KR20230088573A - Master mold for nanoimprinting and nanoimprinting method using the same - Google Patents

Abstract

The present invention relates to a master mold for nanoimprinting and a nanoimprinting method using the master mold. More specifically, the present invention relates to a master mold for nanoimprinting having excellent release properties and durability that can be utilized without separate release treatment by using a nanostructure formed by surface modification of the surface of a fluorine-based polymer as a pattern, and a nanoimprinting method using the same will be.

Description

Master mold for nanoimprinting and nanoimprinting method using the same {Master mold for nanoimprinting and nanoimprinting method using the same}

The present invention relates to a master mold for nanoimprinting and a nanoimprinting method using the master mold. More specifically, the present invention relates to a master mold for nanoimprinting having excellent release properties and durability that can be utilized without separate release treatment by using a nanostructure formed by surface modification of the surface of a fluorine-based polymer as a pattern, and a nanoimprinting method using the same will be.

As a method of forming nano-sized micropatterns to form semiconductors, optical devices, and other nanostructures, nanoimprint technology is attracting attention. In nano-imprint, a mold having a nano-scale pattern is generally manufactured, a curable polymer material that is cured by heat or ultraviolet light is applied on a base substrate, pressure is applied to the base substrate with a nano-sized mold, and heat It is a method of forming a nanopattern by curing a polymer material on which the nanopattern is transferred through ultraviolet light or ultraviolet light. Thereafter, a release process of separating the polymer material and the base substrate from the mold is performed. At this time, it is important to separate the polymer material on which the nanopattern is formed without damaging it during the release process. When the polymer material is damaged during the mold release process, the shape of the nanopattern transferred to the polymer pattern may change and the quality may deteriorate.

1 is a diagram schematically showing problems of a conventional master mold for imprinting. Conventional master molds for imprinting have a problem in that when polymer films such as PET and PEN are used, the polymer does not easily separate from the master mold for imprinting and remains in the master mold unless a separate release treatment is performed. As described above, if the polymer remains in the master mold for imprinting, it is difficult to reuse the master mold and the transferred pattern of the imprinting object is also damaged. The productivity of the nanoimprinting process can be improved only when the polymer is well released from the master mold.

Therefore, conventionally, in order to solve this problem, the release process is facilitated by a release treatment such as using a material having a low surface energy as an intermediate layer so as not to damage the polymer material on which the nanopattern is formed during release while preventing contamination of the mold. did However, these methods may have complicated processes and high costs.

Therefore, there is a need to develop a mold for nanoimprinting that has excellent releasability without a separate release treatment process, excellent durability, and good repeated use efficiency.

As a background of the present invention, Korean Patent Registration No. 10-1342900 discloses a method for manufacturing a replica mold for nano-imprint and a replica mold for nano-imprint.

An object of the present invention is to provide a master mold for nanoimprinting with excellent releasability.

Another object of the present invention is to provide a master mold for nanoimprinting, which has excellent releasability and durability, and thus has excellent reusability.

Another object of the present invention is to provide a method for manufacturing a master mold for nano-imprinting in which a manufacturing process is simplified by omitting a separate release treatment step.

Another object of the present invention is to provide a nanoimprinting method with excellent productivity by enabling easy release of an object to be imprinted and repeated reuse of a master mold.

Other objects and advantages of the present invention will become more apparent from the following detailed description, claims and drawings.

According to one aspect, a master mold for nanoimprinting is provided, including a polymer film on which a plurality of nanostructures are formed, wherein the polymer film is made of a fluorine-based polymer and the nanostructure is formed by ion beam treatment.

According to one embodiment, the shape of the nanostructure may be one or more of a protrusion shape, a cone shape, and a wrinkle shape.

According to one embodiment, the fluorine-based polymer may be one or more of PTFE, FEP, PFA, PVDF, ETFE, and PVF.

According to one embodiment, the nanostructure may be used to form a pattern on an imprinting target.

