KR102031825B1 - Method for manufacturing a micro/nano pattern using spontaneous separation and selective wetting of solution materials - Google Patents

Abstract

The disclosed micropattern manufacturing method comprises coating a coating composition comprising a hydrophilic compound and a hydrophobic compound on a base substrate, and forming a hydrophilic coating layer and a hydrophobic coating layer disposed on the hydrophilic coating layer through spontaneous phase separation, the hydrophilic coating layer and the Patterning a hydrophobic coating layer to form a composite pattern having a hydrophilic region and a hydrophobic region, selectively placing a pattern forming composition on the hydrophilic region or the hydrophobic region upon selective wetting, and forming the pattern Drying or curing the composition to form a pattern.

Description

METHOD FOR MANUFACTURING A MICRO / NANO PATTERN USING SPONTANEOUS SEPARATION AND SELECTIVE WETTING OF SOLUTION MATERIALS}

The present invention relates to a method for manufacturing a micropattern, and more particularly, to a method for manufacturing a micropattern using a spontaneous phase separation and selective wetting of a solution material to form a micro / nano pattern.

Micro / nano patterning process is an essential technology for manufacturing electronic devices, optical devices, and the like, and various methods for manufacturing such micro / nano patterns have been developed.

As a representative example, a micro / nano pattern may be manufactured through an etching technique using photolithography, a micro / nano pattern may be manufactured through a transfer technique or an etching technique using imprinting, or a nano-material may be formed from a nano-sized material. It is known to produce a nano-pattern using the growth method of the particles, or to produce a micro-pattern using printing.

However, in the case of the technologies proposed to date, the process cost is relatively high in the case of including the photolithography process or the etching technique, and the transfer technique using imprinting has a disadvantage in that a large area process is difficult. It is difficult to secure uniformity or yield of patterns, and in the case of printing technology, it is difficult to produce fine patterns.

Particularly, nanopatterns have been mainly applied to high-priced and high-performance products, but recently, the diversity of electronic or optical products is accelerating, and in order to cope with this, low cost, large area fairness, yield and uniformity can be secured. There is an increasing demand for possible processes, but the development of technology that satisfies this has been insufficient.

On the other hand, a number of techniques have been developed to solve the problems of the conventional micropattern manufacturing techniques as described above, in the Republic of Korea Patent Publication No. 10-2014-0077624 as a representative prior art to form the intaglio pattern on the plastic substrate and the doctor blade A process of physically filling ink by a ding method is disclosed.

Republic of Korea Patent Publication No. 10-2014-0077624

Accordingly, the technical problem of the present invention has been conceived in this respect, the object of the present invention is to easily control the width and thickness of the pattern and to produce a large area pattern, the yield and uniformity of the pattern is improved and the process It is possible to reduce the cost and to provide a fine pattern manufacturing method that can further reduce the minimum limit of the pattern.

The micropattern manufacturing method according to an embodiment for realizing the object of the present invention, the coating composition comprising a hydrophilic compound and a hydrophobic compound on the base substrate, and through the spontaneous phase separation on the hydrophilic coating layer and the hydrophilic coating layer Forming a disposed hydrophobic coating layer, patterning the hydrophilic coating layer and the hydrophobic coating layer to form a composite pattern having a hydrophilic region and a hydrophobic region, on the composite pattern, the hydrophilic region or the hydrophobic region upon selective wetting Optionally disposing a pattern forming composition and drying or curing the pattern forming composition to form a pattern.

According to one embodiment, the coating composition comprises at least a hydrophilic compound, a hydrophobic compound and a photoinitiator comprising a polymerizable unsaturated bond.

According to one embodiment, the hydrophilic compound comprising a polymerizable unsaturated bond, at least one selected from the group consisting of urethane acrylate oligomer, polyurethane acrylate, epoxy acrylate oligomer, polyester acrylate and polyether acrylate Include.

According to one embodiment, the hydrophobic compound comprises a perfluoropolyether modified to include a polymerizable unsaturated bond.

