KR100815081B1 - Method for release treatment of stamper - Google Patents

Abstract

The present invention relates to a stamper release treatment method for improving the release property of the stamper surface, and more particularly, preparing a stamper having an embossed pattern; Forming a silicon layer on the pattern of the stamper; And forming a self-assembled monolayer on the silicon layer. According to the present invention, the high adhesion between the silicon layer and the self-assembled monomolecular film is excellent in repetitive releasability, increases the strength of the stamper, and can be re-released through modification by UV-ozone treatment.

Stamper, release treatment, self-assembled monolayer, silicon layer

Description

Method for release treatment of stamper}

1 is a view schematically showing a release process of a stamper according to the present invention,

Figure 2 is a surface photograph of the nickel stamper released in Example 1 of the present invention,

3 is a photograph of the surface of the polymer stamper released in Example 2 of the present invention,

FIG. 4 is an enlarged SEM photograph showing a pattern portion of a polymer stamper released from Example 2 of the present invention.

FIG. 5 is an enlarged view for showing the detailed size of FIG. 2;

6 is a shape photograph of an insulating film subjected to imprinting using a nickel stamper released in Example 1 of the present invention.

<Explanation of symbols for the main parts of the drawings>

10: stamper 20: silicon layer

30: self-assembled monolayer

The present invention relates to a stamper release treatment method, and more particularly to a stamper release treatment method to improve the release property of the stamper surface.

Today, electronic and electric technology is rapidly evolving for more information storage, faster information processing and transmission, and simpler communication network to keep pace with the 21st century's high information and communication society. In particular, under the condition of the finiteness of a given information transmission rate, as a method capable of meeting these requirements, a method for implementing the components as small as possible while increasing reliability and providing new functionality has been proposed.

As described above, in accordance with the trend of light and short size of electronic products, fine patterns, miniaturization, and packaging of printed circuit boards are also progressing simultaneously. Accordingly, a circuit having excellent signal processing capability in a smaller area may be implemented. For this purpose, there is a need for manufacturing high density substrates (line / space ≦ 10 μm / 10 μm, Microvia <30 μm).

One of the most widely used microstructure fabrication techniques to date is UV lithography, a method of forming a circuit pattern by injecting ultraviolet rays onto a substrate coated with a photoresist thin film. However, when manufacturing the substrate using the UV lithography method, there is a limitation that the copper foil used as the circuit must be thick and the wet etching method is used, so that the reliability of the product when forming a fine line width of 10 μm or less with UV lithography This has the problem of falling.

In recent years, the degree of integration of printed circuit boards has been increasing and researches on how to form fine patterns have been actively conducted. As a substitute method of the above-described UV lithography, a high density substrate is used by using a stamper for circuit pattern formation. Attempts to manufacture are receiving attention.

As described above, when manufacturing a large area substrate such as a printed circuit board using a stamper, it is important to protect the expensive stamper and to secure the release property of the stamper for a successful nanoimprint process.

Until now, various surface treatment methods such as release agent treatment, plasma polymerization, self-assembled monolayer (SAM) coating, and NOVEC coating have been used to improve the releasability of metal or polymer stampers in the nanoimprint process. Such release treatment methods still have many problems in the reproducibility and repeatability of the process and there is much room for improvement.

Therefore, in order to manufacture a stamper with high productivity and efficiency, research to secure a release property of the stamper is still needed.

The present invention is to solve the above-mentioned problems of the prior art, an object of the present invention is to provide a stamper release treatment method to improve the release property of the stamper surface.

The present invention to solve the above technical problem,

Preparing a stamper having an embossed pattern;

Forming a silicon layer on the pattern of the stamper; And

Forming a self-assembled monolayer on the silicon layer;

It provides a release treatment method of a stamper comprising a.

According to an embodiment of the present invention, the stamper is a metal stamper or a polymer stamper, and the metal stamper is preferably a nickel stamper.

According to an embodiment of the present invention, the silicon layer may be formed by depositing a silicon layer on a stamper pattern using a silane (SiH ₄ ) gas by chemical vapor deposition (CVD).

Here, the silane (SiH 4) gas is preferably injected at a pressure of 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ Torr and a temperature of 100 to 400 ° C. In addition, the silicon layer is preferably formed to a thickness of 1 to 100nm.

