KR20140023629A - A fabrication method of nano patterned film using photolithography and plating - Google Patents

Abstract

The present invention relates to a fabrication method of a nanopatterned film using photolithography and plating. According to the present invention, a fabrication method, in a method for fabricating a sheet or a film having nanopatterns, includes a first step of spraying photoresist on a substrate, a second step of forming a photoresist pattern where a residual layer of predetermined thickness remains by performing an exposure and development process on the photoresist, a third step of performing a seed layer deposition and a plating process on the photoresist pattern, and a forth step of fabricating the sheet or the film having nanopatterns by removing the photoresist pattern using a solvent. Therefore, the sheet or the film having nanopatterns can be obtained by using a simple process.

Description

A Fabrication Method of Nano Patterned Film Using Photolithography and Plating}

The present invention relates to a method for manufacturing a film in which a nanopattern is formed using photolithography and plating. More particularly, when a photoresist patterning is performed using photolithography, a photosensitive pattern in which a residual layer of a predetermined thickness remains is formed and is left. The present invention relates to a method of manufacturing a film on which a nanopattern is formed using photolithography and plating, in which a metal is deposited on a photoresist in which a layer remains, and plating is performed, and finally a film or a sheet is formed by removing a photoresist. .

In general, in various fields such as sensors, batteries, and capacitors, micro / nano size patterns are formed on electrodes to increase performance. At this time, the easiest method to use is to coat nano / microparticles on the substrate and use it after sintering. This is a method that is widely used because mass production is possible with low production cost.

However, it is difficult to form a desired pattern by the above-described method, and there are restrictions on the temperature and pressure of the sintering process. Therefore, these parameters must be considered in the product design process. In addition, if the dispersion of particles is not controlled, the effect of increasing the surface area is halved, so controlling these parameters is very important for increasing the surface area using nanoparticles.

In the case of an optical element, various characteristics are shown according to the pattern period and size density. In order to utilize such characteristics, a pattern must be formed at a desired position. However, patterning of nanoparticles at desired locations is difficult to use due to inefficiency of cost and time. Accordingly, various methods of patterning have been developed and used industrially. Various methods such as nano-imprint lithography and roll-to-roll imprint lithography have been developed as well as popular photolithography.

However, photolithography has a problem in that it is difficult to use a film / sheet type substrate, and in the case of imprint lithography, a problem to be solved remains, such as a stamp production problem.

According to the related art, Korean Patent Laid-Open Publication No. 2011-0048395 discloses a cleaning body for a liquid crystal display device which repetitively makes a replica cleaner based on a replicated disk cleaner, a manufacturing method thereof, And a method for producing a replica cleaner.

However, such a conventional technique has a disadvantage in that the seeded-layer removal process must be included when the substrate on which the pattern is formed is copied, which complicates the process.

Korean Patent Laid-Open Publication No. 2009-0059641 discloses a method of manufacturing a stamp for imprint through photolithography and nickel plating. However, a disadvantage in that several seed-layer deposition and removal processes are required to manufacture a nickel stamp have.

As such, the nano-patterned film / sheet may be variously applied while maintaining the existing industrial framework. However, in order to produce such films / sheets, a complicated process or low productivity is still difficult to utilize.

The present invention has been made to solve the above problems, by using a photolithography and plating process, to provide a method for producing a film with a nano-pattern formed film that can form a thin sheet form substrate with a nano-pattern formed have.

In addition, by using a photolithography and plating process to simplify the process using the remaining layer of the photoresist, to provide a nano-patterned film manufacturing method that can obtain a nano-patterned film / sheet in a simple process There is this.

In addition, in the film / sheet manufacturing process in which the nano-pattern is formed, the method of manufacturing a film in which the nano-pattern is formed can eliminate the seed-layer removal process and can be easily separated, thereby greatly reducing the process cost and process time. The purpose is to provide.