According to another aspect, a product manufactured using the master mold for nanoimprinting described herein is provided.

According to another aspect, I-i) preparing a fluorine-based polymer film; and I-ii) forming a nanostructure by treating the surface of the fluorine-based polymer film with an ion beam having an ion beam energy of 50 to 2000 eV, wherein the shape of the nanostructure is one of a protrusion shape, a cone shape, and a wrinkle shape. A method for manufacturing a master mold for nanoimprinting that is more than one species is provided.

According to one embodiment, in step I-i), the fluorine-based polymer may be at least one of PTFE, FEP, PFA, PVDF, ETFE, and PVF.

According to an embodiment, the gas used during the ion beam treatment in step I-ii) may include at least one of argon and oxygen.

According to one embodiment, steps I-i) and I-ii) may be performed in a roll-to-roll process.

According to one embodiment, the process speed of the roll-to-roll process may be 0.1 to 10 mpm.

According to another aspect, II-i) applying a curable resin on the surface of the master mold for nanoimprinting described herein or on the base substrate; II-ii) attaching the master mold for nanoimprinting and the base substrate with the curable resin interposed therebetween, and then curing the curable resin; and II-iii) releasing the cured resin and the base substrate from the master mold.

According to one embodiment, in step II-i), the base substrate may be a polymer, silicon, or glass substrate.

According to one embodiment, it is possible to provide a master mold for nano-imprinting, which is provided with a nanostructure formed on a fluorine-based polymer film by ion beam treatment and can be used as a transfer pattern.

According to one embodiment, it is possible to provide a master mold for nanoimprinting having excellent releasability by providing a nanostructure formed by ion beam treatment on a fluorine-based polymer film.

According to an embodiment, it is possible to provide a master mold for nanoimprinting with excellent reusability by having nanostructures formed by ion beam treatment on a fluorine-based polymer film and having excellent releasability and durability at the same time.

According to an embodiment, a method for manufacturing a master mold for nanoimprinting provides a master mold for imprinting having a nanostructure formed by ion beam treatment on a fluorine-based polymer film and having excellent release properties even without a separate release treatment step. This can simplify the manufacturing process.

According to one embodiment, the nanoimprinting method of the present application has excellent productivity because the release process is efficient and repeated transfer is possible by using the master mold for nanoimprinting, which has excellent releasability and durability.

1 is a diagram schematically showing problems of a conventional master mold for nanoimprinting.
2 is a diagram schematically illustrating a method of manufacturing a master mold for nanoimprinting according to an embodiment of the present invention.
3 is an image showing the surface after 10 transfers of the ion beam-treated PEN mold according to a comparative example of the present invention.
4 is an image showing the surface after 10 transfers of an ion beam treated PTFE mold according to an embodiment of the present invention.
FIG. 5 is a graph showing the surface of each imprinting object transferred after being transferred 1, 5, and 10 times using a PEN mold treated with an ion beam according to a comparative example of the present invention.
FIG. 6 is a graph showing the surface of each imprinting object transferred after repeated transfer 1, 5, and 10 times using an ion-beam-treated PTFE mold according to an embodiment of the present invention.
7 is a graph showing a change in transmittance of a film after transferring 10 times using a PEN mold as a comparative example and a PTFE mold as an example of the present invention.
8 is a graph showing the water contact angle of the surface of the fluorine-based polymer after ion beam treatment according to the type of gas according to an embodiment of the present invention.

Terms used in this application are only used to describe specific embodiments, and are not intended to limit the present invention.

Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this application, terms such as 'include' or 'have' are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

In this application, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated. Also, throughout the specification, "on" means to be located above or below the target part, and does not necessarily mean to be located on the upper side with respect to the direction of gravity.

Since the present invention can apply various transformations and have various embodiments, specific embodiments will be illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all conversions, equivalents, or substitutes included in the spirit and scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.

Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. These terms are only used for the purpose of distinguishing one component from another.

