KR100526053B1 - Mold using amorphous fluorine resin and fabrication method thereof - Google Patents

Abstract

The present invention is easy to separate from the substrate to form a pattern, has excellent gas permeability, and can maintain the flexibility and mechanical strength appropriately, the present invention is a mold for forming a pattern on the substrate Unlike the prior art using PDMS, which is a kind of polymer elastomer which is susceptible to deformation due to low mechanical strength and is susceptible to deformation due to swelling due to organic solvents, As a material, amorphous Teflon, i.e., low surface energy, facilitates mold separation, has adequate mechanical strength, high gas permeability, non-swelling properties to organic solvents, and amorphous to provide uniform contact with the substrate surface. By using Teflon, which is a fluororesin, separation from the substrate is easy after patterning, and gas permeation is achieved. The steel with excellent and at the same time, the deformation caused by the particular solvents, has a greater mechanical strength than the elastic member, it is possible to realize uniform contact with the substrate via a secure flexibility.

Description

Mold using amorphous fluororesin and its manufacturing method {MOLD USING AMORPHOUS FLUORINE RESIN AND FABRICATION METHOD THEREOF}

The present invention relates to a mold (mold) for forming a pattern (nm-cm) of various sizes on the substrate, and more particularly, in the manufacturing process of integrated circuits, electronic devices, optical devices, magnetic devices, etc. For example, the present invention relates to a mold using an amorphous fluorine resin used to form a pattern (ultra fine pattern, fine pattern, pattern, etc.) on a silicon substrate, a ceramic substrate, a metal layer, a polymer layer, and the like, and a method of manufacturing the same.

As is well known, a process of forming a fine pattern on a substrate is performed when manufacturing a semiconductor, electronic, photoelectric, magnetic, display device, microelectromechanical device, and the like. Representative techniques include photolithography, which forms fine patterns using light.

The photolithography method is applied to a substrate on which a material to be patterned is laminated (or deposited) on a polymer material having a responsiveness to light (for example, a photoresist, etc.) and designed in a desired pattern. The light is transmitted through the reticle on the polymer material and exposed, and the exposed polymer material is removed through the development process, thereby forming a pattern mask (or an etching mask) having a target pattern on the material to be patterned. Thereafter, by performing an etching process using a pattern mask, the material laminated on the substrate is patterned into a desired pattern.

On the other hand, in the photolithography method as described above, the circuit line width (or pattern line width) is determined by the wavelength of light used in the exposure process. Therefore, in consideration of the current state of the art, it is very difficult to form an ultrafine pattern, for example, an ultrafine pattern having a line width of 100 nm or less, on a substrate using a photolithography process.

In addition, these conventional photolithography methods are complicated because they have to undergo several steps (eg, substrate cleaning, substrate surface treatment, photosensitive polymer coating, low temperature heat treatment, exposure, development, cleaning, high temperature heat treatment, etc.). In addition, there is a problem that not only takes a lot of processing time, but also requires expensive process equipment, and this problem has a fundamental disadvantage of increasing the manufacturing cost and lowering productivity.

As a means for overcoming the limitations of the conventional photolithography method as described above, lithography methods by non-traditional methods have been proposed.

As one of the non-traditional lithography methods, there is a nano-imprint lithography method. In this method, a hard mold such as silicon (Si) having a desired pattern is prepared first. After the thermoplastic polymer thin film is opposed to the coated substrate, the mold is transferred to the polymer thin film pattern of the substrate by separating the mold from the substrate by treating it at a high temperature and high pressure by placing it between press plates.

The advantage of this nanoimprint lithography method is that the use of a hard mold such as Si makes it possible to easily implement ultra fine patterns. In fact, it is reported by the literature that the size of the minimum pattern implemented is approximately 7 nm.

However, the conventional nanoimprint lithography method has a problem that it is difficult to separate the mold and the substrate after performing the high temperature and high pressure process, and there is a problem that the possibility of damage of the mold and the substrate remains due to the high process pressure. Since the patterning is performed using the fluidity of the heated polymer material, there is a problem that the time required for perfect patterning becomes very large, that is, the process time is long.