According to an embodiment of the present invention, the method may further include ultraviolet-ozone treatment of the silicon layer before forming the self-assembled monolayer. At this time, the ultraviolet-ozone treatment is preferably performed by a method of modifying the surface of the silicon layer by irradiating ultraviolet rays for 1 to 30 minutes in an ozone atmosphere.

In addition, according to one embodiment of the present invention, after the ultraviolet-ozone treatment may further comprise the step of cleaning the stamper.

According to an embodiment of the present invention, the self-assembled monolayer is formed by coating a SAM solution by one method selected from the group consisting of spin coating, roll coating, and dip coating. Can be performed. In the case of using the dip coating, it is preferable to immerse the stamper on which the silicon layer is formed in a SAM solution and stir for 5 to 30 minutes to form a self-assembled monolayer. In this case, as the SAM solution, a silane-based SAM material such as heptadecafluoro-1,1,2,2-tetrahydrodecyl-trichlorosilane may be mixed with a non-aqueous solvent.

According to one embodiment of the present invention, after the formation of the in situ monolayer film may further comprise the step of cleaning the stamper. Here, the washing step is preferably washed by alternately using a non-aqueous solvent and deionized water alternately. In addition, the method may further include the step of ultrasonicating the stamper to remove the cluster, etc. of the stamper surface.

The release treatment method according to the present invention may further include the step of desorption of the self-assembled monolayer by forming a self-assembled monolayer, followed by UV-ozone treatment to form a self-assembled monolayer. As described above, reproducibility and repeatability may be improved by repeatedly removing the self-assembled monolayer and re-forming the self-assembled monolayer.

Hereinafter, a stamp release processing method according to the present invention will be described in more detail.

In order to protect the stamper during imprinting and to form a successful nanopattern, it is important to prevent adhesion between the spamper and the polymer.

In general, a surface that can be surface treated using a silane-based self-assembled monolayer (SAM) is basically a surface that can form a hydroxyl group (-OH) or a carboxy group (-COOH) well on the surface. For example, materials such as silica, quartz, glass, and the like are excellent in SAM formation, and aluminum and copper are relatively easy to form SAM.

However, in the case of an imprinting stamp, a metal foil or a polymer, such as nickel, which is generally used, is relatively difficult to form SAM, and thus the adhesion between the stamper and the SAM layer is poor. Therefore, there is an inconvenience in that the releasability is poor at the time of imprinting, and also the adhesive force is weak and the structures that have been separated are removed. Accordingly, the present invention is to improve the releasability by increasing the adhesion between the stamper and the SAM layer during the SAM treatment of the imprinting stamper.

1 is a flowchart schematically showing a stamp release processing method according to the present invention.

Referring to Figure 1, the stamp release processing method according to the present invention comprises the steps of preparing a stamper 10 having an embossed pattern (step a); Forming a silicon layer 20 on the pattern of the stamper 10 (step b); And forming a self-assembled monolayer 30 on the silicon layer 20 (step c).

In the stamp release processing method according to the present invention, first, a stamper 10 having an embossed pattern is prepared. (step a)

As the stamper 10, a metal stamper such as nickel or a polymer stamper such as PET or silicon may be used. More preferably, it is preferable to use a flexible stamp so that the nanopattern can be easily formed even on non-planar layers such as curved surfaces. In order to have such flexibility, in the case of a metal stamper, a thin nickel tool-foil having a thickness of 50 μm or less may be used. A predetermined relief pattern is provided on the stamper 10, and the relief pattern includes a fine pattern of 100 nm or less.

After the stamper 10 having the embossed pattern is prepared, the silicon layer 20 is formed on the pattern of the stamper 10. (step b)

Since the silicon layer 20 exhibits excellent adhesion to the self-assembled monolayer (SAM) 30 formed later, repeated releasability may be improved during imprinting.

The formation of the silicon layer 20 may be performed by depositing the silicon layer 30 on the pattern of the stamper 20 using silane (SiH ₄ ) gas by chemical vapor deposition (CVD).

Here, the silane (SiH ₄ ) gas is preferably injected at a pressure of 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ Torr and a temperature of 100 to 400 ° C. Such pressure and temperature ranges are considered to obtain a solid crystallized Si thin film, and may cause a problem in crystallinity when out of the above ranges.

In addition, the silicon layer is preferably formed to a thickness of 1 to 100nm. If the thickness is less than 1 nm, the adhesion is weak, which is not preferable. If the thickness is more than 100 nm, the dimension is changed, which is not preferable.