According to one aspect, a master mold for nanoimprinting is provided, including a polymer film on which a plurality of nanostructures are formed, wherein the polymer film is made of a fluorine-based polymer and the nanostructure is formed by ion beam treatment.

Although not limited thereto, the shape of the nanostructure formed on the polymer film may be one or more of a protrusion shape, a cone shape, and a wrinkle shape. The nanostructure formed on the polymer film is used to form a pattern on an object to be imprinted.

The fluorine-based polymer may be composed of various known fluorine-based materials. Although not limited thereto, the fluorine-based polymer is polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluoroalkoxy (PFA), polyvinylidene fluoride (Polyvinylidene fluoride (PVDF), ethylene tetrafluoroethylene (ETFE), and polyvinyl fluoride (PVF).

The polymer film on which the nanostructure of the present application is formed is made of a fluorine-based polymer as a polymer film, so that the nanostructure can be easily formed by a simple process using the low surface energy characteristics of the fluorine-based polymer, and can be used as an imprinting master mold. In addition, when used as the imprinting master mold due to the low surface energy characteristics of the fluorine-based polymer, the releasability and durability of the imprinting master mold can be simultaneously improved. Accordingly, according to the present disclosure, it is possible to provide a master mold for nanoimprinting having good reusability due to excellent releasability and durability at the same time.

The nanostructure is formed by ion beam treatment of a fluorine-based polymer film with energy of 50 to 2000 eV. If the energy of the ion beam is less than 50 eV, the formation of nanostructures on the fluorine-based polymer film may not be smooth, and if the ion beam energy exceeds 2000 eV, deformation such as twisting and contraction of the fluorine-based polymer film may occur, which may be used as an imprinting master mold. can't

According to another aspect, a product manufactured using the master mold for nanoimprinting described herein is provided.

The product may include various products requiring the formation of known nanopatterns. Although not limited thereto, the product may include a low-reflection film, an anti-glare film, a super water-repellent material, a highly sensitive nano biosensor, a functional nano device, a functional display, and a film or substrate that can be used for optical communication components. there is. Although not limited thereto, the product may be suitable for an anti-radiation film and an anti-glare film. In addition, when the master mold for nanoimprinting described herein is used for a product requiring high light transmittance, a product having constant light transmittance can be efficiently provided.

According to another aspect, I-i) preparing a fluorine-based polymer film; and I-ii) forming a nanostructure by treating the surface of the fluorine-based polymer film with an ion beam having an ion beam energy of 50 to 2000 eV, wherein the shape of the nanostructure is one of a protrusion shape, a cone shape, and a wrinkle shape. A method for manufacturing a master mold for nanoimprinting that is more than one species is provided.

Step II-I) is a step of preparing a fluorine-based polymer film formed of a fluorine-based polymer.

In step I-i), the fluorine-based polymer may be composed of various known fluorine-based materials. Although not limited thereto, the fluorine-based polymer is polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluoroalkoxy (PFA), polyvinylidene fluoride (Polyvinylidene fluoride (PVDF), ethylene tetrafluoroethylene (ETFE), and polyvinyl fluoride (PVF). The mold for nanoimprinting of the present application has excellent releasability by using the low surface energy characteristics of the fluorine-based material.

In step I-ii), the step of forming the nanostructure by ion beam treatment is a step of surface-reforming the surface of the fluorine-based polymer to form the nanostructure used as the pattern of the master mold for imprinting on the fluorine-based polymer film. At this time, the ion beam energy of 50 to 2000 eV may be suitable for forming nanostructures on the surface of the fluorine-based polymer film, 50 to 1500 eV may be more suitable, 50 to 1000 eV may be more suitable, and 50 to 500 eV may be more suitable. may be more suitable.

Although not limited thereto, when the ion beam energy is less than 50 eV, the surface modification effect may be insufficient, and when the ion beam energy exceeds 2000 eV, distortion and shrinkage of the fluorine-based polymer film may occur.