In order to achieve the above objects, in the method of manufacturing a film or sheet formed with a nano-pattern, the first step of applying a photoresist on the upper substrate, and the exposure layer and the development of the photoresist to the remaining layer of a predetermined thickness Two steps of forming the remaining photosensitive pattern, three steps of depositing and plating a seed layer on the photosensitive pattern, and four steps of manufacturing a film or sheet having a nanopattern formed by removing the photosensitive pattern with a solvent. Provided is a method of manufacturing a film including a nanopattern formed therein.

In the present invention, the step 1 may include applying a photoresist of any one or more of a water-soluble photoresist and a conductive photoresist using a method of spin coating, spraying, or deposition.

In addition, in the first step, in order to easily separate the film or sheet on which the nano-pattern is formed from the substrate, a polymer material used as a sacrificial layer before applying the photoresist is applied by spin coating, spraying, or deposition. It can be made, including the step.

In the present invention, in the second step, the size and height of the photosensitive pattern may be adjusted by adjusting the thickness of the photoresist, the energy of exposure or the development time, and the remaining layer may remain at a predetermined thickness.

The photoresist is characterized in that the coating by applying in the range of 10nm ~ 200㎛.

The photoresist may be exposed by irradiating an energy amount of 1mJ to 1000mJ.

In addition, the time for developing the photoresist is characterized in that the range of 5 seconds to 1 hour.

In the present invention, the third step, the seed layer may be deposited in a single layer or multiple layers.

The seed layer may include an insulator, a metal, or a polymer.

In the present invention, the three steps may be performed, including forming a film or sheet of metal by performing electroplating.

Here, when the electroplating is carried out, it may include the step of forming a film or sheet of metal by changing the direction of the voltage, the on / off period, time, current amount of the current.

In addition, the metal is Ni, Co, Fe, Pt, Au, Ag, Al, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V, Li and Zr One or more selected elements may be monolayer or multilayer plated.

In the present invention, the three steps may be performed, including the step of electroless plating to form a film or sheet.

In the present invention, the step 4 may include separating the substrate on which the nano-patterned film or sheet is formed by dipping or ultrasonic sonication using a solvent.

According to the present invention as described above, by using a conventional photolithography and plating process to simplify the process using the remaining layer of the photoresist, it is possible to obtain a nano patterned film / sheet in a simple process have.

In addition, in the film / sheet fabrication process in which the nano-pattern is formed, it is possible to remove the Seed-layer removal process and to easily separate, thereby significantly reducing the process cost and process time.

The process introduced in the present invention can be applied to various devices whose performance increases as nano patterns, such as sensors, batteries, and supercapacitors, are formed. The photolithography and plating process commonly used in existing industries can be used immediately, and the process is simplified because the Seed-Layer removal process used in the plating process is omitted. As a result, it is possible to reduce the process cost and the process time, and the domestic and international ripple effect is expected to be large.

1 is a cross-sectional view showing a process according to a first embodiment of the present invention.
2 is a cross-sectional view showing a process according to a second embodiment of the present invention.
3A to 3B are TEM photographs showing data according to exposure conditions for each energy in the present invention.
4A to 4B are TEM photographs showing data according to a pattern form in the present invention.
5a to 5b is a TEM photograph showing a metal sheet formed with a nano-pattern after the final process according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the present embodiments are intended to complete the disclosure of the present invention and to those skilled in the art to fully understand the scope of the invention. It is provided to inform you.

In the method of manufacturing a film having a nanopattern formed thereon, patterning is performed on a general silicon or glass substrate using photolithography, and after the photoresist development process is performed, the remaining layer is irradiated with energy weaker than normal exposure conditions. It can be formed. The remaining layer serves to help the nanopatterned metal sheet and the substrate to be easily separated after the plating process. Subsequently, a material such as a metal is deposited, and plating is performed to form a metal film in the form of a film / sheet, and the film / sheet in which the nanopattern is formed can be obtained by dipping in a solvent and removing the photoresist with the remaining layer.

≪ Embodiment 1 >

1 is a cross-sectional view showing a process according to a first embodiment of the present invention.

