KR100926977B1 - Imprint mold with release film and release film formation method of imprint mold - Google Patents

Abstract

The present invention comprises a main body consisting of a nickel base layer patterned with monocytes of nanoparticles and a nickel electroforming layer thereunder; A release membrane filled with lubricating oil in the pores formed by carbon nanotubes on the nickel base layer of the main body; The present invention relates to an imprint mold having a release film formed thereon and a release film forming method of an imprint mold. The present invention relates to a thin film layer of chromium and titanium, which is a base layer material used to improve adhesion in the case of electroforming for producing a nickel mold. In addition to improving the durability of the nickel mold, by using a release film such as SAM can be easily applied, and by forming a pore through the growth of carbon nanotubes on the nickel mold pattern for imprint, and forming a lubricant film It is easy to solve the damage of the molded part and the wear of the mold due to the adhesion problem with the polymer, and the lubricating oil to form the lubricating film is contained in the carbon nanotube pores, which can solve the durability problem of the existing release film (SAM). It can be used semi-permanently to improve productivity. There is an advantage in that.

 Release Film, Imprint Mold, Nickel Base Layer, Nickel Electroforming Layer, Single Hole, Carbon Nanotube, Lubricant, Plasma

Description

A imprint mold for formed mold-releasing film and method for forming Technical Field

The present invention provides a semi-permanent release on the pattern of the imprint mold so that the molded article can be easily released from the imprint mold in order to prevent wear of the mold and damage of the molded article caused by adhesion of the mold and the polymer molding material. It relates to an imprint mold having a release film and a release film forming method of the imprint mold, characterized in that a film is formed.

In general, manufacturing techniques of semiconductors, biotechnology and optical devices are performed through optical lithography, but this has many problems due to long processing time and high initial investment cost.

Therefore, in recent years, the imprint patterning technology through the deformation of the polymer by physical force has received a lot of attention. This has the advantage that the same molding can be repeatedly repeatedly formed, but the shape of the molded article is not properly formed due to the adhesion problem of the polymer in the process of separating the mold and the molding, there is a problem to shorten the life of the mold.

In order to solve the above problems, the release problems are solved by forming release films such as self assembled monolayers (SAM), such as Korean Patent Publication Nos. 553130, 590727, 744550, etc. Due to the problem, the coating of the release film should be performed periodically, which may cause problems such as productivity decrease and production cost increase.

Therefore, there is a high demand for technology development that can form a release film on the surface of an imprint mold at a lower cost and can be used semi-permanently with reliability.

The present invention to solve the above problems when the electroforming for the production of nickel mold, except for the chromium and titanium thin film layer, which is a heterogeneous metal conventionally used in the base layer to improve the adhesive strength when using the thermal deposition or sputtering deposition using nickel It is an object of the present invention to provide an imprint mold having a release film and a method of forming a release film of the imprint mold, wherein the release film is formed by preventing the peeling of the nickel base layer thin film during electroplating by improving adhesion to the substrate by heat treatment.

In addition, the present invention is to form a uniform pore through the growth of carbon nanotubes on the imprint nickel mold pattern and to form a lubricating film to easily eliminate the damage to the molded product and the wear of the mold due to the adhesion problem between the mold and the polymer Another object of the present invention is to provide an imprint mold having a release film formed thereon and a release film forming method of the imprint mold.

In addition, the present invention is a lubricating oil to form a lubricating film is contained in the carbon nanotube pores to solve the durability problems of the conventional release film, such as semi-permanent use is possible because the release film is characterized in that it can greatly improve the productivity Another object is to provide a formed imprint mold and a release film forming method of the imprint mold.

The present invention provides a method for forming a release film on an imprint mold,

(a) the base layer of the imprint mold Plasma etching to form monocytes of nanoparticles on the imprint mold surface;

(b) forming capillary shaped nanosized pores while growing carbon nanotubes on top of the monocytes by plasma enhanced chemical vapor deposition (PECVD) while supplying hydrocarbons;

(c) filling a lubricating oil for forming a release film in the pores;

The method for forming a release film on the imprint mold, characterized in that the through and the imprint mold manufactured by the above method is a problem solving means.

As described above, the present invention first removes the chromium and titanium thin film layers, which are conventionally used for improving adhesion, during electroforming for producing a nickel mold, and improves the durability of the nickel mold, such as SAM and the like. The release film can be easily applied, and by forming carbon pores through the growth of carbon nanotubes on the imprint nickel mold pattern and forming a lubricating film, it is easy to solve the damage of the molded product and the wear of the mold due to the adhesion problem between the mold and the polymer. In addition, the lubricating oil forming the lubricating film is contained in the carbon nanotube pores, so it is possible to semi-permanently use to solve the durability problems such as the existing release film (SAM), there is an advantage that can greatly improve the productivity.

