KR20120067448A - Method for treating surface of mold by using plasma - Google Patents

Method for treating surface of mold by using plasma Download PDF

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Publication number
KR20120067448A
KR20120067448A KR1020100128838A KR20100128838A KR20120067448A KR 20120067448 A KR20120067448 A KR 20120067448A KR 1020100128838 A KR1020100128838 A KR 1020100128838A KR 20100128838 A KR20100128838 A KR 20100128838A KR 20120067448 A KR20120067448 A KR 20120067448A
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KR
South Korea
Prior art keywords
mold
plasma
resist
nanoimprint lithography
plasma treatment
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Application number
KR1020100128838A
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Korean (ko)
Inventor
이재갑
소회섭
이치영
Original Assignee
국민대학교산학협력단
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Priority to KR1020100128838A priority Critical patent/KR20120067448A/en
Publication of KR20120067448A publication Critical patent/KR20120067448A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/002—Component parts, details or accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)

Abstract

PURPOSE: A mold surface treatment method using plasma is provided to perform a plurality of nano imprint lithography processes at the same time by using a plurality of molds because surfaces of molds are simultaneously treated. CONSTITUTION: A mold(10) surface treatment method using plasma is utilized for a nano imprint lithography process. A surface of the mold is plasma-treated, thereby being hydrophobically modified. A plasma-treatment is performed by using fluorine gas. A water contact angle of the surface of the mold is 100° is greater.

Description

Surface treatment method of mold using plasma {METHOD FOR TREATING SURFACE OF MOLD BY USING PLASMA}

The present invention relates to a nanoimprint lithography (NIL) process, and in particular, in the nanoimprint lithography process by ultraviolet (UV) irradiation, the surface of the mold is plasma-processed to facilitate mold and resist. It relates to a surface treatment method of the mold to be separated easily.

The nanoimprint lithography process is an economical and effective technique for fabricating nano-structures, in which spin-coating or dispensing a resist on a substrate and patterning on the surface of the resist It is a technique of transferring a pattern by pressing the formed mold.

Nanoimprint lithography processes can be broadly classified into thermal-type and ultraviolet irradiation methods.

First, a heated process, called hot embossing or thermal imprint lithography, is brought into contact with the mold and the substrate on which the polymer layer is formed, and then heated to provide fluidity to the polymer layer and to apply pressure. It is a method to create a desired pattern on the polymer layer by adding it. Such a heating process has a problem that it is difficult to align the multilayer by thermal deformation, and there is a problem in that the pattern is easily broken because high pressure is required to imprint a resist having a high viscosity.

Ultraviolet irradiation nanoimprint lithography process developed to improve the problems of the heating process is a method using a low-viscosity photocurable resin and ultraviolet rays to cure it, since the process can be carried out at room temperature and low pressure, Suitable for multilayering and mass production.

Figure 1 shows a conventional ultraviolet irradiation nanoimprint lithography process.

As shown in FIG. 1, first, the UV curing resist 30 is coated on the substrate 20 (FIG. 1A), and then the mold 10 is pressed to form a curing resist solution between the patterns of the mold 10. It will be filled (Fig. 1 (b)). At this time, since the viscosity is low, the resist 20 may be easily filled between the patterns of the mold 10 even at a low pressure. Thereafter, when the UV light source exposes the resist 30 through the transparent mold 10, the resist 30 is cured (FIG. 1C). Subsequently, when the mold 10 is removed, the remaining layer 40 remains between the patterns (FIG. 1 (d)), and the process is completed by removing it through oxygen ashing (O 2 Ashing) or the like (FIG. 1 ( e)).

In the above-described conventional UV irradiation process, in order to easily separate the mold 10 and the resist 30 after UV curing, self-assembled monolayers (SAMs) are coated on the surface of the mold 10, The surface of the mold 10 is treated to have hydrophobicity. Hydrophobic self-assembled monolayers include OTS (Octadecyltrichlorosilane) and PFS (Perfluorodecyltrichlorosilane), and OTS has surface group consisting of CH 3 and water contact angle of 110 °, and PFS is composed of CF 3 Water contact angle is 120 degrees.

However, the method of coating the self-assembled monomolecular film on the mold surface to make the mold surface hydrophobic has a disadvantage in that it takes a long processing time. Therefore, when producing a product using a nanoimprint lithography process, there is a problem that the productivity of the product is lowered due to a long process time.

An object of the present invention is to provide a surface treatment method of a mold capable of shortening the surface treatment time by treating the mold surface to have hydrophobicity in a nanoimprint lithography process.

Moreover, it aims at providing the nanoimprint lithography method by which the transfer effect of the pattern was improved by using the mold processed by the above-mentioned surface treatment method.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, a method of treating the surface of the mold used in the nanoimprint lithography process according to an aspect of the present application, to make the surface of the mold hydrophobicly modified by plasma treatment of the surface of the mold.