Next, other examples of non-traditional lithography methods include micro-contact printing (μCP), micro-molding in capillaries (MIMIC) and micro-transfer molding (μTM). There are methods such as molding, soft-molding, capillary force lithography (CFL), etc .. The common methods of these methods are PDMS (polydimethylsiloxane), which is a type of polymer elastomer, as a template. .

The advantage of the PDMS mold used here is elastic, so it is easy to conformally contact the surface of the substrate to be patterned, and because it has a low surface air mass, it is easily separated from the surface of the substrate after patterning because of its low adhesion to other material surfaces. Is also possible, and also due to the high gas permeability due to the three-dimensional net-work structure, the absorption of the solvent is easy.

On the other hand, PDMS molds are elastomers with low mechanical strength, so they are easily deformed, making it impossible to implement a fine pattern (for example, approximately 500 μm or less), and highly dependent on the aspect ratio of the pattern to be implemented, and toluene Since deformation occurs due to swelling by a general organic solvent such as), there are disadvantages such as a significant restriction in selecting a polymer and a solvent to be used for patterning.

The present invention is to solve the above-mentioned problems of the prior art, it is easy to separate from the substrate to form a pattern, has excellent gas permeability, using a non-crystalline fluorine resin that can properly maintain flexibility and mechanical strength The object is to provide a mold and a method for producing the same.

The present invention according to one aspect of one aspect for achieving the above object is a mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side, wherein the material of the mold The amorphous fluororesin is a mold, and the mold is a two-layered mold in which a polymer elastic body having a predetermined thickness is bonded to an opposite side of the pattern structure face.

The present invention according to another aspect of one aspect for achieving the above object, in the mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side, the material of the mold A mold is provided which is a composite in which the amorphous fluororesin and a polymer elastic body are mixed.

The present invention according to one aspect of another aspect for achieving the above object is a method for manufacturing a mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side, The mold is manufactured by a compression molding technique using a master mold having a pattern structure opposite to the ultra fine pattern, and the mold is provided with a mold material, wherein the material of the mold is amorphous fluororesin.

According to another aspect of another aspect of the present invention for achieving the above object, in the method for producing a mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side, The mold is manufactured by an injection molding technique using a mold frame having a pattern structure opposite to the pattern formed on one side thereof, and the mold material is amorphous fluororesin.

The present invention according to another aspect of another aspect for achieving the above object, in the method for manufacturing a mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side And a second step of aligning the master mold having a pattern structure opposite to the pattern at a predetermined position inside the container with its pattern structure surface facing upward. A third step of filling an amorphous fluorine resin solution into the container; A fourth process of curing the amorphous fluororesin solution; And a fifth process of removing the cured amorphous fluorocarbon resin from the container to complete the mold.

The present invention according to another aspect of another aspect for achieving the above object, in the method for manufacturing a mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side Mixing the polymer elastomer oligomer with the amorphous fluororesin solution and then evaporating the solvent; Adding a curing agent to the mixed solution in which the solvent is evaporated to generate a complex; Injecting the composite into a container in which a master mold having a pattern structure opposite to the pattern is aligned therein; Curing the injected composite; And removing the cured complex from the container to complete the complex mold.

The present invention according to another aspect of another aspect for achieving the above object, in the method for manufacturing a mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side Mixing the polymer elastomer oligomer, amorphous fluorine resin, and a curing agent to form a composite; Injecting the composite into a container in which a master mold having a pattern structure opposite to the pattern is aligned therein; Curing the injected composite; And removing the cured complex from the container to complete the complex mold.