The present invention for achieving the effect as described above to grow the carbon nanotubes (carbon nanotubes, hereinafter referred to as "CNTs") on the pattern of the imprint mold for forming the microstructures to form uniform pores, the lubricating oil in the pores The present invention relates to a method of forming a semi-permanent release film through the formation of a lubricating film by heating and cooling during imprinting and to forming a release film of the imprint mold and the imprint mold.

Hereinafter, a method of forming a release film on an imprint mold according to the present invention will be described in detail with reference to the accompanying drawings.

1A to 1D are schematic diagrams illustrating a manufacturing process of an imprint nickel mold having a conventional nickel layer formed thereon, and FIGS. 2A to 2D are nickel layer formed according to the present invention. The schematic diagram which shows the manufacturing process of an imprint nickel mold is related.

Hereinafter, a manufacturing process of an imprint mold having a nickel base layer according to the present invention will be described in detail with reference to FIGS. 2A to 2D.

First, referring to a conventional imprint mold manufacturing process, a pattern having a nano size is formed on a wafer 110 using a photoresist (PR) 120, and then a chromium deposition process is performed on the wafer 110. After forming the chromium seed layer (Seed Layer) (130) through the nickel deposition (Depositon) on top of the nickel base layer (Seed Layer) (140a) is formed (Fig. 1a).

In addition, a nickel electroforming layer 140b having a thickness of 0.5 to 1 mm is formed by using an electroforming process on the nickel base layer 140a to manufacture an imprint mold 100 (FIG. 1B). After separation from the wafer 110 (FIG. 1C), the photoresist (PR) 120 inside the imprint mold is removed using an etching process (FIG. 1D).

Although the thickness of the nickel electroforming layer 140b is limited to 0.5 to 1 mm, it may be appropriately adjusted as necessary.

When the imprint mold 100 is manufactured according to the conventional method as described above, when the thin film is formed using heterogeneous metals such as chromium and nickel as a seed layer, In addition to having a problem in the durability of the mold 100 during imprint, chromium has an unsuitable problem as a catalyst metal for growth of carbon nanotubes for forming pores in the present invention.

Therefore, in the present invention, an imprint mold having a seed layer formed using only a single type of metal, that is, nickel, was fabricated to improve the above problems.

Hereinafter, the manufacturing process of the imprint mold according to the present invention is as follows.

After forming a pattern having a nano size using a photoresist (PR, photoresist) (120) on the wafer (110), a nickel base layer (Seedon) through a nickel deposition process (top) 140a) (FIG. 2A).

The photoresist (PR) 120 used in the present invention does not become a feature of the present invention because it uses the same kind of compound as used in the conventional method. Since photoresist PR varies in type depending on the pattern type, in order to prevent deformation of the photoresist PR during heat treatment if possible, in selecting the photoresist PR, a high glass point transition temperature Tg is high. It is preferable to use photoresist PR.

The nickel layer is a conventional method such as electron beam deposition and sputter deposition.

In the present invention, the deposition rate of the nickel base layer thin film is set to 1.0 ~ 1.5mA per second by setting the current of 100mA ~ 150mA in consideration of the resistance and density of the nickel base layer thin film.

When the deposition condition is less than the above-defined range, the deposition rate is lowered, and when the deposition condition exceeds the above-defined range, an overflow problem may occur.

In addition, an imprint mold 100 is manufactured by forming a nickel nanocasting layer 140b having a predetermined nano-thickness using an electroforming process on top of a nickel layer 140a (FIG. 2B).

Then, the fabrication imprint mold 100 is separated from the wafer 110 (FIG. 2C), and then the photoresist (PR) 120 inside the imprint mold is removed using an etching process.

2B to 2D are performed by the same method as the conventional process.

Although the imprint mold 100 according to the present invention has a high solubility for carbon and an empty 4d electron orbit, it is required to form a matrix through nickel, which is easy to adsorb with acetylene (C ₂ H ₂ ). Looking at the photograph taken a state in which the nickel base layer is bonded to the substrate as shown in the case of nickel, the adhesion to the substrate is degraded, the peeling phenomenon occurs during plating.

Therefore, in the present invention, by forming a nickel base layer through heat treatment at a temperature of 150 ± 20 ℃ in order to solve the above problems, as shown in Figure 3b to the state where the nickel base layer is bonded to the substrate Looking at the photographs taken, it can be seen that the peeling of the nickel thin film for electroplating and adhesion to the substrate is good.