In an exemplary embodiment, the plasma treatment may be performed using a fluorine-based gas, but is not limited thereto. In one embodiment, the fluorine-based gas is F 2 , BF 3 , HF, NF 3 , CF 4 , SF 6 , CH 2 F 2 , CHF 3 , C 2 F 6 , C 2 F 8 , C 3 F 6 , C 3 F 8 , C 4 F 6 , C 4 F 8 , C 4 F 10 , C 6 F 10 , C 5 F 12 , SF 5 , WF 6 , SiF 4 , Si 2 F 6 , XeF 2 and combinations thereof It may be to include one selected from the group consisting of, but is not limited thereto.

In an exemplary embodiment, the mold may be formed of a polymer material, but is not limited thereto.

In an exemplary embodiment, the surface of the mold may be plasma treated such that the water contact angle of the surface of the mold is 100 ° or more, but is not limited thereto.

Nanoimprint lithography method according to another aspect of the present invention, manufacturing a mold of a transparent material with a nano-pattern formed; Plasma treating the surface of the mold such that the mold surface is hydrophobically modified; Coating a resist on a substrate and placing the mold on the resist; Applying pressure to the mold to fill the resist between the nanopatterns of the mold; Irradiating the resist with ultraviolet light through the transparent mold to cure the resist; And removing the mold from the resist.

The surface treatment method of the mold using the plasma of the present application has the following advantageous effects.

First, compared with the conventional method of coating a self-assembled monomolecular film on a mold surface, the time taken for surface treatment can be significantly shortened. In addition, since the surface treatment for several molds can be performed at once, multiple nanoimprint lithography processes can be performed simultaneously using multiple molds. Thus, by reducing the overall process time, it is possible to improve the productivity of the product produced by the nanoimprint lithography process.

In addition, by treating the mold surface with sufficient hydrophobicity, the mold and the resist can be easily separated. Therefore, nanopattern transfer of good quality can be realized.

1 is a cross-sectional view schematically showing a nanoimprint lithography process by a conventional ultraviolet irradiation method.
2 is a cross-sectional view schematically showing a nanoimprint lithography process according to an embodiment of the present disclosure.
3 is a graph showing a change in the water contact angle according to the plasma treatment time when the CF 4 plasma treatment on the mold surface according to an embodiment of the present application, Figure 3 (a) is a result using the induction plasma equipment, Figure 3 (b) is a graph showing the results using the atmospheric plasma equipment.
4 is a graph showing an analysis result of F 1s peak before and after plasma treatment when a CF 4 plasma treatment is performed on a mold surface according to an exemplary embodiment of the present application.
FIG. 5 is a graph showing analysis results of C 1s peaks before and after plasma treatment when CF 4 plasma treatment is performed on a mold surface according to an embodiment of the present disclosure. FIG. 5A is a result of a mold material, and FIG. 5B is an induction. Results of using the plasma equipment, Figure 5c is a graph showing the results using the atmospheric pressure plasma equipment.
6 is a graph showing a change in water contact angle with time before and after plasma treatment when a CF 4 plasma treatment is performed on a mold surface according to an exemplary embodiment of the present application.
FIG. 7 is an SEM image showing the results of transferring a nano pattern using a nanoimprint lithography method according to an embodiment of the present disclosure. FIG.

DETAILED DESCRIPTION Hereinafter, embodiments and examples of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described 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 said to "include" a certain component, it means that it can further include other components, without excluding the other components 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.

Surface treatment method according to an embodiment of the present application, the surface of the mold used in the nanoimprint lithography process F 2 , BF 3 , HF, NF 3 , CF 4 , SF 6 , CH 2 F 2 , CHF 3 , C 2 F 6 , C 2 F 8 , C 3 F 6 , C 3 F 8 , C 4 F 6 , C 4 F 8 , C 4 F 10 , C 6 F 10 , C 5 F 12 , SF 5 , WF 6 , SiF 4 , Si 2 F 6 , XeF 2 And modifying the surface of the mold hydrophobicly by plasma treatment with a fluorine-based gas including one selected from the group consisting of a combination thereof.

The mold may be formed of a polymer material, and by the above-described plasma treatment, since the C-H bond is replaced by the C-F bond on the mold surface, the mold surface becomes hydrophobic. At this time, the water contact angle of the surface of the mold should be treated to be 100 ° or more, the mold surface can exhibit sufficient hydrophobicity.

2 schematically shows a nanoimprint lithography method using the surface treatment method of a mold according to one embodiment of the present application.

As shown in FIG. 2, first, a mold 10 in which a nanopattern is formed is manufactured (FIG. 2A). The mold 10 may be manufactured using a polymer or the like. For example, a mold 10 in which a specific nanopattern is engraved may be manufactured through a transfer process from a previously manufactured master.

