printing method makes it possible to produce a large number of replicas, but until now, it has been limited to replicating patterns of about several hundred μm, and it has not been suitable for the production of fine pattern replicas.

  In view of the above problems, the inventor first forms a first transfer layer by patterning a molecular ink in which molecules of a predetermined polarity are dispersed on a substrate, and molecules that match or do not match the polarity. Invented a method for replicating a fine pattern comprising forming a second transfer layer with a molecular ink in which is dispersed (Japanese Patent Application No. 2000-151157).

However , in the above method, since the density of the ink used for increasing the resolving power is reduced and the transfer is performed with the low density ink, the film of the first transfer layer has a defect, and the first transfer layer Since the second transfer layer is not completely covered, the ink for the second transfer layer enters and contaminates the already formed first transfer layer, resulting in the contrast between the first and second layers. There was a problem that decreased.

Further , if the ink density is increased so as to eliminate defects during the formation of the first transfer layer, there is a problem that the ink bleeds and diffuses and the resolving power decreases.

An object of the present invention is to provide a method for producing a fine pattern replica and a replica capable of easily producing a fine replica at a molecular level with contrast.

The invention according to claim 1 is obtained by coating a resin on a plate having a convex pattern on the surface, and peeling off the resin from the plate to produce a stamp made of the resin and dispersing hydrophobic molecules. Hydrophobic molecular ink is attached to the above-mentioned disc, and a fine pattern composed of a layer of hydrophobic molecules is formed on the substrate using the disc on which the molecular ink is attached, and hydrophilic molecules are applied to the substrate surface around the micro-pattern. in the method for manufacturing a fine pattern replication was subjected to chemical modification by immersing in a hydrophilic molecule ink obtained by dispersing, after formation of the fine pattern, immersed one formed a fine pattern on a substrate in water, According hydrophobic molecules that constitute the fine pattern after allowed set hydrophobic molecules each other by hydrophobic bonding to the hydrophilic molecule ink to the substrate surface around the fine pattern in water And characterized by applying Manabu modified. According to the method for producing a copy of a fine pattern according to the present invention, after formation of a fine pattern composed of a layer of hydrophobic molecules formed by patterning on a substrate using a molecular ink in which hydrophobic molecules are dispersed, Since the hydrophilic molecule ink is chemically modified with the hydrophilic molecule ink on the substrate surface around the fine pattern in a state where the hydrophobic molecule is hydrophobically bonded in an aqueous solution, the probability that the hydrophilic molecule enters the hydrophobic molecule layer is low. As a result, the hydrophobicity of the fine pattern portion is not impaired, and a high contrast with the substrate surface region around the fine pattern chemically modified with hydrophilic molecules can be obtained.

In the invention of claim 1, it was subjected to chemical modification with a hydrophilic molecular ink in water to the substrate surface around the fine pattern, higher density chemically modified with hydrophobic molecules ink onto a fine pattern in alcoholic solution May be. In this second process, the defective portion of the fine pattern is completely repaired.

According to a third aspect of the invention, by coating a resin plate having a convex pattern on the front surface and the resin to produce a stamp made of the resin by peeling from the plate, by dispersing hydrophilic molecules A hydrophilic molecule ink is attached to the disc, and a fine pattern composed of a layer of hydrophilic molecules is formed on the substrate using the discriminator to which the molecular ink is attached, and hydrophobic molecules are formed on the substrate surface around the fine pattern. In the method for producing a fine pattern replica, which is chemically modified by immersing in a hydrophobic molecular ink in which water is dispersed, after forming the fine pattern, the fine pattern formed on the substrate is immersed in an organic solution. the hydrophobic molecule hydrophilic molecules that constitute the fine pattern after allowed set hydrophilic molecules each other by hydrogen bonding, to the substrate surface around the fine pattern in organic solution And characterized by applying chemical modification by links. According to the method for producing a micropattern replica according to the present invention, after forming a micropattern consisting of a layer of hydrophilic molecules formed by patterning on a substrate using a molecular ink in which hydrophilic molecules are dispersed, Since the hydrophobic molecular ink is applied to the substrate surface around the fine pattern in the solution, the probability of the hydrophobic molecule entering the hydrophilic molecule layer is low, resulting in high contrast with the substrate surface region around the fine pattern. Is obtained.