The above and other objects and various advantages of the present invention will become more apparent from the preferred embodiments of the present invention described below with reference to the accompanying drawings by those skilled in the art.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

First, the core technical idea of the present invention is PDMS, which is a type of polymer elastomer which is susceptible to deformation due to low mechanical strength and susceptible to deformation due to swelling due to organic solvent as a template for forming a pattern on a substrate. Unlike the aforementioned prior art used, as a material of the mold for forming a pattern (nm-cm size pattern) on the substrate, amorphous teflon, that is, low surface energy, facilitates mold separation and provides adequate mechanical strength. The use of Teflon, which is an amorphous fluororesin having high gas permeability and non-swelling properties to organic solvents and uniform contact with the substrate surface, makes it easy to achieve the purpose of the present invention through such technical means. Can be achieved.

Here, the mold of the present invention using an amorphous fluororesin may be prepared by compression molding, injection molding, etc. using amorphous fluororesin powder, or by coating or casting using an amorphous fluorine resin solution. can do.

In addition, as the amorphous fluorine resin used as the material for the template, Teflon AF® developed by the US company D can be used, which is a type of amorphous Teflon (tetrafluoroethylene) PDD (2, 2-bistrifluoromethyl-4, 5). -difluoro-1, 3-dioxole) copolymerized polymer resin, the copolymerization ratio is possible over the whole range, and commercial products include AF-1600, AF-2400, etc., the copolymerization ratio of TFE and PDD is different.

Therefore, the mold made of amorphous fluororesin has the following advantages as compared with the conventional PDMS mold.

First, since it has a low surface energy, it is easy to separate from the substrate after patterning.

Second, it is excellent in gas permeability and at the same time resistant to deformation because it is not swollen by a specific solvent.

Third, it has a relatively large mechanical strength compared to an elastic body, for example, the degree to which ultra-fine patterning of 500 nm or less is possible.

Fourth, since a very thin and flexible thin film can be processed, uniform contact with the substrate can be realized.

Next, the process of manufacturing the mold using the amorphous fluorine resin as mentioned above is demonstrated.

Example 1

1A and 1B are process flowcharts illustrating a process of manufacturing a mold using an amorphous fluororesin according to a first embodiment of the present invention.

Referring to FIG. 1A, a master mold 104 having an arbitrary pattern structure, that is, a pattern structure opposed to a pattern of a mold to be manufactured, is arranged inside the prepared jig 102 with its pattern structure face up. And fill the Teflon AF powder 106a by an appropriate thickness that requires the interior of the jig 102.

Subsequently, after preparing a press plate for crimping, more specifically, a press plate 108 having a heater 110 therein, an arbitrary process condition, for example, a process condition of T = 340 ° C. and P = 3000 psi, is prepared. Press plate 108 is press-molded on Teflon AF powder 106a for a predetermined time (for example, t = 120 min).

Thereafter, the press plate 108 is lifted up, and then the compression molded Teflon AF powder is removed (separated) from the jig 102, thereby completing the mold 106 having a pattern structure as shown in FIG. 1B as an example. . As such, the mold using the finished amorphous fluorine resin is used to form a pattern (various patterns of nm-cm size) on the substrate.

On the other hand, in the present invention, unlike the method described above, the inside of the jig is first filled with Teflon AF powder and pressed with a press plate to form a flat plate and then removed from the jig, again having a flat plate and an arbitrary pattern structure surface The master mold may be manufactured by a compression molding method (a kind of imprint method) that is pressed by a press.

On the other hand, the mold using the fluorine resin of the present invention is not a compression molding method as described above, but instead of forming any pattern structure (that is, a pattern structure opposite to the pattern of the mold to be produced by injection molding) on one side. Of course, it can be produced by an injection molding method using a mold or the like.

Example 2

2A and 2B are process flowcharts illustrating a process of manufacturing a mold using an amorphous fluororesin according to a second embodiment of the present invention.

Referring to FIG. 2A, a master mold 204 having an arbitrary pattern structure, that is, a pattern structure opposed to a pattern of a mold to be manufactured, is arranged inside the prepared container 202 with its pattern structure face up. The container 202 is filled with an appropriate amount of Teflon AF solution 206a that requires the inside. Here, as a method of filling a solution into the container 202, for example, spin coating, spray coating, dip coating, solution casting, etc. Can be used.