Although not limited thereto, the gas used during the ion beam treatment in step I-ii) may contain at least one of argon and oxygen, which is suitable for forming nanostructures on the surface of the fluorine-based polymer. In addition, by forming a low surface energy of the surface of the polymer film together with the formation of the nanostructure, it may be suitable for improving the releasability of the master mold for nanoimprinting of the present application.

Although not limited thereto, the above steps may be performed in a roll-to-roll process. When using the roll-to-roll process, there is an advantage in that the master mold for nanoimprinting of the present application can be produced in a large area. Although not limited thereto, it may be suitable that the process speed of the roll-to-roll process is 0.1 to 10 mpm.

According to an embodiment, a method for manufacturing a master mold for nanoimprinting provides a master mold for imprinting having a nanostructure formed by ion beam treatment on a fluorine-based polymer film and having excellent release properties even without a separate release treatment step. This can simplify the manufacturing process.

According to another aspect, II-i) applying a curable resin on the surface of the master mold for nanoimprinting described herein or on the base substrate; II-ii) attaching the master mold for nanoimprinting and the base substrate with the curable resin interposed therebetween, and then curing the curable resin; and II-iii) releasing the cured resin and the base substrate from the master mold.

Step II-i) is a step of applying the curable resin solution on the surface of the master mold for nanoimprinting described herein. In this case, the curable resin may be applied not to the surface of the master mold for nano-imprinting, but to a base substrate capable of supporting and/or compressing the curable resin used in nano-imprinting. As the base substrate, various known base substrates known in the field of nanoimprinting technology may be used. Although not limited thereto, the base substrate may be made of a polymer material such as polycarbonate (PC) or polydimethylsiloxane (PDMS) or a hard material such as silicon, quartz, or glass. As the curable resin, various known curable resins known in the field of nanoimprinting technology may be used, and may be a thermosetting resin or a photocurable resin. Although not limited thereto, an ultraviolet curable polyurethane resin solution may be used for the photocurable resin.

Step II-ii) is a step of curing the curable resin after attaching the master mold for nanoimprinting and the base substrate with the curable resin described herein interposed therebetween. As a method of curing the curable resin, a method of applying heat and a method of irradiating ultraviolet rays may be used depending on the type of the resin. Curing conditions may be applied to each curing condition suitable for a curable resin known in the art of the present invention.

Step II-iii) is a step of separating the resin cured in step II-ii) and the base substrate from the master mold. At this time, due to the excellent releasability of the master mold made of the fluorine-based polymer of the present invention, the cured resin and the base substrate can be easily released from the master mold without a separate release process.

As described above, the nanoimprinting method of the present application is excellent in productivity because repeated transfer is possible using the master mold for nanoimprinting having excellent releasability and durability.

Example

Hereinafter, the present invention will be described in more detail through specific examples and comparative examples of the present invention, and evaluation results of their characteristics.

1. Preparation of master mold for nanoimprinting in which nanostructures are formed by ion beam treatment and comparison of surface results after 10 transfers of transparent film

2 is a diagram schematically illustrating a method of manufacturing a master mold for nanoimprinting according to an embodiment of the present invention.

Referring to FIG. 2, nanostructures were formed on the surface of PEN and PTFE films by ion beam treatment under the following conditions, and the substrate on which the nanostructures were formed was prepared as a master mold for imprinting. The energy of the ion beam used for surface modification to form nanostructures on the surface of the polymer film is distributed in the range of 30% - 80% of the ion beam anode voltage and generally has a Gaussian distribution, so it has an energy of 300 to 1000 eV. An ion beam anode voltage of 0.6 to 1.2 kV was used to irradiate the specimen with the ion beam.

1) Argon (Ar)

- 1 kV, 70 mA, 0.6 mpm, 10 cycles, 1.17 kW/mpm

2) Oxygen (O ₂ )

- 1 kV, 58 mA, 0.1 mpm, 2 times, 1.16 kW/mpm

After applying an ultraviolet curable resin (NOA74 (Norland Optical Adhesive 74), Norland Products) on the master mold, a transparent film, which is the base substrate of the imprinting object, is attached, and a total of 5 J is applied using an ultraviolet LED having a central wavelength of 365 nm. / cm ² energy was irradiated to complete UV curing and transfer. Then, the cured resin and transparent film were released from the master mold. The transfer and release processes were repeated 10 times to confirm the uniformity and release properties of the PEN and PTFE master molds.

