METHACRYLATE COPOLYMERS AND METHODS OF MAKING AND USING SAME - Patent application

Abstract

Described herein are methacrylate copolymers derived from a (meth)acrylate monomer comprising a second terminal olefin group, an alkyl methacrylate monomer, where the alkyl group comprises 1-4 carbon atoms, a mono(meth)acrylate monomer comprising a perfluorinated alkyl group, a perfluorinated polyether group, or a silicone group low surface energy group, and a RAFT agent. Such copolymers can be used to make liquid compositions, which can then be used to make tools for nanoimprint or transfer lithography.

Description

[Technical field]

[0001] The methacrylate copolymers are discussed along with methods of making the polymers using reversible addition-fragmentation polymerization (RAFT) agents. In one embodiment, these methacrylate copolymers can be used in imprint lithography and / or transfer lithography. [Background technology]

[0002] Lithography techniques have been widely investigated as an alternative to traditional photolithography for high-resolution patterning of small-scale features. Imprint or transfer lithography techniques generally use templates containing topography to replicate surface reliefs on a substrate. These templates can then be used to create tools such as patterned rolls that can replicate small-scale features into commodity resins in web-type formats, resulting in high throughput and / or reduced costs. Summary of the Invention

[0003] It is desirable to identify new polymers that can enable high-resolution patterning of small (eg, nanometer) features.

[0004] In one aspect, a polymer is described. The polymer comprises: (a) a (meth)acrylate monomer comprising a second terminal olefin group; and (b) an alkyl methacrylate monomer, the alkyl group of which contains 1 to 4 carbon atoms; (c) a mono(meth)acrylate monomer containing a low surface energy group, which includes a perfluorinated alkyl group, a perfluorinated polyether group, or a silicone group; (d) a RAFT agent,

[0005] In another embodiment, the compound of the formula: [ka] A polymer according to the invention is described, wherein R 1 is a C1-C4 alkyl group, L 1 is a linking group containing 1 to 9 carbon atoms, Y is -L 2 -R 2 Or -L 3 -R 3 wherein L 2 is a linking group containing 1 to 9 carbon atoms and, optionally, at least one catenated ether; R 2 contains a silicone group, L 3 is a linking group containing at least one of an ether, an ester, an amide, or a sulfonamide; R 3 contains a perfluorinated alkyl group or a perfluorinated polyether group, Each Q is independently selected from H or CH; X is -C(CH3)2CN, -C(CH3)2C6H5, -CH(CN)C6H5, or -C(CH3)2C(=O)OC2H5, Z is -CH, -SR 5 where R 5 is an alkyl group containing 1 to 12 carbon atoms or a monovalent pyrrole; a is an integer from 50 to 1000; b is an integer from 5 to 200; and c is an integer from 1 to 50.

[0006] In yet another aspect, a liquid composition is described that includes at least one of the above-mentioned methacrylate copolymers along with a crosslinker; a solvent; an optional photoinitiator; and an optional stabilizer.

[0007] In yet another aspect, a method of producing a patterned surface structure on a resin is described. The method comprises contacting the above-mentioned methacrylate copolymer with a patterned template, the patterned template comprising a relief structure. In one embodiment, the methacrylate copolymer is part of a liquid composition that is coated onto the relief structure and subsequently dried. In another embodiment, the methacrylate copolymer is part of a dry layer, and the relief structure is thermally embossed or thermally imprinted into the methacrylate copolymer.

[0008] The above summary of the invention is not intended to describe every embodiment. The details of one or more embodiments of the invention are also set forth in the following detailed description. Other features, objects, and advantages will be apparent from the detailed description and claims. [Brief description of the drawings]

[0009] The present disclosure may be more fully understood from the following detailed description of various embodiments of the disclosure when considered in conjunction with the accompanying drawings, in which: [Figure 1] 1 is a process for forming a patterned resin from a patterned template illustrated with a cross-sectional view of a structure according to one embodiment. [Diagram 2] FIG. 2 is a top view of a tool substrate including a plurality of nanofeature tiles, according to one embodiment. [Diagram 3] 1 is a cross-sectional image of Example 4 taken by a scanning electron microscope (SEM). [Figure 4] 1 is a cross-sectional image of Example 6 taken by SEM. [Figure 5A] FIG. 13 is a top view of the patterned template used in Example 7. [Figure 5B] FIG. 13 is a cross-sectional view taken by SEM of the patterned template used in Example 7. [Figure 6A] FIG. 13 is a top view of the patterned resin of Example 7. [Figure 6B]FIG. 13 is a side view taken by SEM of the patterned resin of Example 7. [Figure 7] 1 is a photograph of four tiles of patterned resin as described in Example 9.

[0010] While the above-identified drawings, some of which are not drawn to scale, describe various embodiments of the present disclosure, other embodiments are also contemplated, as noted in the Detailed Description. It will be understood that numerous other modifications and embodiments may be devised by those skilled in the art that are within the scope and spirit of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Certain terms are used throughout this specification and claims, most of which are well known, but may require some explanation. "A," "an," and "the" are used interchangeably and mean one or more. The term "and / or" is used to indicate that either or both of the stated things may occur. For example, A and / or B includes (A and B) as well as (A or B); "Crosslinking" refers to the linking of two polymer chains using a chemical bond or chemical group; A "monomer" is a molecule that can undergo polymerization and then form part of the basic structure of a polymer. "Perfluorinated" means a hydrocarbon derived group or compound in which all hydrogen atoms have been replaced with fluorine atoms. However, perfluorinated compounds may contain further atoms other than fluorine and carbon atoms, such as oxygen, chlorine, bromine and iodine atoms.