In the invention according to claim 3, after the substrate surface around the fine pattern is chemically modified with a hydrophobic molecular ink in an organic solution, it is further densified with a hydrophilic molecular ink on the fine pattern in an alcohol solution. It may be chemically modified. In this second process, the defective portion of the fine pattern is completely repaired.

In the invention of any one of claims 1 to 4, the plate as, divorced, quartz or photolithography on a metal or the surface of the laminated body formed by laminating a metal oxide thereon, electron-beam lithography, etc. A plate on which a convex pattern is formed by ionizing radiation lithography or AFM lithography can be applied.

  In the invention according to any one of claims 1 to 4, it is desirable to use polydimethylsiloxane as a resin to be used.

  The invention according to any one of claims 1 to 4, wherein the hydrophobic molecule ink formed by dispersing hydrophobic molecules is a molecule having an SH group at the terminal, a silane coupling agent or a carboxylic acid, a sulfonic acid, a phosphone. An ink in which any of acid, phosphoric acid, or acid chlorides thereof is dispersed can be used.

5. The invention according to claim 1, wherein the hydrophobic molecular ink obtained by dispersing hydrophobic molecules has a moiety represented by any of the following structural formulas: X _1- (CH ₂ ) _n— (part represented by any of the following structural formulas) — (CH ₂ ) _m —Y (where m, n ≧ 0) X ₁ is a hydrophobic group, and Y located at the other end is capable of binding to the substrate —SH, —COOH, —SO ₃ H, —PO ₃ H, —PO ₃ H _2, —COCl, —SO ₂ Cl, -PO ₂ Cl, a molecule with a group such as -PO ₂ Cl ethanol, toluene, ink was dispersed in an organic solvent such as methylene chloride can be used.

In the invention according to any one of claims 1 to 4, as a hydrophilic molecule ink in which hydrophilic molecules are dispersed , a molecule having a phosphate group on the side opposite to the substrate binding group, a molecule having a phosphonic acid group, An ink in which any one of a molecule having a carboxylic acid group, a molecule having an amino group, and a molecule having a hydroxyl group is dispersed can be used.

The invention according to any one of claims 1 to 4, wherein the hydrophilic molecular ink obtained by dispersing hydrophilic molecules has a moiety represented by any of the following structural formulas: X _2- (CH ₂ ) _n— (part represented by any of the following structural formulas) — (CH ₂ ) _m —Y (where m, n ≧ 0) X ₂ is a hydrophilic group, and Y located at the other end is capable of binding to the substrate —SH, —COOH, —SO ₃ H, —PO ₃ H, —PO ₃ H _2, —COCl, —SO ₂ Cl, -PO ₂ Cl, the molecular is a group such as -PO ₂ Cl ethanol, toluene, ink was dispersed in an organic solvent such as methylene chloride can be used.

  In the invention according to any one of claims 1 to 4, when the molecule of the hydrophobic molecule ink in which the hydrophobic molecule is dispersed is a molecule having an SH group at the end, the substrate on which the fine pattern is formed is formed. It is desirable to use a substrate on which gold, silver, or copper is formed on the surface. When a substrate coated with gold or silver or copper is used, the resolving power is improved by the self-organizing action.

  In the invention according to any one of claims 1 to 4, when the molecule of the hydrophilic molecule ink in which the hydrophilic molecule is dispersed is a molecule having an SH group at the terminal, the substrate on which the fine pattern is formed is formed. It is desirable to use a substrate on which gold, silver, or copper is formed on the surface. When a substrate coated with gold or silver or copper is used, the resolving power is improved by the self-organizing action.

  In the invention according to any one of claims 1 to 4, the hydrophobic molecule of the hydrophobic molecule ink formed by dispersing the hydrophobic molecule is a silane coupling agent, carboxylic acid, sulfonic acid, phosphonic acid, phosphoric acid or When these acid acid chlorides are included, it is desirable to use a substrate in which silicon oxide or metal oxide is coated on the surface of the substrate on which a fine pattern is formed. In this case, the resolution is similarly improved by the self-organizing action.

  In the invention according to any one of claims 1 to 4, the hydrophilic molecule of the hydrophilic molecular ink obtained by dispersing hydrophilic molecules is a silane coupling agent, carboxylic acid, sulfonic acid, phosphonic acid, phosphoric acid or When these acid acid chlorides are included, it is desirable to use a substrate in which a silicon oxide or metal oxide is coated on the surface of the substrate on which a fine pattern is formed. In this case, the resolution is similarly improved by the self-organizing action.