If the heat treatment condition is less than the range defined above, there is a risk of peeling of the plating layer and the base layer during washing, and if the heat treatment condition exceeds the range defined above, deformation of the photoresist (PR) is prevented. Can cause.

3A and 3B relate to a photograph of a state in which a nickel base layer is bonded to a substrate.

A method of forming a release film using an imprint mold according to the present invention will be described in detail with reference to FIGS. 4A to 4D.

4A and 4B illustrate a step of forming a terrace by using plasma etching on a pattern of a nickel matrix layer, FIG. 4C is a step of growing CNTs in nickel monocytes, and FIG. 4D is a diagram in which lubricant is infiltrated into pores between CNTs. It is related to the schematic diagram which showed the state.

The present invention provides a method for forming a release film on an imprint mold,

(a) plasma etching the matrix layer 140a of the imprint mold 100 to form the nanoparticles 150 on the surface of the imprint mold; (FIGS. 4A and 4B);

(b) forming capillary nano-sized pores while growing CNTs 200 on top of the sections 150 by plasma enhanced chemical vapor deposition (PECVD) while supplying hydrocarbon; (FIG. 4C);

(c) filling the lubricating oil 300 to form a release film inside the pores; (4d)

It relates to a method of forming a release film on an imprint mold, characterized in that through.

In step (a), as shown in FIG. 4A, the nickel base layer 140a on the imprint mold 100 manufactured by electroforming is used as a catalyst metal for CNTs growth, As shown in FIG. 4B, a terminator 150 of fine catalytic metal particles having a size of several nanometers is formed. The resulting catalytic metal in the form of a trace reacts with the carbon atoms of the carbon gas.

The plasma etching conditions are NH ₃ 170 ~ 190 sccm in 1 ~ 5 minutes 10 ~ 40 mA is recommended to be carried out, if out of the above range of the sphere is not formed properly or nickel cast layer This may be damaged.

In the step (a), the imprint mold 100 includes a nickel base layer 140a and a nickel electroforming layer 140b, and the nickel base layer 140a is a wafer 110 during electroforming of the mold. With) Heat treatment at 150 ± 20 ° C. is preferred to improve adhesion.

In addition, the step (b) is a capillary shape while growing CNTs 200 on top of the monocytes 150 by plasma enhanced chemical vapor deposition (PECVD) while supplying hydrocarbons as shown in FIG. 4C. In the step of forming nano-sized pores, the carbonized gas used in this case has the lowest activation energy for thermal decomposition among the various carbonized gases and can easily supply carbon as a catalyst to acetylene (C ₂ H ₂ ) Mainly use gas. The reaction of the carbon atoms separated from the reaction gas with the catalytic metal occurs preferentially at the edges of the metal particles to facilitate adsorption, and the adsorbed carbon atoms are dissolved and diffused into the catalyst metal to form a carbon layer at the edge. As the carbon layers accumulate, the walls of CNTs form. The CNTs grown on the mold pattern form nano pores.

The growth of the CNTs 200 is a silicon wafer with a Ni matrix layer deposited thereon is heated to 610 ~ 630 ℃ under a high vacuum atmosphere of 5.0 × 10 ^-5 ~ 5.5 × 10 ^-5 Torr, the core of the carbon nanotubes In order to make the catalyst metal particles, NH ₃ is flowed into the chamber at 170 to 190 sccm, and DC power is applied between the two electrodes at a pressure of 2 to 4 Torr to induce NH ₃ plasma. C ₂ H ₂ gas was used as a reaction gas for synthesizing carbon nanotubes, and CNTs 200 were grown by applying DC power while supplying 25 to 35% of NH ₃ gas in the pretreatment condition.

If the growth conditions of the CNTs 200 are less than the above range, there is a concern that the growth of the CNTs may not be performed properly. If the growth conditions of the CNTs 200 exceed the above range, the CNTs may be overgrown. There exists a possibility that the interface of CNTs may become nonuniform.

In the step (c), the lubricating oil for forming the release film is filled in the pores of the CNTs 200 in the pores of the CNTs 200 formed in the step (b), as shown in FIG. 4D.

Inside the pores of the CNTs 200 is sprayed with lubricating oil in a spray type and a vapor (vapor) method and then filled by ultrasonic vibration.

As described above in detail with reference to FIGS. 5A to 5D, the process of forming a release film during molding of a nano-molded product using the imprint mold 100 having the release film manufactured according to the present invention as follows is as follows. .

5A to 5D are schematic diagrams showing a state in which a semi-permanent release film acts in an imprint process using an imprint mold manufactured according to the present invention.