According to one embodiment, the hydrophobic compound comprises at least one selected from the group consisting of octafluoropentyl methacrylate, octafluoropentyl acrylate, glycidyl octafluoropentyl ether, and derivatives thereof.

According to one embodiment, the coating composition further comprises an alcohol solvent.

According to an embodiment, the patterning of the hydrophilic coating layer and the hydrophobic coating layer may include pressing the hydrophilic coating layer and the hydrophobic coating layer with an imprinting mold and photocuring in a state in which the imprinting mold is combined. Forming a hydrophobic pattern having an opening and a hydrophilic pattern having a recess corresponding to the opening, wherein the hydrophobic pattern corresponds to the hydrophobic region, and the recess of the hydrophilic pattern corresponds to the hydrophilic region. It features.

According to one embodiment, the hydrophobic coating layer has a smaller thickness than the hydrophilic coating layer.

In example embodiments, the pattern forming composition may include metal particles, inorganic particles, metal precursors, inorganic precursors, low molecular weight organic compounds, or polymers.

According to an embodiment, the patterning of the hydrophilic coating layer and the hydrophobic coating layer may include forming a mask having an opening on the hydrophobic coating layer, and the hydrophobic coating layer and the hydrophilic layer exposed through the opening using the mask. Etching the coating layer.

According to one embodiment, the forming of the hydrophilic coating layer and the hydrophobic coating layer, coating the coating composition on the base substrate, and heating the coating composition at 60 ℃ to 100 ℃ to promote spontaneous phase separation Steps.

According to embodiments of the present invention, since the micro / nano pattern formed on the imprinting mold is implemented as it is, various and fine patterns may be easily formed.

In addition, a pattern having various thicknesses may be easily formed on the basis of the thickness of the hydrophilic film and the hydrophobic film and the depth of the pattern formed on the imprinting mold, and a fine pattern of a large area may be formed.

In addition, roll-to-roll or roll-to-plate imprinting may be used, and there is no unnecessary loss in the solution used for forming the micropattern, thereby improving manufacturing economics. Can be.

In particular, by using spontaneous phase separation of the hydrophobic layer and the hydrophilic layer, the composite coating layer can be formed at once without coating the hydrophobic composition and the hydrophilic composition, which is advantageous in the process.

In addition, when the hydrophobic coating layer is formed separately on the hydrophilic coating layer, the coating layer strength increases as the coating film thickness increases. Therefore, the imprinting is not easy to refine, but according to the present invention, by using spontaneous phase separation, a very thin thickness, for example, a hydrophobic coating layer of 100 nm or less can be obtained, and imprinting is performed by performing imprinting before curing. The limit can be reduced to a pattern width of 100 nm or less.

1 to 7 are cross-sectional views showing a method for manufacturing a fine pattern according to an embodiment of the present invention.
8 to 12 are cross-sectional views showing a method for manufacturing a fine pattern according to another embodiment of the present invention.

As the inventive concept allows for various changes and numerous modifications, the embodiments will be described in detail in the text. However, this is not intended to limit the present invention to a specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the drawings, similar reference numerals are used for similar elements. Terms such as first and second may be used to describe various components, but the components should not be limited by the terms.

The terms are used only for the purpose of distinguishing one component from another. The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

In this application, the terms "comprise" or "consist of" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

Hereinafter, with reference to the accompanying drawings, it will be described in detail a preferred embodiment of the present invention.

1 to 7 are cross-sectional views showing a method for manufacturing a fine pattern according to an embodiment of the present invention.

Referring to FIGS. 1 and 2, a curable composition including a hydrophilic compound and a hydrophobic compound is provided on a substrate 10 to provide an uncured hydrophilic coating layer 24 and an uncured hydrophobic layer disposed on the uncured hydrophilic coating layer 24. The coating layer 22 is formed.

According to an embodiment, as shown in FIG. 1, the mixed coating layer 20 is first formed by the curable composition, and then the uncured hydrophilic coating layer 24 is formed by spontaneous phase separation using a difference in properties of the components of the curable composition. ) And the uncured hydrophobic coating layer 22 may be formed.