In the invention of any one of claims 1 to 4, on the opposite side of the hydrophilic molecule is a substrate binding groups of the hydrophilic molecular ink formed by dispersing a hydrophilic molecule, a phosphoric acid group, a phosphonic acid group, a sulfonic acid In the case of a molecule having any one of a group, a carboxylic acid group, an amino group, and a hydroxyl group, it is desirable to use a substrate in which silicon oxide or metal oxide is coated on the surface of the substrate on which a fine pattern is formed. Similarly, the resolution is improved by the self-organizing action.

In the invention according to any one of claims 1 to 4 , it is desirable that the molecular ink is adhered to the disc by a wet inking method.

In the invention according to any one of claims 1 to 4 , it is desirable that the molecular ink is attached to the stamp by a contact inking method .

In the invention according to any one of claims 1 to 4 , the fine pattern may be configured by stacking two or more kinds of transfer layers using molecular inks containing different molecules.

A fine pattern replica produced by the method according to claim 1 or 2 is a fine pattern comprising a layer of hydrophobic molecules formed by patterning on a substrate using a hydrophobic molecular ink in which hydrophobic molecules are dispersed. the provided comprises a layer of hydrophilic molecules to the substrate surface around the fine pattern, characterized that you have ready for hydrophobic molecules fine pattern are aggregated by hydrophobic bonding in water.

The fine pattern replica produced by the method according to claim 3 or 4 is a fine pattern comprising a hydrophilic molecule layer formed by patterning on a substrate using a hydrophilic molecule ink in which hydrophilic molecules are dispersed. wherein the comprises a layer of hydrophobic molecules on the substrate surface around the fine pattern, hydrophilic molecules of fine pattern features that you have in a state of aggregation by hydrogen bonding in organic solution.

These duplicates may be formed by transferring a fine pattern twice or more using molecular inks containing different molecules.

As described above in detail, according to the method for producing a fine pattern replica according to the first aspect of the present invention, a hydrophobic pattern formed by patterning on a substrate using a molecular ink in which hydrophobic molecules are dispersed. After the formation of a fine pattern consisting of layers of functional molecules, the fine pattern formed on the substrate is immersed in water, and the hydrophobic molecules constituting the fine pattern are bonded to each other by hydrophobic bonding. Since the hydrophilic molecule ink is chemically modified on the substrate surface around the fine pattern in a state where the hydrophobic molecules are hydrophobically bonded to each other in an aqueous solution, the probability that the hydrophilic molecules enter the hydrophobic molecule layer is low. As a result, the contrast with the substrate surface area around the fine pattern chemically modified with hydrophilic molecules was obtained without impairing the hydrophobicity of the fine pattern portion.

In addition , according to the method for producing a fine pattern replica according to the invention of claim 3, the method comprises a hydrophilic molecule layer formed by patterning on a substrate using a molecular ink in which hydrophilic molecules are dispersed. After the formation of the fine pattern, the fine pattern formed on the substrate is immersed in an organic solution, and the hydrophilic molecules constituting the fine pattern are hydrogen-bonded to gather together the hydrophilic molecules. In the state where the hydrophilic molecules are hydrogen-bonded with each other, the substrate surface around the fine pattern is chemically modified with the hydrophobic molecule ink, so the probability that the hydrophobic molecule enters the hydrophilic molecule layer is low, resulting in fine The hydrophilicity of the pattern portion was not impaired, and a high contrast with the substrate surface area around the fine pattern chemically modified with the hydrophobic molecule was obtained.

  The replica of the present invention can be used for applications such as binding of specific molecules or immobilization of enzymes, cells, DNA, etc., using combinations of different surface properties.

FIG. 5 is a process diagram showing a process of chemically modifying a fine pattern composed of hydrophobic molecules on a substrate and a surrounding substrate surface with hydrophilic molecules according to the first aspect of the present invention. It is process drawing which shows the process of chemically modifying with the fine pattern which consists of a hydrophobic molecule on the board | substrate following the process shown in FIG. 1, and the surrounding substrate surface with a hydrophilic molecule. It is explanatory drawing of the adhesion method of the molecular ink with respect to a stamp. It is a figure explaining the effect of the preparation method of the fine pattern replication of this invention using a hydrophobic bond. FIG. 4 is a process diagram showing a process of chemically modifying a fine pattern made of hydrophilic molecules on a substrate and a surrounding substrate surface with hydrophobic molecules according to the invention of claim 3 . FIG. 6 is a process diagram illustrating a process of chemically modifying a fine pattern made of a hydrophobic molecule on a substrate and a surrounding substrate surface with hydrophilic molecules on the substrate following the process shown in FIG. 5.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a process diagram of a method for producing a fine pattern replica according to claim 1.

