WO2007117107A1

WO2007117107A1 - Treating method of mold

Info

Publication number: WO2007117107A1
Application number: PCT/KR2007/001725
Authority: WO
Inventors: Youn-Sang Kim; Nae-Yoon Lee; Min-Jung Lee
Original assignee: Ewha University-Industry Collaboration Foundation
Priority date: 2006-04-10
Filing date: 2007-04-10
Publication date: 2007-10-18
Also published as: KR100705641B1

Abstract

A method of treating a mold, comprising: providing a mold which has a predetermined pattern; introducing a hydroxyl group to a surface of the mold; and forming an anti-adhesion coating layer by applying a surface treating material represented with the Chemistry Figure 1 (refer to the Technical Solution) to the mold. In the Chemistry Figure 1, R1 may be the same or different and include one of CH3, F and CF3, and R2 is a functional group which is reactable to the hydroxyl group or an amino group. Therefore, a treating method of a mold which reduces adhesion between a mold and an organic layer is provided.

Description

Description TREATING METHOD OF MOLD

Technical Field

[1] Methods consistent with the present invention relate to a treating method of a mold, and more particularly, to a treating method of a mold which forms an anti-adhesion coating layer on a surface of a mold to reduce adhesion to an organic layer. Background Art

[2] A substrate, an inorganic layer or a metal layer is patterned to manufacture a semiconductor or a display device. Such a patterning process is typically performed through photolithography including coating, exposing, developing and etching a photoresist layer. Meanwhile, the etching may be omitted in patterning of the organic layer.

[3] The photolithography has several stages and is thus complicated. To address such a problem, a method of patterning layers with a mold has been developed.

[4] The mold has a predetermined pattern and is pressed to an organic layer on the substrate. After the pattern of the mold is transferred to the organic layer, the mold is removed from the organic layer. The organic layer may include polymer, photoresist polymer or oligomer. Disclosure of Invention Technical Problem

[5] However, the pattern which is transferred to the organic layer is damaged while the mold is removed from the organic layer, due to adhesion between the mold and the organic layer. The pattern becomes damaged more severely as the pattern of the mold is minute. Technical Solution

[6] Accordingly, it is an aspect of the present invention to provide a treating method of a mold which reduces adhesion between a mold and an organic layer.

[7] The foregoing and/or other aspects of the present invention are achieved by providing a method of treating a mold, comprising: providing a mold which has a predetermined pattern; introducing a hydroxyl group to a surface of the mold; and forming an anti- adhesion coating layer by applying a surface treating material represented with the following chemistry figure 1, to the mold.

[8] Chemistry Figure 1

[9] (Here, Rl may be the same or different and include one of CH3, F and CF3, and R2 is a functional group which is readable to the hydroxyl group or an amino group.) [10] According to an aspect of the invention, the R2 includes an expoxy group in the chemistry figure 1. [11] According to an aspect of the invention, the method further comprises introducing an amino group to the surface of the mold after the hydroxyl group is introduced thereto. [12] According to an aspect of the invention, the introducing the amino group comprises applying silane having NH2 as an end group to the mold. [13] According to an aspect of the invention, the silane comprises at least one of, amino- propyltrichlorosilane(NH (CH ) SiCl ), N-

(3-(Trimethoxysilyl)propyl)ethylenediamine, 4-aminobutyltriethoxysilane,

(aminoethylaminomethyl)phenethyltrimethoxysilane, N-

(2-aminoethyl)-3-aminopropylsilanetriol, N-

(2- aminoethyl) - 3 -aminopropyltrimethoxy silane, N-

(2- aminoethyl) - 3 -aminopropyltriethoxy silane, N-

(6-aminohexyl)aminomethyltrimethoxysilane, N-(6-aminohexyl)aminopropyltrimetho xysilane, N-(2-aminoethyl)-l 1-aminoundecyltrimethoxysilane,

3-(m-aminophenoxy)propyltrimethoxysilane, m-aminophenyltrimethoxysilane, p- aminophenyltrimethoxysilane, N-3- [amino(polypropylenoxy)] aminopropy- ltrimethoxysilane, 11-aminoundecyltriethoxysilane,

3-aminopropyltrimethoxysilane(NH (CH ) Si(OCH ) ),

3-aminopropyltriethoxysilane(NH (CH ) Si(OC H ) ). [14] According to an aspect of the invention, the introducing the hydroxyl group comprises treating the mold using oxygen plasma or UV with oxygen (UVO). [15] According to an aspect of the invention, the mold comprises a polyurethane series polymer or an acryl series polymer, and the acryl series polymer comprising at least one of Pentaerythritol propoxylate triacrylate, Bisphenol A propoxylate diacrylate and

Trimethylolpropane ethoxylate triacrylate. [16] The mold, a term used in the present invention, includes a soft mold made of polymer material, a hard mold made of inorganic material, and a master mold for man- ufacturing the soft and hard molds. [17] The present invention is to form an anti- adhesion coating layer by introducing a surface treating material to a mold. A functional group such as a hydroxyl group or an amino group is introduced to the mold to easily introduce a surface treating material.