According to one embodiment, in order to promote spontaneous phase separation and the curable composition includes a solvent, the mixed coating layer 20 may be heated to remove the solvent. For example, the mixed coating layer 20 may be heated at 40 ° C to 120 ° C, and preferably at 60 ° C to 100 ° C. When the heating temperature is excessively low, the time for phase separation may be long, and when excessively high, a non-uniform coating layer may be formed.

According to one embodiment, the curable composition may be a photocurable composition. For example, the photocurable composition may include at least a hydrophilic compound, a hydrophobic compound, and a photoinitiator including a polymerizable unsaturated bond.

The hydrophilic compound including the polymerizable unsaturated bond may form the uncured hydrophilic coating layer 24 by spontaneous phase separation.

For example, the polymerizable unsaturated bond may be an acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, epoxy group, vinyl ether group or oxetane group.

For example, the hydrophilic compound including the polymerizable unsaturated bond may include at least one selected from a monomer including a polymerizable unsaturated bond, an oligomer including a polymerizable unsaturated bond, and a prepolymer including a polymerizable unsaturated bond. have. Specifically, the hydrophilic compound including the polymerizable unsaturated bond may include a urethane acrylate oligomer, polyurethane acrylate, epoxy acrylate oligomer, polyester acrylate, polyether acrylate and the like. These may each be used alone or in combination. As a more specific example, polyurethane acrylates such as NOA (Norland Optical Adhesive) series can be used.

The hydrophilic compound including the polymerizable unsaturated bond may be activated by a photoinitiator and react with each other to form a cured coating layer.

The hydrophobic compound may form the uncured hydrophobic coating layer 22 by spontaneous phase separation.

For example, the hydrophobic compound may include a fluorine-containing compound. Specifically, the hydrophobic compound may include a modified perfluoropolyether (PFPE). The modified perfluoropolyether (PFPE) may include a polymerizable unsaturated bond such as acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, epoxy group, vinyl ether group or oxetane group. Can be. More specifically, DAIKIN's OPTOOL DAC-HP may be used.

In another embodiment, the hydrophobic compound may include an octafluoro derivative. The octafluoro derivative may be a monomer, oligomer or prepolymer. For example, the hydrophobic compound may include octafluoropentyl methacrylate, octafluoropentyl acrylate, glycidyl octafluoropentyl ether, or derivatives thereof.

Examples of the photoinitiator include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, Benzoinpropyl ether, benzyl dimethyl ketal, N, N, N ', N'-tetramethyl-4,4'-diaminobenzophenone, and 1- (4-isopropylphenyl) -2-hydroxymethylpropane- 1-one etc. are mentioned. However, the present invention is not limited thereto. In addition to the compound, a photoinitiator known to be usable in the art may be used without particular limitation.

According to one embodiment, the photocurable composition may further include a solvent in order to control physical properties such as coating properties, viscosity. For example, the solvent may include at least one selected from the group consisting of alcohols, ketones, esters, amides, ethers, and hydrocarbons. The alcohols may include at least one selected from the group consisting of isopropanol, methanol, ethanol, propanol, butanol, benzyl alcohol, propylene glycol and ethylene glycol. The ketones may include at least one selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and methylcyclohexanone. The esters may include at least one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, butyl formate, and ethyl lactate. The amides may include at least one selected from the group consisting of dimethylformamide, diketylacetamide and n-methylpyrrolidone. The ethers may include at least one selected from the group consisting of propylene glycol monomethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol and dimethyl ether. Preferably, the solvent may include alcohols.

When the photocurable composition does not include a solvent, for example, the photocurable composition may include 95 wt% to 99.5 wt% of a hydrophilic compound including the polymerizable unsaturated bond and 0.5 wt% to 5 wt% of the hydrophobic compound. It may include.

When the photocurable composition includes a solvent, for example, the photocurable composition may include 20% by weight to 50% by weight of a hydrophilic compound including the polymerizable unsaturated bond, 0.5% by weight to 5% by weight of the hydrophobic compound, and Extra solvent may be included.