Next, the surface of the mold 10 is F 2 , BF 3 , HF, NF 3 , CF 4 , SF 6 , CH 2 F 2 , CHF 3 , C 2 F 6 , C 2 F 8 , C 3 F 6 , C 3 F 8 , C 4 F 6 , C 4 F 8 , C 4 F 10 , C 6 F 10 , C 5 F 12 , SF 5 , WF 6 , SiF 4 , Si 2 F 6 , XeF 2 And plasma treatment with a fluorine-based gas including one selected from the group consisting of a combination thereof, so that the surface of the mold 10 is hydrophobically modified (FIG. 2 (b)). For example, when the plasma treatment is performed on the surface of the mold 10 using a carbon fluoride-based gas such as CF 4 , the CH bond is substituted with the CF bond on the surface of the mold 10. Surface becomes hydrophobic.

In the conventional ultraviolet irradiation nanoimprint lithography process, self-assembled monolayers (SAMs) are formed on the surface of the mold 10 for separation of the mold 10 and the resist 30 (also referred to as a “sample”) after the ultraviolet curing process. However, in the present application, the surface of the mold 10 on which the nano-pattern is formed is plasma treated.

The plasma processing may use an inductively coupled plasma (ICP) device or an atmospheric pressure plasma (APP) device. In addition, the water contact angle of the mold surface is preferably treated to be 100 ° or more.

Next, the resist 30 is coated on the substrate 20 by spin coating or the like, and the mold 10 is placed on the resist 30 (Fig. 2 (c)). . As the resist 30, an ultraviolet curable polymer may be used. For example, a polymer based on polyacrylate, polyurethane, or polydimethylsiloxane (PDMS) having flexibility even after curing may be used. .

Next, pressure is applied to the mold 10 to fill the resist 30 between the nanopatterns of the mold 10 (FIG. 2 (d)). In this case, the pressure may be applied by using a quartz shaft through which ultraviolet rays pass after the PDMS pad is placed on the mold 10 for uniform pressure application.

Next, ultraviolet rays (UV) are irradiated onto the resist 30 through the transparent mold 10 to cure the resist 30 (FIG. 2E). When ultraviolet light is irradiated through the quartz shaft while the pressure is applied, the resist 30 is ultraviolet cured.

Next, the mold 10 is removed from the resist 30 (Fig. 2 (f)). At this time, as described above, since the surface of the mold 10 is plasma treated to have hydrophobicity, the mold 10 and the resist 30 may be easily separated.

Meanwhile, after removing the mold 10, the remaining layer 40 may remain between the patterns transferred to the resist. This residual layer 40 can be completely removed through oxygen ashing (O 2 Ashing) (Fig. 2 (g)).

3 to 6 show the characteristics of the surface treatment method of the mold according to an embodiment of the present application as a graph.

First, when the CF 4 plasma treatment on the surface of the mold, and shows the change in the water contact angle according to the plasma treatment time, Figure 3 (a) is a case using the induction plasma equipment, Figure 3 (b) This is the case using atmospheric pressure plasma equipment. In FIG. 3, the horizontal axis represents plasma processing time (sec, FIG. 3 (a)) and plasma cycling (Plasma cycling, cycles, FIG. 3 (b)), and the vertical axis represents water contact angle (°). . As shown in FIG. 3, it can be seen that the CF 4 plasma treatment time has a water contact angle of about 105 ° after one minute.

4 is an analysis result by X-ray photoelectron spectroscopy (XPS) of F 1s peaks before and after CF 4 plasma treatment. Here, MINS 311 (manufactured by Minuta Technology), a polyurethane-based composite material, was used as the mold material. In FIG. 4, the horizontal axis represents binding energy (eV), and the vertical axis represents intensity (AU). As shown in FIG. 4, it can be seen that fluorine (F) does not appear before the CF 4 plasma treatment, but fluorine appears after the CF 4 plasma treatment.

5A to 5C show XPS analysis of C 1s peaks before and after CF 4 plasma treatment. FIG. 5A shows C 1s results of mold material. FIG. 5B shows C after CF 4 plasma treatment using an induction plasma apparatus. 1s result, and FIG. 5c is a C 1s result after CF 4 plasma treatment using an atmospheric pressure plasma apparatus. In FIG. 5, the horizontal axis represents binding energy (eV) and the vertical axis represents intensity (AU). As shown in FIG. 5, before the CF 4 plasma treatment, all carbons (C) are bonded to carbon or hydrogen, but after the CF 4 plasma treatment, the carbon bonded to hydrogen is replaced with a fluorine bonded form. It can be seen that. As described above, the CH bond is replaced with the CF bond by the plasma treatment, thereby making the mold surface show hydrophobicity.