The surface treating material reacts to the functional group on the mold to be introduced to a surface of the mold.

[18] The surface treating material is represented as the following chemistry figure 1.

[19]

— R1

[20] Here, Rl may be the same or different and include one of CH3, F and CF3, and R2 is a functional group which is readable to the hydroxyl group or the amino group.

[21] The anti- adhesion coating layer which is formed by introducing the surface treating material provides good non-adhesiveness to other materials. If the anti-adhesion coating layer is formed on the soft mold or the hard mold, the mold is less adhesive to an organic layer to which a pattern is transferred. If the anti-adhesion coating layer is formed on the master mold, the master mold is less adhesive to a material of the soft mold (hard mold), thereby manufacturing high quality soft mold or hard mold.

[22] According to the present invention, a treating method of a mold which reduces adhesion between a mold and an organic layer is provided. Brief Description of the Drawings

[23] FIG. 1 is a flowchart which illustrates a treating method of a mold according to a first exemplary embodiment of the present invention;

[24] FIGS. 2 to 5 illustrate sequentially the treating method of the mold according to the first exemplary embodiment of the present invention;

[25] FIG. 6 illustrates a method of patterning a substrate which uses the mold treated according to the first exemplary embodiment of the present invention;

[26] FIG. 7 is a flowchart which illustrates a treating method of a mold according to a second exemplary embodiment of the present invention; and

[27] FIGS. 8 to 11 illustrate sequentially the method of treating the mold according to the second exemplary embodiment of the present invention. Best Mode for Carrying Out the Invention

[28] A method of treating a mold according to a first exemplary embodiment of the present invention will be described with reference to FIGS. 1 to 5. In the first exemplary embodiment of the present invention, an anti-adhesion coating layer is introduced to a soft mold.

[29] FIG. 1 is a flowchart which illustrates a treating method of a mold according to a first exemplary embodiment of the present invention. FIGS. 2 to 5 illustrate sequentially the treating method of the mold according to the first exemplary embodiment of the present invention.

[30] A soft mold 10 is provided as shown in FIG. 2 (Sl 10). A predetermined pattern 11 is provided in the soft mold 10. The soft mold 10 may include a polyurethane series polymer or an epoxy series polymer. More specifically, the soft mold 10 may include pentaerythritol propoxylate triacrylate, bisphenol A propoxylate diacrylate, trimethy- lolpropane ethoxylate triacrylate, etc.

[31] The pattern 11 may be several micrometers or nanometers large.

[32] Then, a hydroxyl group (OH) is introduced to a surface of the soft mold 10 as shown in FIG. 3(Sl 11). The introduction of the hydroxyl group may be accomplished by treating the soft mold 10 using oxygen plasma or UV with oxygen, but not limited thereto. For example the soft mold 10 may be treated using oxygen plasma, with intensity of about 25W, at a pressure of 0.2Torr and for approximately 20 seconds.

[33] An amino group is introduced to the surface of the soft mold 10 as shown in FIG. 4

(Sl 12). The amino group may be introduced with silane having an NH2 group. More specifically, the silane may include one of aminopropyltrichlorosilane(NH (CH ) SiCl ), N-(3-(Trimethoxysilyl)propyl)ethylenediamine, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N- (2-aminoethyl)-3-aminopropylsilanetriol, N- (2- aminoethyl) - 3 -aminopropyltrimethoxy silane, N- (2- aminoethyl) - 3 -aminopropyltriethoxy silane, N- (6-aminohexyl)aminomethyltrimethoxysilane, N- (6-aminohexyl)aminopropyltrimethoxysilane, N- (2- aminoethyl)- 11-aminoundecyltrimethoxysilane,

3-(m-aminophenoxy)propyltrimethoxysilane, m-aminophenyltrimethoxysilane, p- aminophenyltrimethoxysilane, N-3- [amino(polypropylenoxy)] aminopropy- ltrimethoxysilane, 11-aminoundecyltriethoxysilane, 3-aminopropyltrimethoxysilane (NH (CH ) Si(OCH ) ), 3-aminopropyltriethoxysilane(NH (CH ) Si(OC H ) , hereinafter, to be called APTES).