In order to manufacture the film on which the nanopattern of the present invention is formed, first, the photoresist 12 is coated on the substrate 10 (FIG. 1A).

As the substrate 10, a general silicon or glass substrate may be used, and in order to facilitate separation of the finally obtained film and the substrate 10, it is advantageous to increase the thickness of the photoresist 12.

Preferably, the photoresist 12 may be applied to a thickness in the range of 10 nm to 200 μm, so that the formation of the nanopattern and separation from the substrate 10 may be easily performed during the subsequent process.

According to the experiments of the applicant, when the thickness of the photoresist 12 is applied to less than 10nm, not only the pattern area that can be increased is too small, but also the remaining layer in the subsequent process is made of too thin thickness of the photoresist pattern. Formation is not easy and this may make it difficult to separate from a board | substrate. In addition, when the thickness of the photoresist 12 is greater than 200 μm, uniform coating of the photoresist 12 is difficult, and there is a disadvantage in that excessive consumption of the photoresist 12 and uniformity of the pattern are inferior.

In addition, the photoresist 12 used in the present invention may use any one or more of a water-soluble photoresist and a conductive photoresist according to the purpose, but the present invention is not limited thereto.

In addition, the method of applying the photoresist 12 may be a method of spin coating, spraying or vapor deposition.

Thereafter, an exposure process is performed on the photoresist 12 using the mask 20 (FIG. 1B).

In this case, in the present invention, the exposure process may be performed by irradiating weaker energy than general normal exposure conditions.

As described above, when the exposure energy is set lower than the general conditions, the photosensitive pattern 12a in which the remaining layer remains in the photoresist 12 may be formed after development.

In this case, it is preferable that the exposure conditions irradiated to the photoresist 12 are exposed by irradiating an amount of energy in the range of 1 mJ to 1000 mJ.

3A to 3B are TEM photographs showing data according to energy exposure conditions according to the present invention. FIG. 3A is an exposure energy of 30 mJ, and FIG. 3B is an exposure energy of 50 mJ. When setting it to 100 mJ, FIG. 3D shows the case where exposure energy is set to 200 mJ.

According to the experiment of the applicant, since the photosensitive pattern appears very thin when the exposure energy condition is 200 mJ, the exposure energy is preferably set to 200 mJ or less.

However, this is a result of the photoresist experimented by the applicant, and by adjusting the type of photoresist and the development time to be described later, the amount of exposure energy can be adjusted.

In the present invention, the photoresist energy of the photoresist is set to be lower than the normal condition, and the development process is also performed for a shorter time than the normal condition.

In the photolithography process, the exposure energy amount and the development time are complementary to each other, and if necessary, only one of the process conditions may be changed.

When the development is performed after the exposure process as described above, as illustrated in FIG. 1C, a photosensitive pattern 12a in which a residual layer having a predetermined thickness remains is formed on the substrate 10.

Here, the developing time is shorter than the normal conditions so that the remaining layer of the photoresist 12 can be formed.

In this case, the photoresist 12 is preferably developed in the range of 5 seconds to 1 hour.

According to the applicant's experiment, when the photoresist 12 is developed in less than 5 seconds, the development time is too small to form a photosensitive pattern, and the photoresist 12 is developed for more than 1 hour. It is difficult for the remaining layer of photoresist 12 to be formed.

As described above, in the present invention, the exposure energy amount and the development time are complementary to each other, and if necessary, only the conditions of one process may be changed.

That is, in the present invention, the size and height of the photosensitive pattern 12a may be variously manufactured by adjusting the thickness, exposure condition, or development condition of the photoresist 12.

In the present invention, the remaining layer serves to facilitate the separation of the nano-patterned metal sheet 30 and the substrate 10 after the plating process.

Thereafter, a seed layer 14 is deposited by depositing a material such as a metal on the remaining layer on which the photosensitive pattern 12a is formed (FIG. 1D).

In this case, since the material to be deposited first becomes the surface of the finally obtained film or sheet, the seed layer 14 may proceed with a single layer or multilayer deposition of a desired material such as an insulator, a metal, and a polymer.

