KR20140099409A - Pattern transferring method using modification by self assembled monolayer - Google Patents

Abstract

The present application relates to a method for transferring a solvent pattern which comprises the steps of: forming a hydrophilic self-assembling monolayer having hydrophilicity to a substrate; obtaining a patterned mold; forming a hydrophilic solvent pattern on a surface of the patterned mold by applying a hydrophilic solvent to the patterned mold; and transferring the hydrophilic solvent pattern of the mold to the substrate by enabling the mold having the hydrophilic solvent pattern to come into contact with the substrate in which the hydrophilic self-assembling monolayer is formed.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of transferring a pattern using a surface modification of a monolayer self-assembled monolayer,

The present invention relates to a method of selectively transferring a homogeneous solvent pattern using surface modification of a substrate using a self-assembled monolayer.

The pattern can be formed by various methods such as a photolithography method using a photoresist, a silk screen method using a metal paste, and the like. However, as industrial technology is gradually developed, a method of forming a pattern in a simpler, convenient and inexpensive manner is required. From this point of view, the micro contact printing method, which has recently become popular, has many advantages.

The microcontact printing method is a method of forming a pattern by contacting a substrate with an organic molecule or an organometallic compound having catalytic activity by using a frame made of a polymer.

The polymer mold is advantageous in that it has low surface energy, is chemically stable, and can be formed into various shapes. Therefore, various patterns can be easily formed on a substrate, and various pattern forming techniques using the same are introduced.

However, in general, the surface of a polymer has a hydrophobic property, and due to this property, its use is restricted due to weak adhesion with other kinds of materials [Korean Patent Registration No. 2003-005891].

It is an object of the present invention to provide a method of improving surface adhesion and adhesion of a transferred pattern by using a self-assembled monolayer film.

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a hydrophilic self-assembled monolayer on a substrate to modify a surface of the substrate; Obtaining a patterned mold; Applying a hydrophilic solvent to the patterned mold to form a hydrophilic solvent pattern on the patterned mold surface; And a step of transferring the hydrophilic solvent pattern of the mold onto the substrate by contacting the mold having the hydrophilic self-assembled monolayer formed thereon with the mold having the hydrophilic solvent pattern formed thereon.

According to one embodiment of the invention, the substrate comprises a substrate such as quartz, silicon wafer, glass, ceramic, glass-ceramic, metal, metal oxide, polycarbonate, PET, polyethersulfone or polyimide substrate , But is not limited thereto.

According to one embodiment of the present invention, before the step of modifying the surface of the substrate, the method may further include the step of irradiating UV onto the surface of the substrate to form an OH- group on the surface of the substrate, no.

According to one embodiment of the present invention, the hydrophilic self-assembled monolayer includes APS (3-aminopropyl) trimethoxysilane, MUA (11-mercaptoundecanoic acid), DET (3-trimethoxysilylpropyl) diethylenetriamine, EDA (N- ] -3-aminopropyl trimethoxysilane), and combinations thereof. However, the present invention is not limited thereto.

According to one embodiment of the present invention, the hydrophilic self-assembled monolayer may be formed on the substrate by a dipping coating method, a spin coating method, a roll-to-roll method, or a vapor deposition method. no.

According to one embodiment of the present invention, the mold may be selected from the group consisting of polydimethylsiloxane (PDMS), polyurethane, polyimides, and combinations thereof, but is not limited thereto.

According to one embodiment, the hydrophilic solvent is selected from the group consisting of poly (4-vinylphenol), PMF (polyamine-co-formaldehyde), PGMEA (propylene glycol monomethyl ether acetate) But are not limited to, those selected from solvents.

According to one embodiment of the present invention, the hydrophilic solvent may be applied by a surface treatment method through a vaporizer, a spin coating method, a roll-to-roll coating method, a spray coating method, a dip coating method or a flow coating method, no.

