KR100768705B1 - Method of manufacturing polymeric stamp for imprinting and polymeric stamp manufactured using the same - Google Patents

Abstract

A method for manufacturing an imprinting polymeric stamp and the polymeric stamp manufactured by the same are provided to improve the releasing ability of the stamp by forming a silicon-based polymer layer on an elastic film and imprinting a master on the film. A master(10) having a predetermined pattern is prepared, and then a silicon-based adhesive layer(30) is formed on an elastic film(20). A silicon-based polymer layer(40) is formed on the silicon-base adhesive layer. The master comes in contact with an upper surface of the silicon-based polymer layer to press the latter, and then the master is detached from the silicon-based polymer layer. A releasing agent is applied on the master.

Description

Method of manufacturing polymeric stamp for imprinting and polymeric stamp manufactured using the same}

1 is a process chart showing a manufacturing method of an imprinting polymer stamp according to the present invention,

Figure 2 is a photograph showing an image of a silicone polymer stamp prepared in an embodiment of the present invention,

3a and 3b are electron micrographs showing the pattern of the silicon polymer stamp,

4 is a photograph showing an image of an insulating film for a substrate on which a pattern is formed using a silicon polymer stamp prepared in an embodiment of the present invention.

5A and 5B are electron micrographs showing patterns formed on the insulating film for the substrate.

<Explanation of symbols for main parts of the drawings>

10: master 11: self-assembled monolayer

20: elastic film 30: silicone polymer layer

40: adhesive layer

The present invention relates to a method of manufacturing a polymer stamp for imprinting and a polymer stamp thereby, and more particularly, to a method for producing an imprinting polymer stamp capable of imprinting fine and deep patterns as well as being excellent in release property and economical. It relates to a polymer stamp.

In order to implement a circuit having excellent signal processing capability in a smaller area, there is a need for manufacturing a high-density substrate (line / space ≦ 10 μm / 10 μm, Microvia <30 μm). However, there are more and more problems to be overcome in the manufacturing process and manufacturing cost of the UV lithography method, which has been used in the manufacture of substrates, as the density of substrates increases. Therefore, attempts to manufacture high-density substrates using the imprint method as an alternative method of UV lithography have attracted attention.

When manufacturing a substrate using an imprint process, a large area imprint process should be considered for mass production. In this case, development of a stamp that is easy to pressurize uniformly, is easy to use, and has excellent mold release property is an important problem. Soybeans.

In the conventional substrate imprinting process, a method of manufacturing a soft polymer stamp is prepared by a master, and then mixed with a polymer mold material to form a stamp using the same, and the polymer mold material is poured onto the master. After curing the polymer mold in the hot chamber, the polymer stamp is completed by peeling off the cured elastomeric stamp from the master. The polymer stamp prepared in this manner is advantageous in terms of release treatment, but the mechanical strength of the stamp itself is low, so that the resolution is poor and many defects are generated to produce a fine pattern by the imprinting process.

In order to solve such a problem, there is a method of manufacturing a stamp which is more economical and improves mechanical strength by forming and imprinting an acrylate-based polymer layer on a flexible and rigid substrate such as PET. However, the acrylate-based polymer has a limitation in controlling ductility, and thus, there is a problem in that defects are likely to occur when a complex and deep micropattern is manufactured.

The present invention is to solve the above-mentioned problems of the prior art, an object of the present invention by using a silicon-based polymer layer as the material of the stamp is excellent in releasability, the production of an imprinting polymer stamp that can imprint fine and deep patterns To provide a method and thereby a polymer stamp.

According to one aspect of the invention,

Preparing a master having a predetermined pattern;

Forming a silicone adhesive layer on the elastic film;

Forming a silicon-based polymer layer on the silicon-based adhesive layer;

Pressing the master by contacting the upper surface of the silicon polymer layer; And

Separating the master;

It provides a method for producing an imprinting polymer stamp comprising a.

According to a preferred embodiment, the master is preferably a silicon master.

In the present invention, the manufacturing method may further comprise the step of applying a release agent on the surface of the master. It is preferable to use a perfluoro silane compound as the release agent, and the perfluoro silane compound may be represented by the following Chemical Formula 1.

[Formula 1]

Wherein R ₁ to R ₃ are each independently a halogen element, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 20 .

Specific examples of the perfluoro silane compound include perfluorodecyltrichloro silane.

The elastic film is selected from the group consisting of polyethylene terephthalate, polyethylene, polypropylene, polycarbonate and polymethyl methacrylate.

The silicone adhesive layer is a copolymer of silicon and epoxy, it is preferable to use a copolymer of epoxy and silicon having an epoxy content of 20 to 80% by weight.