Thereafter, plating is performed to form a metal film 16 in the form of a film or sheet.

The plating may be performed by electroplating. When the electroplating is performed, a film having a desired thickness at a high speed may be changed by changing the direction of voltage, on / off period of current, current density, current application form, time, and current amount. A sheet can be obtained.

Wherein the metal is selected from the group consisting of Ni, Co, Fe, Pt, Au, Ag, Al, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V, Li and Zr One or more selected elements may be monolayer or multilayer plated.

Alternatively, in forming the metal film 16, electroless plating may be used as necessary.

Subsequently, when a metal film or sheet having a desired thickness is formed, the substrate 10 on which the metal film 16 is formed is immersed in a solvent to melt the photoresist 12 to separate the substrate 10 and the film / sheet 30.

In this case, it is advantageous to select a solvent used in the process that does not affect the substrate 10 and the deposition material. When the photoresist 12 and the remaining layer 12a formed in the previous process are dissolved in a solvent, they can be separated without removing the seed layer 14 and a film / sheet easily formed with a nano pattern ( 30) can be obtained.

In this case, the substrate 10 on which the metal layer 16 is formed may be separated by dipping or ultrasonic sonication using a solvent.

4A to 4B are TEM photographs showing data according to a pattern form in the present invention.

As seen from this, in the case of the pattern type shown in Fig. 4A, the thickness of the photoresist is 1.23 mu m. In the case of the pattern type shown in Fig. 4B, the height of the photosensitive pattern is 3.16 mu m and the height of the remaining layer is 1.19 mu m. Able to know.

The metal sheet finally completed through such a process is shown in FIGS. 5A and 5B.

Figure 5a is a photograph showing a metal sheet formed with a nano pattern after the final process according to the present invention, Figure 5b is a cross-sectional view.

As described above, according to the manufacturing method of the present invention, a metal sheet on which a nanopattern is formed can be obtained.

Second Embodiment

2 is a cross-sectional view showing a process according to a second embodiment of the present invention.

In order to manufacture the film having the nanopattern of the present invention, first, the photoresist 12 must be applied to the top of the substrate 10. In the second embodiment of the present invention, the film or sheet having the nanopattern is formed on the substrate 10. In order to easily separate from), the sacrificial layer 11 is applied before the photoresist 12 is applied.

The sacrificial layer 11 may be formed by applying a polymer material by spin coating, spraying, or deposition.

At this time, the polymer forming the sacrificial layer 11 is advantageously selected that does not react with the developing solution.

In the second embodiment, since the sacrificial layer 11 polymer is coated, the process may be performed without worrying about the remaining layer. As a result, when forming a pattern using photolithography, the exposure energy and the developing time can be freely changed as necessary to proceed with the process.

Thereafter, an exposure process is performed on the photoresist 12 using the mask 20 (FIG. 2B).

When the development is performed after the exposure process, the photosensitive pattern 12a is formed on the sacrificial layer 11 as illustrated in FIG. 2C.

In the present invention, the exposure energy amount and the development time are complementary to each other, and if necessary, the process may be performed by changing only one process condition.

That is, in the present invention, the size and height of the photosensitive pattern 12a may be variously manufactured by adjusting the thickness, exposure condition, or development condition of the photoresist 12.

The sacrificial layer 11 serves to help the nano-patterned metal sheet 30 and the substrate 10 to be easily separated after the plating process.

Subsequently, a seed layer 14 is deposited by depositing a material such as a metal on the photosensitive pattern 12a (FIG. 2D).

In this case, since the material to be deposited first becomes the surface of the finally obtained film or sheet, the seed layer 14 may proceed with a single layer or multilayer deposition of a desired material such as an insulator, a metal, and a polymer.

Thereafter, plating is performed to form a metal film 16 in the form of a film or sheet.

The plating may be performed by electroplating. When the electroplating is performed, a film having a desired thickness at a high speed may be changed by changing the direction of voltage, on / off period of current, current density, current application form, time, and current amount. A sheet can be obtained.