After the silicon layer 20 is formed in this manner, a self-assembled monolayer 30 is formed. (step c)

According to an embodiment of the present invention, the step of forming the self-assembled monolayer 30 may further comprise the step of ultraviolet-ozone treatment of the silicon layer 20. This is because it is necessary to form a hydroxyl group (-OH) on the surface in order to form the self-assembled monolayer 30 on the surface of the silicon layer 20 of the stamper. As such a surface modification method, in general, a stamper is put in sulfuric acid or the like to perform pyranha treatment. However, in the present invention, metal stampers such as nickel may corrode, and therefore, it is preferable to modify the surface through ultraviolet-ozone treatment. More specifically, the ultraviolet-ozone treatment may be performed by irradiating ultraviolet rays for 1 to 30 minutes in an ozone atmosphere to modify the surface of the silicon layer 20. If the UV-ozone treatment time is less than 1 minute, surface modification may not be performed well, and in terms of processability, the UV-ozone treatment time does not need to exceed 30 minutes.

The method may further include cleaning the stamper after the ultraviolet-ozone treatment. Specifically, washing with a polar solvent is preferable. According to one embodiment of the present invention, washing may be performed in the order of acetone, isopropyl alcohol, deionized water, and the like, followed by drying.

After the surface modification is performed through the ultraviolet-ozone treatment of the silicon layer 20, the self-assembled monolayer 30 is easily formed on the silicon layer 30.

Self-assembled monolayers can be generally formed through a liquid phase method and a vapor phase method. In the case of a vapor phase method, it is difficult to secure reproducibility and repeatability in a large area stamper process. Therefore, the present invention solves this problem by forming a self-assembled monolayer by using a liquid phase method.

Preferably, the self-assembled monolayer 30 is formed by coating a SAM solution by one method selected from the group consisting of spin coating, roll coating, and dip coating. Can be. In the case of using the dip coating of the coating method, according to an embodiment of the present invention, it is preferable to immerse the stamper on which the silicon layer 20 is formed in a SAM solution and stir for 5 to 30 minutes to form a self-assembled monolayer 30. . In this case, the SAM solution may be used by mixing a silane-based SAM material such as heptadecafluoro-1,1,2,2-tetrahydrodecyl-trichlorosilane with a non-aqueous solvent, but is not limited thereto.

Stamper release treatment method according to the invention may further comprise the step of cleaning the stamper after the formation of the site assembly monolayer (30). Here, the washing step is preferably washed by alternately using a non-aqueous solvent and deionized water alternately.

In addition, the method may further include the step of ultrasonicating the stamper to remove the cluster, etc. of the stamper surface.

In the release treatment method according to the present invention, after the self-assembled monolayer 30 is formed, the self-assembled monolayer 30 may be detached by UV-ozone treatment, and the self-assembled monolayer 30 may be formed again. As described above, the self-assembled monolayer 30 may be detached and then re-formed to improve reproducibility and repeatability.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for illustrative purposes only and are not intended to limit the present invention.

<Example 1>

First, cleansing was performed with argon gas before forming the silicon layer on the nickel stamper having a nano pattern (Condition: Base pressure: 1.0 × 10 -5torr, RF Bias: -600V (rf 13.56 Mhz), Gas flow: Ar 40) sccm). Subsequently, a 10 nm thick silicon layer was deposited on the stamp by using chemical vapor deposition (conditions: working pressure: 1.0 × 10 −3 torr, RF Bias: −300 V (rf 13.56 Mhz), and gas flow: SiH ₄ 40). sccm). UV-ozone treatment of the stamper for about 10 minutes prior to SAM coating, followed by washing the stamper in the order of acetone, isopropyl alcohol and deionized water and drying. Next, hexane and SAM reagent (heptadecafluoro-1,1,2,2-tetrahydrodecyl-trichlorosilane) were mixed at a ratio of 1000: 1 and mixed in a stirrer for 5 to 10 minutes. The stamper was immersed in the SAM solution and stirred for 10 minutes in a stirrer. The stamper was taken out and washed three times in the order of hexane and deionized water. Subsequently, the SAM-coated stamper was sonicated in HFE for about 3 to 5 minutes and then washed the same method.

<Example 2>

The same procedure as in Example 1 was performed except that PMMA polymer was used as a stamper, and the release treatment was performed.