As shown in FIG. 5A, first, the polymer molding material 400 is pressed onto the surface on which the pattern of the imprint mold 100 according to the present invention is formed.

In the heating process for the flow of the polymer molding material 400 during the imprint process, when heated above the glass-transition temperature (Tg) of the polymer, as shown in FIG. The lubricating oil filled in the pores rises on the pattern surface of the imprint mold 100 due to thermal expansion, and is formed between the imprint mold 100 and the polymer molding material 400 so that the mold and the molding material do not adhere to each other in the pressing process. A very thin lubricating film release film is formed on the film.

In the cooling process of the imprint, as shown in FIG. 5C, the lubricant is refilled in the pores of the CNTs again due to the cooling of the lubricant.

Since the polymer molded article in which the imprint process is completed is easily separated from the imprint mold by a release film formed between the imprint mold 100, an imprint limitation may be overcome due to the adhesion problem between the imprint mold and the polymer molded article.

As such, the CNTs can be used as a semi-permanent release membrane through the repetition of capillary refilling due to heat shrinkage of the lubricating oil during generation of the release membrane due to thermal expansion of the lubricating oil during the imprint heating process.

The configuration of the imprint mold having a semi-permanent release film produced by the above method is as follows.

A main body consisting of a nickel matrix layer patterned into monocytes of nanoparticles and a nickel electroforming layer below;

And a release film filled with lubricating oil in the pores formed by carbon nanotubes on the nickel base layer of the main body.

And the nickel base layer is characterized in that formed by monocytes.

Since the lubricating oil used in the imprint mold of the present invention has already been described in detail above, the description thereof will be omitted.

As described above, the present invention has been described in detail, but it will be understood that the present invention can be variously modified and changed without departing from the spirit and scope of the invention as set forth in the claims below. .

1A to 1D are schematic views showing a manufacturing process of a conventional imprint mold;

2A to 2D are schematic diagrams showing a manufacturing process of an imprint nickel mold having a nickel seed layer according to the present invention;

3A and 3B are photographs of a state in which a nickel base layer is bonded to a substrate;

Figures 4a to 4d is a schematic diagram showing the step of forming a semi-permanent release film by growing carbon nanotubes on the pattern of the nickel base layer in which the termination is formed in accordance with the present invention;

5A to 5D are schematic diagrams showing a state in which a semi-permanent release film acts in an imprint process using an imprint mold manufactured according to the present invention.

Explanation of symbols on the main parts of the drawings

100: imprint mold 110: wafer

120: photoresist (PR) 130: chrome seed layer

140a: Nickel Base Layer 140b: Nickel Electroforming Layer

150: terminal 200: carbon nanotubes (CNTs)

300: lubricant

Claims (7)

In the method of forming a release film in an imprint mold, (a) the base layer of the imprint mold Plasma etching to form monocytes of nanoparticles on the imprint mold surface; (b) forming capillary shaped nanosized pores while growing carbon nanotubes on top of the monocytes by plasma enhanced chemical vapor deposition (PECVD) while supplying hydrocarbons; (c) filling a lubricating oil for forming a release film in the pores; Method for forming a release film on the imprint mold, characterized in that through. The method of claim 1, The method of forming a release film on the imprint mold, characterized in that (im) the imprint mold comprises a nickel base layer and a nickel electroforming layer. The method of claim 2, The nickel base layer is in contact with the wafer during electroforming of the mold. A method of forming a release film on an imprint mold, characterized in that the heat treatment at 150 ± 20 ℃ to improve the adhesion. The method of claim 1, In step (b), the hydrocarbon is acetylene (C ₂ H ₂ ), characterized in that to form a release film on the imprint mold. The method of claim 1, In the step (b), the carbon nanotube growth condition is performed by supplying acetylene (C ₂ H ₂ ) to a silicon wafer having a Ni substrate layer deposited thereon under a high vacuum atmosphere of 5.0 × 10 ⁻⁵ to 5.5 × 10 ⁻⁵ Torr. Heated to 610 ~ 630 ℃, NH ₃ is flowed into the chamber at 170 ~ 190sccm to make catalytic metal particles, which are the nucleus of carbon nanotubes, and the NH ₃ plasma is induced by applying DC power between two electrodes at a pressure of 2 ~ 4Torr. Growing to form a release film on the imprint mold. A main body consisting of a nickel matrix layer patterned into monocytes of nanoparticles and a nickel electroforming layer below; A release membrane filled with lubricating oil in the pores formed by carbon nanotubes on the nickel base layer of the main body; Imprint mold formed with a release film, characterized in that consisting of. The method of claim 6, The nickel-based layer is an imprint mold formed with a release film, characterized in that formed in the monocyte.

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