3 is an image showing the surface after 10 transfers of the ion beam-treated PEN mold according to a comparative example of the present invention.

4 is an image showing the surface after 10 transfers of an ion beam treated PTFE mold according to an embodiment of the present invention.

FIG. 5 is a graph showing the surface of each imprinting object transferred after being transferred 1, 5, and 10 times using a PEN mold treated with an ion beam according to a comparative example of the present invention.

FIG. 6 is a graph showing the surface of each imprinting object transferred after repeated transfer 1, 5, and 10 times using an ion-beam-treated PTFE mold according to an embodiment of the present invention.

Referring to FIGS. 3 and 4, when the transfer was repeated 10 times on a transparent film using the PEN master mold as a comparative example, a large area of UV curable resin residue was found on the surface of the master mold as the number of transfers increased. On the other hand, in the case of repeated transfer to the transparent film 10 times using the PTFE master mold as an example, almost no UV curing resin residue was found on the surface of the mold even after 10 repeated transfers.

Referring to FIGS. 5 and 6, the transparent film transferred using the PEN master mold as a comparative example is transferred repeatedly 10 times, as the number of transfers increases, the UV curable resin is not released from the master mold well, leaving a residue. and the untransferred portion increased. On the other hand, in the transparent film transferred using the PTFE master mold as an example, almost no UV curing resin residue was found even after 10 repeated transfers, and the pattern was transferred uniformly.

As a result, the master mold for nanoimprinting of the present application forms a nanostructure that can be used as a pattern by performing ion beam treatment on a fluorine-based polymer, and has excellent releasability of the master mold even after repeated use and transfer, so that the nanostructure formed in a pattern It can be confirmed that a uniform pattern can be formed on an object to be imprinted due to less damage and excellent durability.

2. Transmittance change of imprinted object after repetitive transfer and release

7 is a graph showing a change in transmittance of a film after transferring 10 times using a PEN mold as a comparative example and a PTFE mold as an example of the present invention.

Referring to FIG. 7, the film transferred using the PEN mold as a comparative example had an initial total transmittance (%) of 93.6% initially, but decreased to 82.3% after 10 repeated transfers, with an average of 85.5% and a standard deviation of 3.74%. appeared as a value of

On the other hand, the total transmittance (%) of the film transferred using the PTFE mold as an example was initially 90.4%, but after 10 repeated transfers, it slightly decreased to 89.5%, with an average of 89.3% and a standard deviation of 0.44%. .

As a result, it was confirmed that the film imprinted using the master mold for nanoimprinting including the fluorine-based polymer film of the present application did not change its permeability properties even after repeated transfer. This means that even if the master mold for nanoimprinting of the present application is repeatedly used and transferred, the releasability of the master mold is excellent, so that the nanostructure formed in the pattern is less damaged, and the durability is also excellent, so that almost the same pattern can be maintained even after repeated use. It is the result that represents

3. Surface energy characteristics of fluorine-based polymers after ion beam treatment according to gas type

Fluorine-based polymer PTFE, FEP, and PFA substrates are prepared, and ion beam treatment is performed on the surface of each polymer film using a different type of gas under the following conditions to form a surface modification layer, and the polymer having the surface modification layer is formed. The water contact angle of the film surface was measured. The energy of the ion beam used for surface modification to form nanostructures on the surface of the polymer film is distributed in the range of 30% - 80% of the ion beam anode voltage and generally has a Gaussian distribution, so it has an energy of 300 to 1000 eV. An ion beam anode voltage of 0.6 to 1.2 kV was used to irradiate the specimen with the ion beam.