<Example 3>

After the release treatment of Example 1, the stamper was placed in an ultraviolet-ozone treatment machine and treated for about 10 seconds to desorb the self-assembled monolayer, and washed with acetone, isopropyl alcohol, and deionized water, followed by drying. Subsequently, the self-assembled molecule formation process in Example 1 was repeated to release.

The surface photograph of the nickel stamper released in Example 1 is shown in FIG. 2, and the surface photograph of the polymer stamper released in Example 2 is shown in FIG. 3. FIG. 4 is an enlarged SEM photograph of the pattern portion of the polymer stamper released in Example 2; FIG.

5 is to show the detailed size of FIG. 2, wherein the width indicated by 1 is 1403.61 μm, the lower diameter of the two-stage pattern represented by 2 is 66.11 μm, and the upper diameter of the two-stage pattern represented by 3 is The pattern thickness shown by 31.65 micrometers and 4 is 17.89 micrometers, and the space | interval between patterns represented by 5 is 44.03 micrometers.

As shown in FIGS. 2 to 5, in the stamper released according to the present invention, the self-assembled monolayer was well attached to the stamper by the silicon layer, and in particular, the strength of the polymer stamper was increased. In addition, it was confirmed that the pattern with high resolution was maintained even after the release process.

In addition, a shape photograph of the insulating film subjected to imprinting using the nickel stamper released in Example 1 is shown in FIG. 6. Referring to FIG. 6, it can be seen that when imprinting is performed by using a nickel stamper released according to the present invention, a pattern having excellent releasability and a high resolution can be made.

As described above, the stamper release treatment method according to the present invention exhibits excellent repeat release property due to the high adhesion between the silicon layer and the self-assembled monolayer, and increases the strength of the stamper and enables re-release treatment through modification by UV-ozone treatment. Do.

The present invention is not limited to the above embodiments, and many variations are possible by those skilled in the art within the spirit of the present invention.

As described above, the stamper release treatment method according to the present invention is excellent in repetitive releasability due to the high adhesion between the silicon layer and the self-assembled monolayer, increases the strength of the stamper, and the re-release treatment is carried out through modification by UV-ozone treatment. It is possible. In addition, since the self-assembled monomolecular film is formed by a liquid phase method rather than a gas phase method, process reproducibility and repeatability can be secured.

Claims (16)

Preparing a stamper having an embossed pattern; Forming a silicon layer on the pattern of the stamper; And Forming a self-assembled monolayer on the silicon layer; Release method of the stamper comprising a. The method of claim 1, The stamper is a release method of a stamper is a metal stamper or a polymer stamper. The method of claim 1, The silicon layer is formed by a chemical vapor deposition (CVD) method using a silane (SiH ₄ ) gas by depositing a silicon layer on the stamper's pattern. The method of claim 3, wherein The silane (SiH4) gas is a release process of a stamper is injected at a pressure of 1 × 10 ^-5 to 1 × 10 ^-1 Torr and 100 to 400 ℃ temperature range. The method of claim 1, The silicon layer is a release treatment method of a stamper is formed to a thickness of 1 to 100nm. The method of claim 1, And releasing the ultraviolet-ozone treatment of the silicon layer before forming the self-assembled monolayer. The method of claim 6, The ultraviolet-ozone treatment is a release treatment method of a stamper performed by a method of modifying the surface of the silicon layer by irradiating ultraviolet rays for 1 to 30 minutes in an ozone atmosphere. The method of claim 6, And releasing the stamper after the ultraviolet-ozone treatment. The method of claim 1, The self-assembled monolayer is formed by spin coating, spin coating, roll coating, dip coating, and the like. The method of claim 1, The self-assembled monomolecular film formation is performed by immersing the stamper with the silicon layer formed in a SAM solution and stirring for 5 to 30 minutes. The method of claim 10, The SAM solution is a release method of a stamper is a solution of heptadecafluoro-1,1,2,2-tetrahydrodecyl-trichlorosilane mixed with a non-aqueous solvent. The method of claim 1, And removing the stamper after the self-assembled monolayer is formed. The method of claim 12, The washing step is a release treatment method of a stamper which is a step of washing by using alternately repeated non-aqueous solvent and deionized water. The method of claim 1, And stamping the stamper after forming the self-assembled monolayer. The method of claim 1, The release treatment method further comprises the step of detaching the self-assembled monolayer by forming a self-assembled monolayer by UV-ozone treatment, and re-forming the self-assembled monolayer. The method of claim 15, And detaching the self-assembled monolayer and repeating the step of forming the self-assembled monolayer again.

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