The Teflon AF solution is then cured by evaporation of the solvent by treatment at a predetermined process temperature (eg 25 ° C.) for a predetermined time (eg 240 min). This curing process can be realized more quickly by performing under high temperature heat treatment (or high temperature vacuum heat treatment) conditions to promote the evaporation of the solvent contained in the solution, as well as by rotating the vessel containing the Teflon AF solution at high speed to remove the solvent contained in the solution. It can be realized more quickly by promoting the evaporation.

Thereafter, the cured Teflon AF is removed (separated) from the container 202 to complete the mold 206 having a pattern structure as shown in FIG. 2B as an example. As such, the mold using the finished amorphous fluorine resin is used to form a pattern (various patterns of nm-cm size) on the substrate.

Meanwhile, in the present embodiment, the process of repeatedly evaporating the solvent after containing the Teflon AF solution in the container 202 in which the master mold 204 is contained, and again containing the Teflon AF solution thereon is repeated as many times as necessary. Of course, a mold having a desired target thickness can be obtained through the method.

Example 3

3A and 3B are process flowcharts illustrating a process of manufacturing a mold using an amorphous fluororesin according to a third embodiment of the present invention.

Referring to FIG. 3A, the master mold 304 having an arbitrary pattern structure inside the prepared jig or container 302 is aligned with its pattern structure surface facing upward, and the above-described embodiment 1 or 2 Method and variations thereof to form a compressed or cured Teflon AF template layer 306 having a thickness of several micrometers to several hundred micrometers in the jig or vessel 302.

Subsequently, a polymer elastomer solution 308a such as PDMS or PU is filled in a predetermined amount on the compression molded or cured Teflon AF mold layer 306, and then a curing process is performed to cure the polymer elastomer mold 308a. .

Then, by removing (separating) the two-layer mold of the Teflon AF mold layer 306 and the polymer elastomer mold layer 308 from the jig or the container 302, the pattern structure as shown in FIG. The two-layer structure mold which has is completed. In this manner, a two-layered mold using the completed amorphous fluorine resin is used to form a pattern (various patterns of nm-cm size) on a substrate.

Therefore, the mold prepared according to the present embodiment has a form in which a polymer elastomer (a polymer elastomer such as PDMS, PU, etc.) is added to an amorphous fluororesin mold, so that molds for forming patterns of various sizes on a substrate may be handled more. I can do it smoothly.

On the other hand, the mold according to the present invention is formed of a material of amorphous resin Teflon or attached to a polymer elastomer (polymer elastomer such as PDMS, PU, etc.) on one side of the teflon (that is, the side where the pattern structure is not formed) It is not limited to forming in a two-layer structure, Of course, it can also be formed from the composite material which mixed amorphous fluororesin and a polymeric elastic body.

As described above, the composite mold made of a mixture of amorphous fluorine resins such as Teflon and polymer elastomers such as PDMS and PU is obtained by mixing oligomer () and amorphous fluorine resin solution of polymer turnable body in an appropriate ratio. The solvent is then evaporated, then the curing agent is added and then mixed well to form a composite, which is poured into a container into which the master mold is inserted and cured (e.g., cured using heat, ultraviolet light, etc.) and then removed from the master mold. It can be produced by peeling off.

Here, in order to accelerate the removal of the solvent, as in the above-described embodiment, it is a matter of course to perform a high temperature heat treatment or a high temperature vacuum heat treatment process or a process of rotating the vessel at high speed.

In addition, the composite mold, unlike the above method, simultaneously forms a composite by mixing a very fine amorphous fluorine resin powder having a size of nanometer, a polymer elastomer oligomer and a curing agent, and pouring it into a container into which a master mold is inserted to cure (for example, , By curing with heat, ultraviolet rays, or the like, and then peeling away from the master mold. Here, too, it can harden | cure using heat, an ultraviolet-ray, etc. similarly to the above.

The inventors of the present invention prepared a mold using an amorphous fluorine resin, and performed an experiment to form a fine pattern on the substrate using the same, the experimental results are as shown in Figures 4a and 4b.