First, as shown in FIG. 1A, a plate 1 having a convex pattern 1a having a desired step on the surface is prepared. As the material of the plate 1, silicon, quartz, or a material in which a metal or a metal oxide is laminated thereon is used. Then, they divorced patterned by lithography thereon, quartz, to form a more convex pattern 1a to the metal or an oxide thereof. The step formed by the convex pattern 1a is preferably about 0.1 to 5 μm.

Next, as shown in FIG. 1B, after the resin 2 is coated on the surface of the plate 1 having the convex pattern 1a , the resin 2 is peeled off to remove the resin as shown in FIG. 1C. A maker 3 is prepared. As the resin used as the size 3, it is preferable to use a polydimethylsiloxane resin (PDMS). The size 3 is prepared by spin-coating this PDMS resin, taking a mold by heat treatment.

Next, as shown in FIG. 1 (d), a molecular ink 4 in which hydrophobic molecules are dispersed is attached to a stamp 3, and using the stamp 3 , a glass plate or the like is used as shown in FIG. 1 (e). A fine pattern 6 made of hydrophobic molecules is formed on a substrate 5 formed by coating gold on the surface.

The hydrophobic molecule ink may be molecules having an SH group in end end, a silane coupling agent or a carboxylic acid, sulfonic acid, phosphonic acid, an ink prepared by dispersing either phosphoric acid or their acid chlorides . Here, when using a substrate coated with gold on the surface as the base plate, the resolution is improved by self-organizing action contained in the ink.

  There are two methods for attaching the molecular ink 4 to the seal 3 as shown in FIG. The method shown in FIG. 3 (a) is a wet inking method in which ink is placed on the stamp 3 and the ink 4 is applied to the entire surface. The method shown in FIG. This is a contact inking method in which the ink 4 is applied only to the tip of the size 3 by pressing the PDMS resin 8 against the size 3. The contact inking method is superior to the wet inking method in terms of resolving power because ink diffusion can be reduced.

Next , as shown in FIG. 2A, the substrate 5 on which the fine pattern 6 is formed is immersed in water 9. Hydrophobic molecules constituting the fine pattern 6 are hydrophobically bonded to each other to aggregate the hydrophobic molecules, thereby forming a fine pattern with few defective portions.

Then, the substrate surface which is not covered with a fine pattern on the substrate 5 formed with hydrophobic binding processing a fine pattern 6 having a water HS (CH _{2) Y} -COOH into an aqueous solution containing a solution or KOH is dispersed The substrate surface is chemically modified using a solution in which HS (CH ₂ ) _Y —COOH is dispersed. This makes it possible to form a hydrophilic region around the hydrophobic fine pattern forming region without impairing the hydrophobicity and form a fine pattern with high contrast with respect to the periphery of the pattern.

FIG. 4 is a diagram for explaining the effect of the method for producing a fine pattern replica of the present invention using a hydrophobic bond. FIG. 4 (a) shows a state like that were assembled hydrophobic molecules that constitute a fine pattern by immersing the fine pattern 6 formed in the water by hydrophobic bonding schematically. Coated with a hydrophobic component child area of a fine pattern 6 by hydrophobic bonding process that collectively As can be seen, less fine pattern 6 'defects are formed. That is, a fine pattern film that does not expose the metal base surface is formed.

Then, the substrate surface around the fine pattern 6 ', immersed in a solution containing dispersed HS (CH _{2) Y} -COOH in an aqueous solution containing water in HS (CH ₂₎ a solution or KOH is dispersed _Y -COOH the region 7 of the hydrophilic component element formed around the the subjected to chemical modification FIG 4 (b) the fine pattern 6 without impairing the hydrophobic fine pattern as shown 'due to, for a region of ambient Thus, a fine pattern 6 'having a high contrast is formed.