In other embodiments, a thermosetting composition may be used instead of the photocurable composition.

Referring to FIG. 3, an imprint process is performed by pressing the uncured hydrophilic coating layer 24 and the uncured hydrophobic coating layer 22 with a mold 29. The mold 29 may include a protrusion protruding from the base substrate toward the coating layer. By the imprint process, the protrusion of the mold 29 may pass through the uncured hydrophobic coating layer 22 and be inserted into the uncured hydrophilic coating layer 24. The shape of the mold 29 and the arrangement of the patterns may be determined to correspond to the shape and size of the micro pattern to be formed.

Next, in the state in which the mold 29 is bonded to the coating layer, the uncured coating layer is exposed to cure the uncured hydrophilic coating layer 24 and the uncured hydrophobic coating layer 22. Accordingly, the cured hydrophilic pattern 28 and the cured hydrophobic pattern 26 may be formed.

The thickness of the cured hydrophilic pattern 28 and the cured hydrophobic pattern 26 may be controlled by the content of the coating composition. According to the present invention, the uncured hydrophilic coating layer 24 and the uncured hydrophobic coating layer 22 are formed using spontaneous phase separation. Thus, the uncured hydrophobic coating layer 22 and the cured hydrophobic pattern 26 formed therefrom may have a very thin thickness, for example, 100 nm or less, several nm to several tens of nm thick. The uncured hydrophilic coating layer 24 and the cured hydrophilic pattern 28 formed therefrom have a thickness greater than the uncured hydrophobic coating layer 22 and the cured hydrophobic pattern 26 formed therefrom, eg, from several hundred nm to several It may have a thickness of μm.

Referring to FIG. 4, the cured hydrophobic pattern 26 is patterned by the mold 29 to cover a portion of the cured hydrophilic pattern 28 and to expose an upper surface of the cured hydrophilic pattern 28. Has an opening. The cured hydrophilic pattern 28 may be patterned by the mold 29 to form an intaglio pattern. For example, the cured hydrophilic pattern 28 may overlap with the opening and have a recess formed in an engraved pattern, and the recess may be exposed. In the plan view, the portion where the cured hydrophobic pattern 26 is disposed may be defined as a hydrophobic region A1 and overlaps the exposed region or the opening of the cured hydrophobic pattern 26. The region may be defined as a hydrophilic region A2. The cured hydrophobic pattern 26 and the cured hydrophilic pattern 28 may be referred to as a composite pattern.

Referring to FIG. 5, the pattern forming composition 30 is provided on the composite pattern having the hydrophobic region A1 and the hydrophilic region A2. The pattern forming composition 30 may have hydrophilicity or hydrophobicity. According to one embodiment, the pattern forming composition is hydrophilic. Therefore, it may not be disposed on the hydrophobic region A1 by the repulsive force, but may be disposed only on the hydrophilic region A2 by selective wetting. Specifically, the pattern forming composition 30 may be disposed in the recess of the cured hydrophilic pattern 28.

In another embodiment, the pattern forming composition 30 may have hydrophobicity. For example, the hydrophobic region may have a recess, and the pattern forming composition having hydrophobicity in the recess may be selectively disposed. In another embodiment, when the hydrophobic region is formed of a material such as Cytop, the hydrophobic region may have a repulsive force with respect to a hydrophobic solvent such as chlorobenzene, and thus may be selectively disposed using a hydrophobic pattern forming composition.

The pattern forming composition may include various materials such as metal particles, inorganic particles, metal precursors, inorganic precursors, low molecular weight organic compounds, and polymers according to a desired pattern, and may include spin coating, dip coating, slot-die coating, and inkjet. It may be provided by various methods such as printing.

6 and 7, the pattern forming composition is dried or cured to form a fine pattern 32. According to an embodiment, the thickness of the micropattern 32 may be smaller than, equal to, or larger than the depth of the recess. In addition, the thickness of the micropattern 32 may be adjusted by varying the concentration of components of the pattern forming composition or by repeating application and drying several times.