The method of manufacturing the polymer stamp for imprint may further include forming a silicone adhesive layer on the elastic film and then performing thermosetting or ultraviolet curing. In the case of thermosetting, it is preferably carried out for 1 to 30 minutes at a temperature of 80 to 200 ℃.

The silicone-based polymer layer is an elastic polymer including a silicone polymer. Specific examples of the silicon polymer include PDMS (polydimethylsiloxane).

In the pressing of the master on the upper surface of the silicon-based polymer layer, thermosetting or ultraviolet curing may be further performed. In the case of thermosetting, it is preferable to carry out for 1 to 3 hours by raising the temperature to a temperature of 120 to 200 ℃ in a state in which the master is pressurized.

According to another aspect of the invention, it provides an imprinting polymer stamp prepared according to the manufacturing method.

Hereinafter, a method of manufacturing an imprinting polymer stamp and a polymer stamp according to the present invention will be described in more detail with reference to the accompanying drawings.

1 is a process chart showing the process of the manufacturing method of the imprinting polymer stamp according to the present invention in order. Looking at the manufacturing method of the imprinting polymer stamp according to the present invention with reference to FIG.

First, a master 10 having a predetermined pattern is prepared.

The master 10 is preferably made of a material that can withstand thermal curing, or a material that can transmit ultraviolet rays when UV curing, it is preferable to use a silicon master made of a silicon wafer or the like. In some cases, quartz, which is a silicon oxide, may be used as the master.

Such a master 10 can also be used by processing the surface of the master in which the pattern is formed with a mold release agent. The treatment of the releasing agent is to separate the master 10 from the silicone polymer layer 30 in a subsequent process, more easily without damaging the cured polymer layer 30. The release agent may be suitably used according to the material of the master 10 and the silicone polymer layer 30 used. According to an embodiment of the present invention, it is preferable to use a perfluoro silane compound as the release agent. The perfluoro silane compound may be represented by the following Chemical Formula 1.

 [Formula 1]

Wherein R ₁ to R ₃ are each independently a halogen element, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, n is an integer of 1 to 20 to be.

Here, "substituted" means that at least one hydrogen atom of the alkoxy group or the alkyl group is substituted with a halogen element.

Specific examples of the compound of Formula 1 may include perfluorodecyltrichlorosilane.

Such a release agent is surface-treated on one surface on which the pattern of the master 10 is formed by a vaporization method or the like to form a strong bond with the master 10, thereby obtaining a physically and chemically stable self-assembled monolayer 11 having excellent mechanical properties. ).

Next, the silicon adhesive layer 30 is formed on the elastic film 20.

The elastic film 20 is a transparent and flexible film, and is selected from the group consisting of polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, and polymethyl methacrylate.

Before forming the silicone-based polymer layer 40 on the elastic film 20, the silicone-based adhesive layer 30 is formed, which may cause difficulty in bonding the silicone polymer layer on the elastic film, as opposed to the release property of the silicone-based polymer. Because. According to an embodiment of the present invention as a material used for the silicon-based adhesive layer 30 as a copolymer of silicon and epoxy, it is preferable to use a copolymer of epoxy and silicon having an epoxy content of 20 to 80% by weight. . The silicone adhesive layer 30 may be applied onto the elastic film 20 by using a method such as hand casting.

Subsequently, a silicon-based polymer layer 40 is formed on the silicon-based adhesive layer 30.

As the silicon-based polymer layer 40, an elastomer including a silicon polymer is used. In the present invention, the silicon polymer used as the material of the silicon-based polymer layer 40 is transparent but has low reactivity and interfacial energy with respect to the polymer material, and thus may transmit light in the imprinting lithography process. Due to the releasability, the mold can be easily released without being sticky after imprinting. As a specific example of the silicone polymer, PDMS (polydimethylsiloxane) can easily prepare a stamp having various physical properties compared to the conventional acrylate polymer because PDMS of various physical properties are commercialized at present.

The silicon-based polymer layer 40 may be formed by any method that is commonly used in the art, such as handcasting, droplet dispensing, spin coating, or spraying. It is preferable to apply using a handcasting method from the viewpoint of ease of use. Here, the silicon polymer layer 40 is preferably applied to have the same thickness as the thickness of the pattern formed on the master (10).

After the silicon-based polymer layer 40 is formed, the master 10 is then contacted with an upper surface of the silicon polymer layer 40 and pressurized to a predetermined pressure. In this case, the silicone polymer layer 40 may be thermally cured or ultraviolet cured in the pressurized state of the master 10. In the case of thermal curing, the temperature is raised to a temperature of 80 to 200 ° C. for 1 to 3 hours. It is preferable to add. In the case of ultraviolet curing, ultraviolet rays of the same range can be cured by irradiating moisture or more.