On the other hand, Figure 6 is a graph showing the water contact angle change with time after CF 4 plasma treatment. It can be seen that the water contact angle does not change significantly even after 3 hours after the CF 4 plasma treatment.

Next, the result of transferring the nano-pattern using the nanoimprint lithography method according to an embodiment of the present application is shown in FIG. That is, after CF 4 plasma treatment of a mold having a nano pattern in the form of a line, the pattern is transferred to a resist, and the image of the transferred pattern by Scanning Electron Microscopy is shown in FIG. 7. Indicated.

As shown in Fig. 7, it can be seen that even the edge portion of the line pattern is well transferred.

As shown in FIG. 3 to FIG. 7, the plasma surface treatment of the mold according to the embodiment of the present application can shorten the processing time of the nanoimprint lithography process, and the mold and the resist are easily separated, thereby providing excellent pattern transfer. The effect can be obtained.

Hereinbefore, the present invention has been described in detail with reference to the embodiments and examples, but the present invention is not limited to the above embodiments and embodiments, and may be modified in various forms, and is commonly used in the art within the technical spirit of the present application. It is evident that many variations are possible by those of skill in the art.

10: Mold
20: description
30: resist
40: remaining layer

Claims (10)

In a method for treating the surface of a mold used in a nanoimprint lithography process,
And hydrophobically modifying the surface of the mold by plasma treating the surface of the mold.
The method of claim 1,
The plasma treatment is performed using a fluorine-based gas, the surface treatment method of the mold.
The method of claim 1,
Plasma treating the surface of the mold such that the water contact angle of the surface of the mold is 100 ° or more.
The method of claim 2,
The fluorine-based gas is F 2 , BF 3 , HF, NF 3 , CF 4 , SF 6 , CH 2 F 2 , CHF 3 , C 2 F 6 , C 2 F 8 , C 3 F 6 , C 3 F 8 , C 4 F 6 , C 4 F 8 , C 4 F 10 , C 6 F 10 , C 5 F 12 , SF 5 , WF 6 , SiF 4 , Si 2 F 6 , XeF 2 And combinations thereof, the surface treatment method of the mold.
The method of claim 1,
Wherein said mold is formed of a polymeric material.
In the nanoimprint lithography method,
Manufacturing a mold of a transparent material having a nano pattern formed thereon;
Plasma treating the surface of the mold such that the mold surface is hydrophobically modified;
Coating a resist on a substrate and placing the mold on the resist;
Applying pressure to the mold to fill the resist between the nanopatterns of the mold;
Irradiating the resist with ultraviolet light through the transparent mold to cure the resist; And
Detaching the mold from the resist; the nanoimprint lithography method.
The method according to claim 6,
Wherein said plasma treatment is performed using a fluorine-based gas.
The method according to claim 6,
Plasma treatment of the surface of the mold, so that the water contact angle of the surface of the mold is 100 ° or more, nanoimprint lithography method.
The method of claim 7, wherein
The fluorine-based gas is F 2 , BF 3 , HF, NF 3 , CF 4 , SF 6 , CH 2 F 2 , CHF 3 , C 2 F 6 , C 2 F 8 , C 3 F 6 , C 3 F 8 , C 4 F 6 , C 4 F 8 , C 4 F 10 , C 6 F 10 , C 5 F 12 , SF 5 , WF 6 , SiF 4 , Si 2 F 6 , XeF 2 And combinations thereof, nanoimprint lithography method.
The method according to claim 6,
Wherein said mold is formed of a polymeric material.
KR1020100128838A 2010-12-16 2010-12-16 Method for treating surface of mold by using plasma KR20120067448A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3214117A4 (en) * 2014-10-29 2018-06-27 Toyo Seikan Group Holdings, Ltd. Plastic molded body
KR102363524B1 (en) * 2020-10-21 2022-02-16 인제대학교 산학협력단 Mold for microneedle manufacturing and manufacturing method thereof
CN115283030A (en) * 2022-08-03 2022-11-04 广东顺德工业设计研究院(广东顺德创新设计研究院) Bonding method of polymer microfluidic chip and polymer microfluidic chip

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3214117A4 (en) * 2014-10-29 2018-06-27 Toyo Seikan Group Holdings, Ltd. Plastic molded body
US10737835B2 (en) 2014-10-29 2020-08-11 Toyo Seikan Group Holdings, Ltd. Plastic molded body
KR102363524B1 (en) * 2020-10-21 2022-02-16 인제대학교 산학협력단 Mold for microneedle manufacturing and manufacturing method thereof
KR20220052864A (en) * 2020-10-21 2022-04-28 인제대학교 산학협력단 Mold for microneedle manufacturing and manufacturing method thereof
CN115283030A (en) * 2022-08-03 2022-11-04 广东顺德工业设计研究院(广东顺德创新设计研究院) Bonding method of polymer microfluidic chip and polymer microfluidic chip

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