According to an embodiment of the present invention, the method of contacting the substrate with the mold may be a micro-contact printing method, an imprinting method, a roll-to-roll method, or a dip pen lithography Dip pen lithography), but the present invention is not limited thereto.

According to one embodiment of the present invention, the patterned mold may include a hydrophilization treatment on the surface of the mold, but the present invention is not limited thereto.

According to one embodiment of the invention, the hydrophilization treatment of the mold may be an atmospheric plasma treatment, but is not limited thereto.

According to the above-mentioned problem solving means of the present invention, the selective transfer method of the solvent using the surface modification of the self-assembled monolayer film has the following advantageous effects.

First, by using the surface modification of the self-assembled monolayer, a strong adhesive force can be formed between the solution and the substrate. Therefore, fine pattern transfer of good quality can be realized.

In addition, a large area pattern using the surface modification can be used, and various transfer methods can be used.

In addition, patterns of organic materials using solvents are possible and can provide a method as an alternative means of photolithography.

FIGS. 1A to 1D are views showing a process of manufacturing a mold according to an embodiment of the present invention.
FIGS. 2A and 2B are diagrams showing a hydrophilization process of a mold according to an embodiment of the present invention.
FIGS. 3A to 3D are diagrams showing a pattern transfer method of a homogeneous solvent according to an embodiment of the present invention. FIG.
FIG. 4 is a conceptual view showing the shape of self-assembled monomers according to one embodiment of the present invention. FIG.
FIG. 5 is a photograph of a substrate when contact printing is performed without forming a conventional self-assembled monolayer. FIG.
FIG. 6 is a photograph of a substrate when contact printing is performed in a state where a self-assembled monolayer film according to an embodiment of the present invention is formed.
7 is an AFM photograph showing transfer of a solvent pattern according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is " on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

Throughout this specification, the term " combination thereof " included in the expression of the machine form means one or more combinations or combinations selected from the group consisting of the constituents described in the expression of the machine form, And the like.

FIGS. 1A and 1D are cross-sectional views illustrating a process of forming a mold according to an embodiment of the present invention.

As shown in Fig. 1A, a substrate 10 is prepared and a photoresist film 20 is formed on the surface of the substrate 10. In the embodiment of the present invention, the silicon wafer is used as the substrate 10, but the present invention is not limited thereto.

First, the substrate 10 is washed according to a conventional method to remove impurities, and a photoresist film 20 is formed on the substrate 10. After the substrate 10 is cleaned in this way, the formation of the photoresist film 20 is intended to remove organic substances present on the substrate 10. [ When organic matter is present on the substrate 10, there is a problem that a uniform photoresist film 20 can not be obtained in the subsequent photoresist 20 forming process.

The substrate 10 may be a rigid substrate or a flexible substrate, but is not limited thereto. The rigid substrate may be, for example, a silicon wafer, glass, ceramic, glass-ceramic, metal or metal oxide, but is not limited thereto. The flexible substrate may be, for example, polycarbonate, PET, polyethersulfone or polyimide, but is not limited thereto.

 The film of the photoresist 20 is uniformly applied onto the substrate 10 by a spin coating method, and then a pattern is formed on the film of the photoresist 20. For example, a method of forming a pattern on a photoresist can form a pattern using an electron beam lithography method, but is not limited thereto.

Then, as shown in FIG. 1B, a pattern is formed on the photoresist film 20. At this time, the shape of the photoresist 20 pattern is opposite to the pattern formed on the mold 30. That is, a portion corresponding to the engraved portion on the mold 30 is formed as a protruding relief portion, and a portion corresponding to the relief portion on the mold 30 forms a relief portion.

 Next, a PDMS (poly dimethyl siloxane) mixture 30 'is applied on the substrate 10 on which the pattern of the photoresist 20 is formed according to one embodiment of the present invention. PDMS can stably adhere to a wide area on a substrate, uniformly applied to a non-flat surface, and can be used for a long time in a mold because of its high durability. There is an advantage such that adhesion is not generated well and molding processability is good. At this time, the PDMS mixture 30 'is formed to a thickness enough to completely cover the pattern of the photoresist 20 formed on the substrate 10, as shown in FIG. 1C. The PDMS mixed material 30 used in the present invention is a mixture of a sylgard and a curing agent at a weight ratio of about 10: 1.