Wherein the metal is selected from the group consisting of Ni, Co, Fe, Pt, Au, Ag, Al, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V, Li and Zr One or more selected elements may be monolayer or multilayer plated.

Alternatively, in forming the metal film 16, electroless plating may be used as necessary.

Subsequently, when a metal film or sheet having a desired thickness is formed, the substrate 10 on which the metal film 16 is formed is immersed in a solvent to melt the photosensitive pattern 12a of the photoresist 12 and the polymer of the sacrificial layer 11. 10) and the film / sheet 30.

In this case, it is advantageous to select a solvent used in the process that does not affect the substrate 10 and the deposition material. When the photosensitive pattern 12a and the sacrificial layer 11 formed in the previous process are dissolved in a solvent, they can be separated without removing the seed layer 14, and a film / sheet easily formed with a nano pattern ( 30) can be obtained.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation in the embodiment in which said invention is directed. It will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the appended claims.

10 substrate 11 sacrificial layer
12 photoresist 12a photosensitive pattern
14 seed layer 16 metal film
20: mask 30: film / sheet with a nano-pattern formed

Claims (14)

In the method for producing a film or sheet with a nano-pattern is formed,
Applying a photoresist on top of the substrate;
Exposing and developing the photoresist to form a photosensitive pattern in which a residual layer having a predetermined thickness remains;
Performing a seed layer deposition and plating on the photosensitive pattern; And
Removing the photosensitive pattern with a solvent to prepare a film or sheet having a nanopattern formed thereon;
Nano-pattern formed film manufacturing method comprising a. The method according to claim 1,
In the first step,
Applying at least one of the water soluble photoresist and the conductive photoresist using a method of spin coating, spraying or vapor deposition;
Nano-pattern formed film production method characterized in that it comprises a. The method according to claim 1,
In the first step,
Applying a spin coating, spraying, or depositing polymer material to be used as a sacrificial layer before applying the photoresist so as to easily separate the nanopattern-formed film or sheet from the substrate;
Nano-pattern formed film production method characterized in that it comprises a. The method according to claim 1,
In the second step,
And controlling the thickness and energy of the photoresist, the exposure energy, or the development time, thereby controlling the size and height of the photosensitive pattern and leaving the remaining layer at a predetermined thickness. The method of claim 4,
The photoresist is a film manufacturing method with a nano-pattern characterized in that the coating by exposure to a thickness in the range of 10nm ~ 200㎛. The method of claim 4,
1mJ ~ 1000mJ energy amount of the photoresist is exposed to the film manufacturing method characterized in that the exposure. The method of claim 4,
The method of manufacturing a film with a nano-pattern characterized in that the development of the photoresist for 5 seconds to 1 hour. The method according to claim 1,
The third step,
Nano patterned film manufacturing method characterized in that the seed layer is deposited in a single layer or multiple layers. The method according to claim 8,
The seed layer is a nano pattern formed film manufacturing method, characterized in that comprising an insulator, a metal or a polymer. The method according to claim 1,
The third step,
Performing electroplating to form a film or sheet of metal;
Nano-pattern formed film production method characterized in that it comprises a. The method of claim 10,
Forming a film or sheet of metal by changing the direction of voltage, on / off period, time, and amount of current when electroplating is performed;
Nano-pattern formed film production method characterized in that it comprises a. The method of claim 10,
The metal is one selected from the group consisting of Ni, Co, Fe, Pt, Au, Ag, Al, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V, Li and Zr Single layer or multi-layer plating of the above elements, The film manufacturing method with a nanopattern formed. The method according to claim 1,
The third step,
Performing electroless plating to form a film or sheet;
Nano-pattern formed film production method characterized in that it comprises a. The method according to claim 1,
In the fourth step,
Separating the substrate on which the nanopatterned film or sheet is formed by dipping or ultrasonic sonication using a solvent;
Nano-pattern formed film production method characterized in that it comprises a.

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