Further in the above invention, fine after chemical modification of hydrophilic molecules to the substrate surface around the pattern, hydrophobicity ink higher density or chemical modification of hydrophobic molecules on the fine pattern in an alcohol solution of, Hydrophobic molecules may be transferred onto the fine pattern by using a seal with hydrophobic ink attached again. In this second process, the defective portion of the fine pattern is completely repaired.

  The fine pattern of the fine pattern replica formed as described above is a chemically modified AFM (Atomic Force Microscope) chip (the surface of a gold-coated AFM chip chemically modified with 1 mK of 1-eicosanethiol. ) Using a chemical force microscope.

Next , a method for producing a fine pattern replica according to the third aspect of the present invention will be described with reference to FIG. First, as shown in FIG. 5A, a plate 1 having a convex pattern 1a having a desired step on the surface is prepared. As the material of the plate 1, silicon, quartz, or a material in which a metal or a metal oxide is laminated thereon is used. Then, they divorced patterned by lithography thereon, quartz, to form a more convex pattern 1a to the metal or an oxide thereof. The step formed by the convex pattern 1a is preferably about 0.1 to 5 μm.

  Next, as shown in FIG. 5 (b), the resin 2 is coated on the surface of the plate 1 having the convex pattern 1a, and then the resin 2 is peeled off, thereby removing the resin as shown in FIG. 5 (c). A stamp 3 is prepared. As the resin used as the size 3, it is preferable to use a polydimethylsiloxane resin (PDMS). The size 3 is prepared by spin-coating this PDMS resin, taking a mold by heat treatment.

Next, as shown in FIG. 5 (d), a molecular ink 14 in which hydrophilic molecules are dispersed is attached to the stamp 3, and using the stamp 3 , a glass plate or the like as shown in FIG. 5 (e). A fine pattern 16 made of hydrophilic molecules is formed on a substrate 5 formed by coating gold on the surface.

As hydrophilic molecule ink, a molecule having a phosphate group, a molecule having a phosphonic acid group, a molecule having a carboxylic acid group, a molecule having an amino group, or a molecule having a hydroxyl group is dispersed on the side opposite to the substrate binding group. Ink dispersed in any of the above inks can be used. Here, when a substrate coated with silicon oxide or metal oxide is used as the substrate, the resolution is improved by a self-organizing action.

As the adhesion method of the molecular ink 14 to the stamp 3, there are a wet inking method and a contact inking method as described above with reference to FIG . The contact inking method is superior in terms of resolution because the ink inking can be reduced by the wet inking method.

Next , as shown in FIG. 6A, the substrate 5 on which the fine pattern 16 is formed is immersed in the organic solution 17 . In the organic solution 17, the hydrophilic molecules constituting the fine pattern 16 are difficult to mix with the organic solution, and the hydrophilic molecules are aggregated by hydrogen bonding, so that the substrate surface around the fine pattern 16 contains hydrophobic molecules. In the process of chemical modification with a solution, the probability that hydrophobic molecules adhere to the fine pattern is low. As a result, as shown in FIG. 6 (b), a region 7 chemically modified with a hydrophobic molecule is formed around the hydrophilic fine pattern forming region without impairing the hydrophilicity, and the contrast around the periphery of the pattern is formed. High fine pattern can be formed.

In the above invention, after the chemical modification of the hydrophobic molecule ink in an organic solvent to the substrate surface around the fine pattern, a hydrophilic molecule further high density on a fine pattern in alcoholic solution of the parent water molecules ink Hydrophilic molecules may be transferred onto the fine pattern by chemical modification or by using a seal with hydrophilic ink attached again. In this second process, the defective portion of the fine pattern is completely repaired.

  The fine pattern of the fine pattern replica formed as described above is a chemically modified AFM (Atomic Force Microscope) chip (the surface of a gold-coated AFM chip chemically modified with 1 mM 1-eicosanethiol). ) Using a chemical force microscope.