1) Argon (Ar)

- 1 kV, 70 mA, 0.6 mpm, 10 cycles, 1.17 kW/mpm

2) Oxygen (O ₂ )

- 1 kV, 58 mA, 0.1 mpm, 2 times, 1.16 kW/mpm

3) hydrogen (H ₂ )

- 1 kV, 80 mA, 0.1 mpm, 2 times, 1.6 kW/mpm

4) Argon (Ar) and hydrogen (H ₂ )

- Argon (Ar): 0.6 kV, 26 mA, 0.1 mpm, 2 times, 0.31 kW/mpm

- Hydrogen (H ₂ ): 1.2 kV, 80 mA, 0.1 mpm, 2 times, 1.92 kW/mpm

- Total 2.23 kW/mpm

8 is a graph showing the water contact angle of the surface of the fluorine-based polymer after ion beam treatment according to the type of gas according to an embodiment of the present invention.

Referring to FIG. 8, the contact angles of argon or oxygen ion beam-treated PTFE, FEP, and PFA substrate surfaces with water are all 100° or more, and hydrogen ion beam or argon and hydrogen ion beam-treated PTFE, FEP, and PFA substrate surfaces have water and water contact angles. All of the contact angles were less than 50°. This is a result that can be seen that the contact angle with water is remarkably high in the case of argon ion beam treatment or oxygen ion beam treatment. A high contact angle with water means that the surface energy is low, it is easy to separate or release when attached to other materials, and it indicates that the fluorine-based polymer is suitable for use as a master mold for nanoimprinting.

Therefore, it can be seen that the master mold for nanoimprinting of the present application can be excellent in releasability by treating argon or oxygen ion beam on a fluorine-based polymer to form a nanostructure and use it as a pattern while maintaining a low surface energy.

Claims (12)

Including; polymer film in which a plurality of nanostructures are formed,
The polymer film is made of a fluorine-based polymer,
The nanostructure is formed by ion beam treatment,
Master mold for nanoimprinting. According to claim 1,
The shape of the nanostructure is at least one of a protrusion shape, a cone shape, and a wrinkle shape, the master mold for nano-imprinting. According to claim 1,
The fluorine-based polymer is at least one of PTFE, FEP, PFA, PVDF, ETFE and PVF, a master mold for nano-imprinting. According to claim 1,
Wherein the nanostructure is used to form a pattern on an object to be imprinted, a master mold for nanoimprinting. A product manufactured using the master mold for nanoimprinting according to any one of claims 1 to 4. Ii) preparing a fluorine-based polymer film; and
I-ii) forming a nanostructure by treating the surface of the fluorine-based polymer film with an ion beam having an ion beam energy of 50 to 2000 eV;
The shape of the nanostructure is at least one of a protrusion shape, a cone shape, and a wrinkle shape, a method for manufacturing a master mold for nano-imprinting. According to claim 6,
In step Ii), the fluorine-based polymer is at least one of PTFE, FEP, PFA, PVDF, ETFE and PVF, Manufacturing method of a master mold for nano-imprinting. According to claim 6,
The method of manufacturing a master mold for nano-imprinting, wherein the gas used in the ion beam treatment in step I-ii) includes at least one of argon and oxygen. According to claim 6,
Step Ii) and step I-ii) are performed as a roll-to-roll process, a method for manufacturing a master mold for nano-imprinting. According to claim 9,
The process speed of the roll-to-roll process is 0.1 to 10 mpm, a method for manufacturing a master mold for nano-imprinting. II-i) applying the curable resin on the surface of the master mold for nanoimprinting or on the base substrate according to any one of claims 1 to 4;
II-ii) attaching the master mold for nanoimprinting and the base substrate with the curable resin interposed therebetween, and then curing the curable resin; and
II-iii) releasing the cured resin and the base substrate from the master mold; comprising a nano-imprinting method. The nanoimprinting method of claim 11, wherein the base substrate in step II-i) is a polymer, silicon, or glass substrate.

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