4A is a photograph taken with an optical microscope of the surface of an amorphous Teflon mold having a pattern of 1 μm line width and spacing prepared under arbitrary process conditions in accordance with the present invention.

Referring to FIG. 4A, the amorphous Teflon mold according to the present experimental example uses a silicon substrate having a pattern formed as a master mold, and is naturally cooled to a process condition of room temperature of 340 ° C., pressure of 2000 psi, and time of 5 minutes at room temperature. Prepared.

FIG. 4B is a photograph taken with an optical microscope of a pattern formed on a substrate using the amorphous Teflon mold shown in the photograph in FIG. 4A.

Referring to FIG. 4B, in the present experimental example, a silicon substrate was used, a polystyrene was used as the polymer material, and a capillary force lithography method using an amorphous Teflon template (process condition: temperature 150 ° C., time 30 minutes). Patterning was carried out).

According to the experimental results by the present inventors, it is easy to separate from the substrate after patterning, has excellent gas permeability, and is resistant to deformation caused by a specific solvent, has a large mechanical strength compared to the elastic body, and secures flexibility through An amorphous Teflon template capable of uniform contact with was obtained, and it was clearly seen that the amorphous Teflon template can be used to form a stable and reliable fine pattern on a substrate.

As described above, according to the present invention, as a mold for forming a pattern on a substrate, PDMS, which is a kind of polymer elastomer, which is susceptible to deformation due to low mechanical strength and susceptible to deformation due to swelling caused by organic solvent, is used. Unlike the prior art described above, as a material of the mold for forming patterns of various sizes on the substrate, amorphous Teflon, that is, low surface energy, facilitates mold separation, has appropriate mechanical strength, high gas permeability and By using Teflon, an amorphous fluorine resin that can provide non-swelling properties to organic solvents and uniform contact with the substrate surface, separation with the substrate is easy after patterning, and excellent in gas permeability and at the same time due to specific solvents. It is resistant to deformation, has greater mechanical strength than elastic body, and secures flexibility with substrate. It is possible to realize the same touch.

1A and 1B are a process flowchart showing a process of manufacturing a mold using an amorphous fluororesin according to a first embodiment of the present invention;

2A and 2B are process flowcharts illustrating a process of manufacturing a mold using an amorphous fluororesin according to a second embodiment of the present invention;

3A and 3B are process flowcharts illustrating a process of manufacturing a mold using an amorphous fluororesin according to a third embodiment of the present invention;

4A is a photograph taken with an optical microscope of the surface of an amorphous Teflon mold having a pattern of 1 μm line width and spacing prepared under arbitrary process conditions in accordance with the present invention;

FIG. 4B is a photograph taken with an optical microscope of a pattern formed on a substrate using an amorphous Teflon mold shown in the photograph in FIG. 4A.

<Description of Symbols for Main Parts of Drawings>

102: jig 104, 204, 304: master mold

106,206: Template 106a: Teflon AF Powder

108: press plate 110: heater

206a: Teflon AF solution 306: Teflon AF template layer

308: polymer elastomer template layer 308a: polymer elastomer solution

Claims (22)