Although the foregoing invention your information, by coating a resin plate having a convex pattern on the surface and the resin to produce a stamp element composed of the resin by removing the plate or al, is dispersed hydrophobic molecules comprising a hydrophobic molecule ink deposited on the-size children, to form a fine pattern comprising a layer of hydrophobic molecules on a substrate using the adhered determine terminal of the molecule ink, the substrate surface around the fine pattern those in the method for manufacturing a fine pattern replication was subjected to chemical modification by hydrophilic molecules dispersed is immersed in a hydrophilic molecule ink comprising, after formation of the fine pattern to form a fine pattern on a substrate was immersed in water, the hydrophobic molecules that constitute the fine pattern after allowed set hydrophobic molecules each other by hydrophobic bonding in the hydrophilic molecule ink to the substrate surface around the fine pattern in water chemistry Osamu It is subjected to. In such a case, the substrate surface around the fine pattern is chemically modified with hydrophilic molecular ink in water, and then chemically modified with a hydrophobic molecular ink on the fine pattern in an alcohol solution to a higher density or again hydrophilic. Hydrophilic molecules may be transferred onto the fine pattern using a sample with a hydrophilic ink attached. In this second process, the defective portion of the fine pattern is completely repaired.

Instead of doing so, hydrophilic is formed by coating a resin on a plate having a convex pattern on the surface, and peeling the resin from the plate to produce a stamp made of the resin and dispersing hydrophilic molecules. A molecular ink is attached to the disc, a fine pattern composed of a hydrophilic molecule layer is formed on the substrate using the disc to which the molecular ink is attached, and hydrophobic molecules are dispersed on the substrate surface around the fine pattern. In the method for producing a fine pattern replica that is chemically modified by immersing in a hydrophobic molecular ink, the fine pattern formed on the substrate is immersed in an organic solution after the formation of the fine pattern. the hydrophilic molecules that constitute from brought set hydrophilic molecules each other by hydrogen bonds and the hydrophobic molecule to the substrate surface around the fine pattern in organic solution It can also be made of fine pattern replica by performing chemical modification by links. In that case, after performing chemical modification with a hydrophobic molecular ink in an organic solution on the substrate surface around the fine pattern, it is further chemically modified with a hydrophilic molecular ink on the fine pattern in an alcohol solution. The hydrophilic molecule may be transferred onto the fine pattern by using a sizer to which the hydrophilic ink is attached again. In this second process, the defective portion of the fine pattern is completely repaired.

In addition to the above-described hydrophobic molecular ink obtained by dispersing hydrophobic molecules, the hydrophobic molecular ink described in paragraph 0015 can be used.

In addition to the above-described hydrophilic molecular ink obtained by dispersing hydrophilic molecules, the hydrophilic ink described in paragraph 0024 can be used.

Example 1
First, a chromium thin film was formed on the surface of the quartz plate by sputtering, a resist pattern having a thickness of 4000 mm was formed on the chromium thin film deposited on the quartz plate, and a plate having a step on the surface was produced. Then, PDMS resin was spin-coated on the surface provided with the resist pattern of this plate, heat-treated at 65 ° C. for 4 hours, and then the plate was peeled off from the cured PDMS resin to form a stamp. Next, an ink made of an ethanol solution of CH ₃ (CH ₂ ) ₁₉ SH was attached to the disc by the contact inking method.

  On the other hand, a fine pattern is prepared by preparing a substrate on which a gold vapor deposition layer is formed by vapor deposition on a glass plate, and transferring the molecular ink onto the substrate by pressing the surface layer of the molecular ink on the surface layer of the substrate. Formed.

Next, the substrate having a minute pattern was immersed in water, and CH ₃ (CH ₂ ) ₁₉ SH was hydrophobically bonded and aggregated. In this state, the substrate surface around the fine pattern was chemically modified using an aqueous solution of HOOC (CH ₂ ) ₁₀ SH to produce a replica having a high contrast between the fine pattern and the surrounding substrate surface.

(Example 2)
After a replica was produced according to Example 1, the hydrophobic molecule was chemically modified on the fine pattern by using a stamper to which the hydrophobic ink was attached again. In this second process, the defective portion of the fine pattern was completely repaired, and a copy with a higher contrast could be obtained.

(Example 3)
According to Example 2, after hydrophilic modification of the hydrophilic molecule in water on the substrate surface around the fine pattern, the hydrophobic molecule was chemically modified on the fine pattern again in higher density in an alcohol solution. In this process, the defective portion of the fine pattern was completely repaired, and a replicate with a higher contrast could be obtained.

Example 4
In the same manner as in Example 1, except that a substrate having a silicon oxide deposited on the surface is used as a base material, and an ethanol solution of OH (CH ₂ ) ₁₀ COOH is used as a molecular ink, and the substrate is composed of hydrophilic molecules. A fine pattern was formed.