Next, the applied PDMS mixed material 30 'is cured. There are various methods of curing, but in the embodiment of the present invention, a thermosetting method is used. For example, the substrate 10 to which the PDMS mixed material 30 'is applied may be put into an oven and cured at a temperature of about 80 DEG C for about 1 hour, but the present invention is not limited thereto.

The cured PDMS mixed material 30 'has a rigid structure. When the mold 30 is separated from the substrate 10, the mold 30 is completed as shown in FIG. 1D.

FIGS. 2A and 2B are cross-sectional views illustrating the hydrophilization process of the obtained mold 30. FIG.

2A, a surface of the mold 30 is subjected to a plasma treatment to form a hydroxyl group (OH-) on the surface of the mold 30 to hydrophilize the surface. For example, the surface can be hydrophilized by irradiating atmospheric plasma with N ₂ 400 slm (standard litters per minute), Air 10 slm, 12 kV for about 1 minute to form OH groups on the surface of the specimen. But is not limited to.

On the surface of the hydrophilized mold 30, the hydrophilic solvent 40 is diluted with ethyl alcohol and applied as shown in FIG. 2B. The hydrophilic solvent 40 may be a solvent selected from the group consisting of poly (4-vinylphenol), PMF (polyamine-co-formaldehyde), PGMEA (propylene glycol monomethyl ether acetate) But are not limited thereto.

The hydrophilic solvent 40 may be applied by a surface treatment method using a vaporizer, a spin coating method, a roll-to-roll coating method, a spray coating method, a dip coating method or a flow coating method, but is not limited thereto. For example, when the hydrophilic solvent 40 is applied by the spin coating method, the hydrophilic solvent 40 can be uniformly coated on the mold 30 as compared with the spray coating method.

3A and 3D are sectional views showing a transfer method of a solvent pattern according to an embodiment of the present invention.

First, the substrate 100 is prepared by washing according to a conventional method. Washing the substrate 100 in this way is for removing organic matter present on the substrate 100. When the organic material exists on the substrate 100, there is a problem that the self-assembled monolayer 110 can not be uniformly applied in a subsequent self-assembled monolayer (SAMs) 110 forming process. After immersing the substrate 100 in the detergent for a predetermined period of time, the organic material is removed in the order of rinsing the substrate 100. The detergent used is prepared by mixing sulfuric acid (H ₂ SO ₄ ) and hydrogen peroxide (H ₂ O ₂ ) at a ratio of 4: 1. In the step of rinsing the substrate 100, it is preferable to clean the surface of the substrate 100 by using DI (Deionized) Water to prevent re-contamination of the substrate. The substrate 100 is not particularly limited and may be, for example, a silicon wafer, glass, ceramic, glass-ceramic, metal, metal oxide, polycarbonate, PET, polyethersulfone or polyimide substrate. But is not limited to.

As shown in Fig. 1A, ultraviolet rays are irradiated onto the cleaned substrate 100. For example, when a step of irradiating ultraviolet rays having a wavelength of 184 nm and 254 nm is performed, a hydroxyl group (-OH) is formed on the surface of the substrate 100.

Subsequently, as shown in FIG. 3B, a self-assembled monolayer 110 may be formed on the surface of the substrate 100. Self Assembled Monolayers (SAMs) refers to regularly aligned organic molecules spontaneously deposited on the surface of a given substrate, and consists of three parts as shown in FIG. First, the reactor 11 of the head part coupled to the substrate, the long alkalic chain 12 of the body part enabling regular molecular film formation, and the functional part 13 of the tail part, which functions as a molecular membrane, Loses. Self-assembled monolayers often have direct chemical bonds between the surface of the substrate and the molecules that make up the membrane, making it very robust. In addition, it is not affected by the shape and size of the substrate, and thus it is possible to manufacture the substrate even on complicated shaped substrates, and it is easy to maximize the size.