[34] If APTES is used, the soft mold 10 having the hydroxyl group is dipped into deionized water in which 0.5 wt. % APTES is dissolved. The soft mold 10 may be dipped thereinto for approximately 5 to 20 minutes. During the dipping process, the silane group of the ATPES and the hydroxyl group react to each other, thereby in- troducing the amino group to the soft mold 10.

[35] Then, the soft mold 10 is cleansed with the deionized water (Sl 13).

[36] Then, as shown in Fig. 5, the soft mold 10 is applied with a surface treating material to form an anti-adhesion coating layer 12 (Sl 14). The surface treating material includes a poly (demethylsiloxane) series as an end group. For example, the surface treating material may include one of poly(dimethylsiloxane) monoglycidyl ether terminated (hereinafter, to be called PDMS-mget) which is represented with a following chemical formula 2, Epoxycyclohexylethylmethylsiloxane dimethylsiloxane copolymers, mono-(2,3-epoxy)propylether terminated polydimethylsiloxane, poly(dimethylsiloxane-co-(2-(3,4-epoxycyclohexyl)ethyl)methylsiloxane, poly(dimethylsiloxane-co-(3-(2-(2- hydroxyethoxy)ethoxy)propyl)methylsiloxane.

[37] ChemistryFigure 2

CH3 CH3 CH3

I y I _x I

^^\ 0^/^ Si 4- 0 — Si + 0 — Si — CH3 \ / \ ^X I 'n i

0 CH3 CH3 CH3

[38] The PDMS-mget is introduced to the soft mold 10 having the amino group and reacts thereto at 6O⁰C to 9O⁰C for about 1 to 5 hours. Here, the epoxy group of the

PDMS is combined with the amino group formed in the soft mold 10, thereby forming the anti-adhesion coating layer 12. [39] Then, the soft mold 10 is cleansed (Sl 15), which is performed using supersonic waves while the soft mold 10 is dipped into isopropyl alcohol or toluene. [40] The foregoing exemplary embodiment may vary. For example, the operation Sl 12 which introduces the amino group may be omitted. Here, the PDMS-mget directly reacts to the hydroxyl group of the soft mold 10, and a higher reaction temperature is required. [41] Hereinafter, a method of patterning a substrate which uses the mold treated according to the first exemplary embodiment of the present invention will be described with reference to FIG. 6. FIG. 6 illustrates a method of patterning a substrate (wafer).

Alternatively, the present invention is applicable to patterning a metal layer or an inorganic layer. [42] An organic layer 110 is coated to a substrate 100 including silicon. For example, the organic layer 110 may include NOA 63, a UV-curable adhesive manufactured by

Norland, the U.S. [43] The soft mold 10 having the anti- adhesion coating layer 12 is pressed to the organic layer 110, and the organic layer 110 is cured by UV for about 30 minutes. [44] After the organic layer 110 is cured, the soft mold 10 is removed therefrom. Then, the organic layer 110 having a pattern 111 is formed on the substrate 110. That is, the pattern 11 of the soft mold 10 is transferred to the organic layer 110.

[45] Here, the soft mold 10 is separated from the organic layer 110 without damaging the pattern 111 of the organic layer 110 by the anti-adhesion coating layer 12 formed on the surface of the soft mold 10.

[46] If an interval between the patterns 11 of the soft mold 10 becomes shorter, e.g., if the interval is ID and below, the pattern 11 may be paired with each other.

[47] According to the surface treating method of the present invention, the surface of the soft mold 10 is selectively treated not be adhered to the organic material. The soft mold 10 may include a polymer, an inorganic material as well as soft materials.

[48] As the surface of the soft mold 10 is treated as mentioned above, the mold may include hard materials regardless of the surface properties of the mold. Therefore, the pairing problem may be reduced, which occurs due to the soft properties of the mold material.

[49] The organic layer 110 remaining between the patterns 111 is removed by reactive ion etching (RIE), thereby exposing the substrate 110 between the patterns 111.

[50] Then, the exposed substrate 100 is removed by RIE. Preferably, the RIE is performed to selectively etch the substrate 100.