In addition, when the micropattern 32 is formed by repeating the application and drying several times, the multilayer film micropattern including different kinds of materials may be manufactured using one or more kinds of solutions.

If necessary, at least some of the cured hydrophobic pattern 26 and the cured hydrophilic pattern 28 may be removed. For example, as shown in FIG. 7, the cured hydrophobic pattern 26 and the cured hydrophilic pattern 28 may be etched using the micropattern 32 as a mask. The cured hydrophilic pattern 28 disposed under the fine pattern 32 may remain to form a residual pattern 34.

According to the embodiments of the present invention as described above, since the micro / nano pattern formed on the imprinting mold is implemented as it is, it is possible to easily form a variety of fine patterns.

In addition, a pattern having various thicknesses may be easily formed on the basis of the thickness of the hydrophilic film and the hydrophobic film and the depth of the pattern formed on the imprinting mold, and a fine pattern of a large area may be formed.

In addition, roll-to-roll or roll-to-plate imprinting may be used, and there is no unnecessary loss in the solution used for forming the micropattern, thereby improving manufacturing economics. Can be.

In particular, by using spontaneous phase separation of the hydrophobic layer and the hydrophilic layer, the composite coating layer can be formed at once without coating the hydrophobic composition and the hydrophilic composition, which is advantageous in the process.

In addition, when the hydrophobic coating layer is formed separately on the hydrophilic coating layer, the coating layer strength increases as the coating film thickness increases. Therefore, the imprinting is not easy to refine, but according to the present invention, by using spontaneous phase separation, a very thin thickness, for example, a hydrophobic coating layer of 100 nm or less can be obtained, and imprinting is performed by performing imprinting before curing. The limit can be reduced to a pattern width of 100 nm or less.

8 to 12 are cross-sectional views showing a method for manufacturing a fine pattern according to another embodiment of the present invention.

Referring to FIG. 8, a curable composition including a hydrophilic compound and a hydrophobic compound is provided on a substrate 10 to form a hydrophilic coating layer 44 and a hydrophobic coating layer 42 disposed on the hydrophilic coating layer 44.

The hydrophilic coating layer 44 and the hydrophobic coating layer 42 may be formed in a similar manner to the above-described embodiment. For example, the hydrophilic coating layer 44 and the hydrophobic coating layer 42 may be formed by spontaneous phase separation after providing a curable composition including a hydrophilic compound and a hydrophobic compound including a polymerizable unsaturated bond on the substrate 10. have. According to an embodiment, the hydrophilic coating layer 44 and the hydrophobic coating layer 42 may be cured by photocuring or the like.

Referring to FIG. 9, a mask 50 is formed on the hydrophobic coating layer 42. The mask 50 may have an opening that partially exposes the hydrophobic coating layer 42. The mask 50 may be formed through various methods. For example, after applying the photoresist composition on the hydrophobic coating layer 42, it may be formed through exposure and development. In another example, the curable composition may be applied onto the hydrophobic coating layer 42, and then patterned by imprinting to form the mask 50.

Referring to FIG. 10, the hydrophilic coating layer 44 and the hydrophobic coating layer 42 may be patterned using the mask 50. For example, the hydrophilic coating layer 44 and the hydrophobic coating layer 42 may be patterned through anisotropic dry etching. Accordingly, a hydrophilic pattern 48 and a hydrophobic pattern 46 disposed on the hydrophilic pattern 48 may be formed. The hydrophobic pattern 46 may have an opening, and the hydrophilic pattern 48 may have an opening overlapping the opening of the hydrophobic pattern 46.

In FIG. 10, although the hydrophilic pattern 48 is removed to form an opening that exposes the top surface of the substrate 10, the present invention is not limited thereto. As shown in FIG. 6, the hydrophilic pattern may be removed. The pattern 48 may cover the entire upper surface of the substrate 10.

Referring to FIG. 11, the mask 50 is removed to expose the top surface of the hydrophobic pattern 46. In the plan view, a portion in which the hydrophobic pattern 46 is disposed may be defined as a hydrophobic region A1, and a portion overlapping the opening of the hydrophobic pattern 46 may be defined as a hydrophilic region A2. The hydrophobic pattern 46 and the hydrophilic pattern 48 may be referred to as a composite pattern.