The self-assembled monolayer may be formed by a combination of APS (3-aminopropyl) trimethoxysilane, MUA (11-mercaptoundecanoic acid), DET (3-trimethoxysilylpropyl) diethylenetriamine, EDA (N- Combinations thereof, but are not limited thereto.

The self-assembled monolayer 110 may be formed by a dipping coating method, a spin coating method, a roll-to-roll method, or a vapor deposition method, but the present invention is not limited thereto. For example, in the case of using the dip coating method, the self-assembled monolayer can be deposited on a substrate as opposed to the vapor deposition method.

3C, the hydrophilic solvent pattern 40 formed on the mold 30 is transferred to the substrate 100 by contacting the mold 30 and the substrate 100 formed in FIG. 2B. For example, the method of contacting the substrate 100 with the mold 30 may be a microcontact printing method, an imprinting method, a roll-to-roll method, or a dip pen lithography method, but is not limited thereto.

When the mold 30 is brought into contact with the substrate 100, the hydrophilic solvent 40 formed on the embossed portion of the mold 30 is brought into contact with the surface of the substrate 100 and bonded to the self-assembled monolayer 110 of the substrate . However, the hydrophilic solvent 40 formed on the engraved portion of the mold 30 does not contact the surface of the substrate 100. 3D, only the hydrophilic solvent 40 formed on the embossed portion of the mold 30 is transferred to the substrate 110. As shown in FIG. After the mold 30 is separated from the substrate 100, only ethyl alcohol vaporized at a low temperature is selectively removed due to a difference in boiling points of the thin-film-treated solution through an annealing process in a vacuum oven, Thereby forming a pattern.

<Examples>

A SiO ₂ substrate was used as a substrate, and a photoresist layer was formed on the substrate by spin coating at 5 μm. The photoresist layer was patterned by an electron beam lithography method. The patterned substrate was polymerized with a sylgard and a curing agent at a ratio of 10: 1 for about 10 minutes. The polymerized solution was poured onto the substrate and cured in an oven at 80 DEG C for about 1 hour.

The hardened PDMS mold was removed from the substrate and the normal pressure plasma was irradiated to the specimen for about 1 minute under conditions of N ₂ 400 slm (standard litters per minute), Air 10 slm, and 12 kV to form a hydroxyl group (OH- ) Was formed to hydrophilize the surface of the mold.

A hydrophilic solvent was applied to the mold through spin coating. The hydrophilic solvent was prepared by dissolving 3 wt% of PVP (polyvinylphenol) and 1.5 wt% of poly (melamine-co-formaldehyde) in a solvent of propylene glycol monomethyl ether acetate (PGMEA) for about 24 hours as a PVP solution. The PVP solution was spin-coated on the mold at 500 rpm for 5 seconds and at 3500 rpm for 35 seconds to apply the PVP solution onto the mold.

On the other hand, ultraviolet rays are irradiated onto a SiO ₂ substrate subjected to piranha cleaning (H ₂ SO ₄ : H ₂ O ₂ = 4: 1) to form a hydroxyl group (OH-) on the surface of the substrate, . 0.1 mM of APS ((3-aminopropyl) trimethoxysilane) and 1 uM of acetic acid were added to 50 mL of ethyl alcohol, followed by dipping for about 1 hour to coat APS self-assembled monolayer The surface of the substrate was made hydrophilic.

The mold onto which the PVP solution was applied was selectively transferred to the substrate through a micro contact printing method.

After separating the mold from the substrate, the substrate was heated in a vacuum oven at 200 ° C for about 2 hours to selectively remove only ethyl alcohol vaporized at low temperatures due to differences in boiling point in the thinned solution, and PVP Are crosslinked to form a pattern.