[51] A method of treating a mold according to a second exemplary embodiment of the present invention will be described with reference to FIGS. 7 to 11. In the second exemplary embodiment, a soft mold is manufactured using a master mold.

[52] FIG. 7 is a flowchart which illustrates a treating method of a mold according to a second exemplary embodiment of the present invention. FIGS. 8 to 11 illustrate sequentially the method of treating the mold according to the second exemplary embodiment of the present invention.

[53] First, a master mold 20 is provided (S210). The master mold 20 may include silicon or silica. The master mold 20 includes a concave part 21 corresponding to a pattern 11 of a soft mold 10.

[54] As shown in FIG. 8, an anti-adhesion coating layer 22 is formed on a surface of the master mold 20 (S211). The method of forming the anti-adhesion coating layer 22 is the same as that of forming the anti-adhesion coating layer 12 on the soft mold 10. Thus, the detailed description will be avoided here. Here, the master mold 20 including silicon may be treated with oxygen plasma, e.g., with intensity of about 50W, at a pressure of 0.2 Torr and for about 10 minutes.

[55] As shown in FIG. 9, a soft mold forming layer 15 is coated to the master mold 20

(S212). For example, the soft mold forming layer 15 may include NOA, UV-curable adhesion of a polyurethane series, manufactured by Norland, the U.S., or SU-8 2035, a UV-curable photoresist material of an epoxy series manufacted by Microchem, the

U.S. [56] A Polyethylene terephthalate (PET) plate 16 is provided on the soft mold forming layer 15. [57] As shown in FIG. 10, heat and/or UV is applied to the soft mold forming layer 15 to cure the soft mold forming layer 15 (S213). [58] As shown in FIG. 11, the soft mold 10 is separated from the master mold 20 (S214).

The soft mold 10 is separated from the master mold 20 without damaging the pattern

11 by the anti-adhesion coating layer 22 formed on the surface of the master mold 20. [59] The soft mold 10 may be cured again by heat and/or UV.

Industrial Applicability [60] Although a few exemplary embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes may be made in these exemplary embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims

[1] A method of treating a mold, comprising: providing a mold which has a predetermined pattern; introducing a hydroxyl group to a surface of the mold; and forming an anti-adhesion coating layer by applying a surface treating material represented with a following chemistry figure 1, to the mold.

RI Rt R1 I _/ I

R2 !— Si + 0 — Si + 0 — Si — R1 i \ i ' 'nn I I

RI R1 R1

(Here, Rl may be the same or different and include one of CH3, F and CF3, and

R2 is a functional group which is readable to the hydroxyl group or an amino group.) [2] The method according to claim 1, wherein the R2 includes an expoxy group in the chemical formula 1. [3] The method according to claim 1 or 2, further comprising introducing an amino group to the surface of the mold after the hydroxyl group is introduced thereto. [4] The method according to claim 3, wherein the introducing the amino group comprises applying s [5] The method according to claim 4, wherein the silane comprises at least one of, aminopropyltrichlorosilane(NH (CH ) SiCl ), N-

(3-(Trimethoxysilyl)propyl)ethylenediamine, 4-aminobutyltriethoxysilane,

(aminoethylaminomethyl)phenethyltrimethoxysilane, N-

(2- aminoethyl) - 3 -aminopropylsilanetriol, N-

(2- aminoethyl) - 3 -aminopropyltrimethoxy silane, N-

(2- aminoethyl) - 3 -aminopropyltriethoxy silane, N-

(6-aminohexyl)aminomethyltrimethoxysilane, N-

(6-aminohexyl)aminopropyltrimethoxysilane, N-(2-aminoethyl)- 11-aminound ecyltrimethoxysilane, 3-(m-aminophenoxy)propyltrimethoxysilane, m- aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, N-

3-[amino(polypropylenoxy)]aminopropyltrimethoxysilane,

11-aminoundecyltriethoxysilane, 3-aminopropyltrimethoxysilane(NH (CH )

Si(OCH ) ), [6] The method according to claim 1 or 2, wherein the introducing the hydroxyl group comprises treating the mold using oxygen plasma or UV with oxygen (UVO).

[7] The method according to claim 1 or 2, wherein the mold comprises a polyurethane series polymer or an acryl series polymer, and the acryl series polymer comprising at least one of Pentaerythritol propoxylate triacrylate, Bisphenol A propoxylate diacrylate and Trimethylolpropane ethoxylate triacrylate.