Next, the substrate having a fine pattern is immersed in a benzene solution of CH ₃ (CH ₂ ) ₁₀ COOH, and in that state, chemical modification of CH ₃ (CH ₂ ) ₁₉ COOH is applied to the substrate surface around the fine pattern, A replica having a high contrast between the fine pattern and the surrounding substrate surface area was produced.

(Example 5)
After producing the replica according to Example 3, the hydrophilic molecule was chemically modified on the fine pattern using a sealer to which hydrophilic ink was attached again. In this second process, the defective portion of the fine pattern was completely repaired, and a copy with a higher contrast could be obtained.

(Example 6)
According to Example 4, after hydrophilic modification of the hydrophilic molecules in water on the substrate surface around the fine pattern, the hydrophilic molecules were further chemically modified on the fine pattern in an alcohol solution at a higher density. In this process, the defective portion of the fine pattern was completely repaired, and a replicate with a higher contrast could be obtained.

1 edition 1a convex pattern 2 resin 3 Hanko 4 molecule ink 5 substrate 6 fine pattern 6 'fine pattern 7 area <br/> 8 PDMS resin 9 water 14 molecular ink 16 micropattern 17 organic solution

Claims (6)

A plate having a convex pattern on its surface is coated with a resin, and the resin is peeled off from the plate to produce a disc made of the resin, and a hydrophobic molecular ink in which hydrophobic molecules are dispersed is attached to the plate. The hydrophilic molecular ink is formed by forming a fine pattern composed of a layer of hydrophobic molecules on a substrate using a sticker to which the molecular ink is adhered, and dispersing hydrophilic molecules on the substrate surface around the fine pattern. in the method for manufacturing a fine pattern replication was subjected to chemical modification by immersion, after formation of the fine pattern, immersed one formed a fine pattern on a substrate in water, hydrophobic molecules that constitute a fine pattern the by hydrophobic bonding, characterized in that after allowed set hydrophobic molecules together, subjected to chemical modification by the hydrophilic molecule ink to the substrate surface around the fine pattern in water The method for manufacturing a fine pattern replica that. 2. The substrate surface around the fine pattern is chemically modified with hydrophilic molecular ink in water, and then the hydrophobic molecular ink is further chemically modified on the fine pattern in an alcohol solution. A method for producing a fine pattern replica described in 1. A plate having a convex pattern on the surface is coated with a resin, and the resin is peeled off from the plate to produce a disc made of the resin, and a hydrophilic molecular ink in which hydrophilic molecules are dispersed is attached to the plate. The hydrophobic molecular ink is formed by forming a fine pattern composed of a layer of hydrophilic molecules on a substrate using a sticker attached with the molecular ink, and dispersing hydrophobic molecules on the substrate surface around the fine pattern. In the method for producing a fine pattern replica which is chemically modified by dipping, hydrophilic molecules constituting the fine pattern are formed by immersing the fine pattern formed on the substrate in an organic solution after the formation of the fine pattern. the by hydrogen bonding facilities from allowed set hydrophilic molecules each other, the chemical modification with the hydrophobic molecule ink to the substrate surface around the fine pattern in organic solution The method for manufacturing a fine pattern copies, characterized in that. The substrate surface around the fine pattern is chemically modified with a hydrophobic molecular ink in an organic solution, and then further chemically modified with a hydrophilic molecular ink on the fine pattern in an alcohol solution. Item 4. A method for producing a fine pattern replica according to Item 3. A fine pattern replica produced by the method according to claim 1, comprising a layer of hydrophobic molecules formed by patterning on a substrate using a hydrophobic molecular ink in which hydrophobic molecules are dispersed. with a fine pattern, the comprises a layer of hydrophilic molecules to the substrate surface around the fine pattern, the fine features that you have ready for hydrophobic molecules fine pattern are aggregated by hydrophobic bonding in water pattern Duplicate. A fine pattern replica produced by the method according to claim 3, comprising a hydrophilic molecule layer formed by patterning on a substrate using a hydrophilic molecule ink in which hydrophilic molecules are dispersed. with a fine pattern, the comprises a layer of hydrophobic molecules on the substrate surface around the fine pattern, hydrophilic molecules of fine pattern features that you have in a state of aggregation by hydrogen bonding in organic solution Fine pattern replica.

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