delete In the mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side, The mold is made of amorphous fluorine resin, and the mold is a two-layered mold in which a polymer elastic body having a predetermined thickness is bonded to an opposing surface of the pattern structure surface. In the mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side, The mold is characterized in that the material of the mold is a composite in which an amorphous fluororesin and a polymer elastic body are mixed. In the method for manufacturing a mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side, The mold is manufactured by a compression molding technique using a master mold having a pattern structure opposite to the pattern, wherein the material of the mold is amorphous fluorine resin. The method of claim 4, wherein the manufacturing method is: Aligning the master mold at a predetermined position inside a jig with its pattern structure face upward; Embedding amorphous fluororesin powder in the jig; Contact-aligning the prepared flat surface of the press plate with the amorphous fluororesin powder and then compression molding under predetermined process conditions; And And removing the compression-molded amorphous fluororesin from the jig to complete the mold. The method of claim 4, wherein the manufacturing method is: Embedding the amorphous fluorine resin powder in the jig flat by a predetermined thickness; Making a flattening plate by contact-aligning the prepared flat surface of the press plate with the amorphous fluororesin powder and compression molding under a predetermined process condition; Squeezing the flattening plate removed from the jig and the master mold after aligning the pattern structure surface; And Mold manufacturing method comprising the step of completing the mold by separating the flattening plate from the master mold. The method of claim 5 or 6, wherein the manufacturing method is: Filling the PDMS elastomer solution on the compression molded amorphous fluorine resin in the jig; Curing the PDMS elastomer solution; And And removing the two-layer structure of the compression molded amorphous fluorine resin and the cured PDMS elastomer from the jig to complete a two-layer structure mold. In the method for manufacturing a mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side, The mold manufacturing method, characterized in that for producing the mold by an injection molding technique using a mold frame formed on one side of the pattern structure opposite to the pattern, the material of the mold is amorphous fluororesin. In the method for manufacturing a mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side, A second step of aligning a master mold having a pattern structure opposite to the pattern at a predetermined position inside the container with its pattern structure face upward; A third step of filling an amorphous fluorine resin solution into the container; A fourth process of curing the amorphous fluororesin solution; And And a fifth process of removing the cured amorphous fluorocarbon resin from the container to complete the mold. The method of claim 9, wherein the manufacturing method further comprises a step of promoting removal of a solvent contained in the amorphous fluorine resin solution through a high temperature heat treatment process. The method of claim 9, wherein the manufacturing method further comprises a step of promoting removal of a solvent contained in the amorphous fluorine resin solution through a high temperature vacuum heat treatment process. The method of claim 9, wherein the manufacturing method further comprises the step of promoting the removal of the solvent contained in the amorphous fluorine resin solution by rotating the container at high speed. The method according to any one of claims 9 to 12, wherein the amorphous fluorine resin solution is filled into the container through spin coating, spray coating, dip coating or solution casting. The method according to any one of claims 9 to 12, wherein the manufacturing method further comprises a step of completing the mold of the target thickness by performing the fifth process after performing the third and fourth processes repeatedly. Mold production method comprising a. The method of claim 9, wherein the manufacturing method is: Filling a PDMS elastomer solution on top of the cured amorphous fluorine resin; Curing the PDMS elastomer solution; And And removing the cured amorphous fluororesin and the PDMS elastomer from the two-layer structure to complete the two-layer structure mold. In the method for manufacturing a mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side, Mixing the polymer elastomer oligomer and the amorphous fluororesin solution and then evaporating the solvent; Adding a curing agent to the mixed solution in which the solvent is evaporated to generate a complex; Injecting the composite into a container in which a master mold having a pattern structure opposite to the pattern is aligned therein; Curing the injected composite; And And removing the cured composite from the container to complete the composite mold. The method of claim 16, wherein the manufacturing method further comprises the step of promoting the removal of the solvent contained in the mixed solution through a high temperature heat treatment process. The method of claim 16, wherein the manufacturing method further comprises the step of promoting the removal of the solvent contained in the mixed solution through a high temperature vacuum heat treatment process. 17. The method of claim 16, wherein the manufacturing method further comprises the step of promoting removal of the solvent contained in the mixed solution by rotating the vessel at high speed. The method for producing a mold according to claim 16, wherein the manufacturing method hardens the composite using heat or ultraviolet rays. In the method for manufacturing a mold used to form a target pattern on a substrate using a pattern of at least one layer structure formed on one side, Mixing a polymer elastomer oligomer, an amorphous fluororesin, and a curing agent to form a composite; Injecting the composite into a container in which a master mold having a pattern structure opposite to the pattern is aligned therein; Curing the injected composite; And And removing the cured composite from the container to complete the composite mold. The method for producing a mold according to claim 21, wherein the manufacturing method hardens the composite using heat or ultraviolet rays.