Fig. 5 shows a photograph of a pattern experimented according to the conventional method, and Fig. 6 shows a photograph of a pattern according to the embodiment. As shown in FIG. 5, when the pattern is transferred by the conventional method, the PVP solvent transfer is not uniformly carried out due to the low adhesive force with the substrate, and when the mold and the substrate are separated from each other, there was.

However, referring to the photograph according to the embodiment of the present invention, as shown in FIG. 6, it was found that the PVP solvent was transferred to the entire surface. It was found that the PVP solvent was uniformly transferred due to strong adhesive force between the solvent pattern and the substrate by the self-assembled monolayer process.

Figure 7 is an AFM image of the PVP solvent transferred to the substrate. Referring to FIG. 7, it can be seen that the PVP solvent was transferred at a constant width and height, and the height of the PVP solvent was about 450 nm.

In this manner, when a base material on which a hydrophilic self-assembled monolayer film is formed and a mold on which a hydrophilic solvent pattern is formed are transferred onto a base material through contact printing, a pattern can be transferred clearly with a strong adhesive force between the base material and the base material As a matter of course, a large area pattern using the surface modification becomes possible, and a pattern of an organic material using a solvent can be made possible.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

10: substrate
20: Photoresist
30: PDMS mold
30 ': PDMS mixed material
40: hydrophilic solvent
100: substrate
110: self-assembled monolayer

Claims (11)

Modifying the surface of the substrate by forming a hydrophilic self-assembled monolayer on the substrate;
Obtaining a patterned mold;
Applying a hydrophilic solvent to the patterned mold to form a hydrophilic solvent pattern on the patterned mold surface; And
Contacting the mold having a hydrophilic self-assembled monolayer formed thereon with a hydrophilic solvent pattern to transfer the hydrophilic solvent pattern of the mold to the substrate
, A method of transferring a solvent pattern
The method according to claim 1,
Wherein the substrate is a quartz, silicon wafer, glass, ceramic, glass-ceramic, metal, metal oxide, polycarbonate, PET, polyethersulfone or polyimide.
The method according to claim 1,
Further comprising the step of irradiating the surface of the substrate with UV to form an OH- group on the surface of the substrate before the step of modifying the surface of the substrate.
The method according to claim 1,
The hydrophilic self-assembled monolayer may be formed by a combination of APS (3-aminopropyl) trimethoxysilane, MUA (11-mercaptoundecanoic acid), DET (3-trimethoxysilylpropyl) diethylenetriamine, EDA (N- 2-aminoethyl) -3-aminopropyltrimethoxysilane, Wherein the self-assembled monolayer is selected from the group consisting of combinations of:
The method according to claim 1,
Wherein the hydrophilic self-assembled monolayer is formed on the substrate by a dipping coating method, a spin coating method, a roll-to-roll method, or a vapor deposition method.
The method according to claim 1,
Wherein the mold is selected from the group consisting of polydimethylsiloxane (PDMS), polyurethane, polyimides, and combinations thereof.
The method according to claim 1,
Wherein the hydrophilic solvent comprises a solvent selected from the group consisting of poly (4-vinylphenol), PMF (polyamine-co-formaldehyde), PGMEA (propylene glycol monomethyl ether acetate) Of the solvent pattern.
8. The method of claim 1 or 7,
Wherein the hydrophilic solvent is applied by a surface treatment method using a vaporizer, a spin coating method, a roll-to-roll coating method, a spray coating method, a dipping coating method or a flow coating method.
The method according to claim 1,
The method of bringing the substrate into contact with the mold may be a micro-contact printing method, an imprinting method, a roll-to-roll method, or a dip pen lithography method. , A solvent pattern transfer method.
The method according to claim 1,
And a hydrophilic treatment is performed on the surface of the patterned mold.
11. The method of claim 10,
Wherein the hydrophilic treatment is an atmospheric plasma treatment.

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