Referring to FIG. 12, the pattern forming composition 60 is provided on the composite pattern having the hydrophobic region A1 and the hydrophilic region A2. The pattern forming composition 60 may have hydrophilicity or hydrophobicity. According to one embodiment, the pattern forming composition is hydrophilic. Therefore, it may not be disposed on the hydrophobic region A1 by the repulsive force, but may be disposed only on the hydrophilic region A2 by selective wetting. In detail, the pattern forming composition 60 may be disposed in an opening or a recess of the hydrophilic pattern 48.

Next, the pattern forming composition is dried or cured to form a fine pattern.

Although the above has been described with reference to a preferred embodiment of the present invention, those skilled in the art will be able to variously modify and change the present invention without departing from the spirit and scope of the invention as set forth in the claims below. It will be appreciated.

The micropattern manufacturing method according to the present invention has industrial applicability that can be used for the production of micro / nano patterns used for manufacturing electronic devices, optical devices, and the like.

10 base substrate 20 mixed coating layer
22: uncured hydrophobic coating layer 24: uncured hydrophilic coating layer
26: curing hydrophobic pattern 38: curing hydrophilic pattern
29: imprinting mold 30, 60: pattern forming composition
32: fine pattern
A1: hydrophobic region A2: hydrophilic region

Claims (11)

Coating a coating composition comprising a hydrophilic compound and a hydrophobic compound on a base substrate, and forming a hydrophilic coating layer and a hydrophobic coating layer disposed on the hydrophilic coating layer through spontaneous phase separation;
Patterning the hydrophilic coating layer and the hydrophobic coating layer to form a composite pattern having a hydrophilic region and a hydrophobic region;
Selectively placing a pattern forming composition on the composite pattern in the hydrophilic region or the hydrophobic region upon selective wetting; And
Drying or curing the pattern forming composition to form a pattern,
Patterning the hydrophilic coating layer and the hydrophobic coating layer,
Pressing the hydrophilic coating layer and the hydrophobic coating layer with an imprinting mold having protrusions so that the protrusions penetrate the hydrophobic coating layer and contact the hydrophilic coating layer; And
Photocuring while the imprinting mold is coupled to form a hydrophobic pattern having an opening and a hydrophilic pattern having a recess corresponding to the opening;
The hydrophobic pattern corresponds to the hydrophobic region, and the recess of the hydrophilic pattern corresponds to the hydrophilic region. The method of claim 1, wherein the coating composition comprises at least a hydrophilic compound, a hydrophobic compound, and a photoinitiator including a polymerizable unsaturated bond. The method of claim 2, wherein the hydrophilic compound containing a polymerizable unsaturated bond, at least one selected from the group consisting of urethane acrylate oligomer, polyurethane acrylate, epoxy acrylate oligomer, polyester acrylate and polyether acrylate Method for producing a fine pattern, characterized in that it comprises a.

The method of claim 2, wherein the hydrophobic compound comprises a perfluoropolyether modified to include a polymerizable unsaturated bond. The hydrophobic compound of claim 2, wherein the hydrophobic compound comprises at least one selected from the group consisting of octafluoropentyl methacrylate, octafluoropentyl acrylate, glycidyl octafluoropentyl ether, and derivatives thereof. Method for producing a fine pattern to be. The method of claim 2, wherein the coating composition further comprises an alcohol solvent. delete The method of claim 1, wherein the hydrophobic coating layer has a thickness smaller than that of the hydrophilic coating layer. The method of claim 1, wherein the pattern forming composition comprises metal particles, inorganic particles, metal precursors, inorganic precursors, low molecular weight organic compounds, or polymers. delete The method of claim 1, wherein the forming of the hydrophilic coating layer and the hydrophobic coating layer,
Coating the coating composition on the base substrate; And
Method of producing a micropattern, characterized in that to promote the spontaneous phase separation by heating the coating composition at 60 ℃ to 100 ℃.

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