After pressing and curing the master 10, the master stamp 10 may be separated from the silicon-based polymer layer 40 to complete the imprinting polymer stamp.

Thus, according to the manufacturing method of the imprinting polymer stamp according to the present invention by forming a silicone polymer layer on a flexible elastic substrate having a soft and strong, such as PET, the release process is easier, finer and deeper due to the release of the silicone polymer. In addition to imprinting the pattern, due to the various physical properties of the silicone polymer it can be easily produced stamps of various physical properties.

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>

First, to release the silicon master, the silicon master was left in a solution containing sulfuric acid and hydrogen peroxide at 7: 3 for 20 minutes at about 90 ° C., followed by rinsing with pure water. This was placed in a vacuum oven and left under reduced pressure to completely remove moisture, and then, using a 1 ml of perfluorodecyltrichlorosilane as a release agent, the temperature was raised under reduced pressure to vaporize and bonded to the silicon master.

On the other hand, after the epoxy content of 50% by weight of the silicone oligomer and the curing agent was well mixed in a ratio of 10: 1, bubbles generated by the deaerator were removed. This solution was made on the PET film by hand casting to produce a thin film of about several micrometers. After leaving the film at 100 ° C. for 5 minutes to adjust the viscosity of the silicone film, a thin film of about 35 μm was formed on the film by a handcasting mixture of the silicone oligomer and the curing agent. After placing the silicon master here, it was maintained for 3 hours at 150 ℃ while applying a pressure of 3-5 bar under reduced pressure. The silicone master was removed from the film to produce a silicone rubber stamp.

Figure 2 is a photograph showing an image of the silicone rubber stamp prepared in the embodiment, Figures 3a and 3b is an electron micrograph showing the pattern of the silicone rubber stamp. 3A and 3B, it can be seen that the silicone rubber stamp is manufactured without defects.

An imprinting test was performed on the insulating film for epoxy substrates using the silicon rubber stamp thus prepared. 4 is a photograph showing an image of a patterned insulation film for a substrate, and FIGS. 5A and 5B are electron micrographs showing a pattern formed on the insulation film for a substrate. 5A and 5B, it can be seen that the silicon rubber stamp manufactured according to the manufacturing method of the present invention can transfer a pattern without defects to the insulating film for a substrate by maintaining sufficient mechanical properties.

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 manufacturing method of the imprinting polymer stamp according to the present invention forms a silicon-based polymer layer on the elastic film and then imprints the master, thereby providing excellent releasability, and capable of imprinting a deep and fine pattern without defects. Stamps can be produced.

Claims (13)

Preparing a master having a predetermined pattern; Forming a silicone adhesive layer on the elastic film; Forming a silicon-based polymer layer on the silicon-based adhesive layer; Pressing the master by contacting the upper surface of the silicon polymer layer; And Separating the master; Method of producing a polymer stamp for imprinting comprising a. The method of claim 1, The master is a silicon master manufacturing method of the imprinting polymer stamp. The method of claim 1, The method of manufacturing an imprinting polymer stamp further comprising the step of applying a release agent on the surface of the master. The method of claim 3, wherein The release agent is a method of producing a polymer stamp for imprinting is a perfluoro silane compound. The method of claim 1, The elastic film is a method for producing an imprinting polymer stamp selected from the group consisting of polyethylene terephthalate, polyethylene, polypropylene, polycarbonate and polymethyl methacrylate. The method of claim 1, The silicone adhesive layer is a method for producing an imprinting polymer stamp is a copolymer of epoxy and silicon with an epoxy content of 20 to 80% by weight. The method of claim 1, Forming a silicone-based adhesive layer on the elastic film and then performing a thermosetting or ultraviolet curing step further comprising the method of manufacturing an imprinting polymer stamp. The method of claim 7, wherein The thermosetting is a method for producing an imprinted polymer stamp is carried out for 1 to 30 minutes at a temperature of 80 to 200 ℃. The method of claim 1, The silicon-based polymer layer is a method for producing an imprinting polymer stamp is an elastomer containing a silicone polymer. The method of claim 9, The silicone polymer is a method for producing an imprinting polymer stamp of PDMS. The method of claim 1, In the step of pressing the master on the upper surface of the silicon-based polymer layer, the manufacturing method of the imprinting polymer stamp for further performing heat curing or ultraviolet curing. The method of claim 11, The thermosetting is a method for producing an imprinting polymer stamp is carried out for 1 to 3 hours by raising the temperature to 120 to 200 ℃ in the pressurized state. An imprinting polymer stamp prepared according to any one of claims 1 to 12.

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