[0012] Further herein, the recitation of ranges by endpoints includes all numbers subsumed within that range (eg, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0013] Further, as used herein, references to "at least one" include all numbers greater than or equal to one (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).

[0014] As used herein, "comprising at least one of" A, B, and C refers to a single element A, a single element B, a single element C, A and B, A and C, B and C, and combinations of all three.

[0015] In the present disclosure, it has been discovered that the polymers disclosed herein (ie, methacrylate copolymers) can be advantageously used to enable the patterning of nanostructures.

[0016] polymer

[0017] The polymers of the present disclosure are methacrylate copolymers derived from the copolymerization of at least three different (meth)acrylate monomers; (a) a (meth)acrylate monomer comprising a second terminal olefin group, (b) an alkyl methacrylate monomer, and (c) a mono(meth)acrylate monomer comprising a low surface energy group.

[0018] The (meth)acrylate monomer (a) comprises an additional (or second) terminal olefin group in addition to the acrylate group (CH2=CHC(O)O-) or the methacrylate group (CH2=C(CH3)C(O)O-). In one embodiment, such a monomer has the formula CH2=CQC(=O)L 1 CH=CH2, where Q is H or CH3, and L 1 is a linking group containing 1, 2, 3, 4, 5, 6, 7, 8, or 9 carbon atoms. 1is -CH-, -CHCH-, -C(CH)HCH-, or -CH-. Exemplary (meth)acrylate monomers containing a second terminal olefin group include CH=CCHC(=O)OCHCH=CH, CH=CCHC(=O)OCH=CH, and CH=CHC(=O)OCH=CH.

[0019] The alkyl methacrylate monomer (b) comprises an alkyl group containing 1 to 4 carbon atoms. In one embodiment, such a monomer has the formula CH2=C(CH3)C(=O)OR 1 wherein R 1 is an alkyl group. 1 The alkyl group in may be linear or branched. In one embodiment, the alkyl group is -CH3, -CH2CH3, -CH(CH3)CH3, -CH2CH2CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)CH3, -CH2CH(CH3)CH3, -CH2CH(CH3)2, -C(CH3)3, and -CH2CH2CH2CH3. Typically, the alkyl methacrylate monomer (b) should be such that a homopolymer of the alkyl methacrylate monomer has a glass transition temperature near or above room temperature (e.g., greater than 23°C, 25°C, 28°C, 30°C, or even 35°C).

[0020] The mono(meth)acrylate monomer (c) contains low surface energy groups, such as perfluorinated alkyl groups, perfluorinated polyether groups, and / or silicone groups.

[0021] In one embodiment, the mono(meth)acrylate monomer (c) has the formula CH2=CQC(=O)OL 2 R 2 (Wherein, Q is H or CH3, and L 2 is a linking group containing 1 to 9 carbon atoms and, optionally, at least one catenated ether group; R 2 contains a silicone group). In one embodiment, the silicone group is -[Si(CH3)2-O] r -Si(CH3)2R4 In the formula, r is an integer from 1 to 200, and R 4 R is an alkyl group containing 1 to 8 carbon atoms. 4 The alkyl group of R may be linear, branched, or cyclic in nature. 4 The alkyl groups are -CH3, -CH2CH3, -CH(CH3)CH3, -CH2CH2CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)CH3, -CH2CH(CH3)CH3, -CH2CH(CH3)2, -C(CH3)3, -CH2CH2CH2CH3, and -(CH2)7CH3. Such mono(meth)acrylate monomers include CH2=CHC(=O)O(CH2)3Si(CH3)2-[O-Si(CH3)2] n CH2CH2CH2CH3, where n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 12.

[0022] In another embodiment, the mono(meth)acrylate monomer (c) has the formula CH2=CQC(=O)OL 3 R 3 (Wherein, Q is H or CH3, and L 3 is a linking group containing at least one of an ether, an ester, an amide, or a sulfonamide; R 3 includes a perfluorinated alkyl group, or a perfluorinated polyether group. Exemplary linking groups include -(CH2) r NHC(=O)-, where r is an integer of 1 to 4. 3 The perfluorinated alkyl group or the perfluorinated polyether group may contain 1 to 20 carbon atoms. 3 Exemplary perfluorinated alkyl groups or perfluorinated polyether groups include -(C p F 2p )-, -(C p F 2p O)-, -(CF(Q 1 ))-, -(CF(Q 1 )O)-, -(CF(Q 1 ) C p F 2p O)-, -(C p F 2p CF(Q1 )O)-, -(CF2CF(Q 1 )O)-, or combinations thereof. In these repeat units, p is typically an integer from 1 to 10. In some embodiments, p is an integer from 1 to 8, 1 to 6, 1 to 4, 1 to 3, or 1 to 2. Q 1 The group is a fluorine atom, a perfluoroalkyl group, a perfluoroether group, a nitrogen-containing perfluoroalkyl group, a perfluoropolyether group or a perfluoroalkoxy group, all of which may be linear, branched or cyclic. 1 The group typically has no more than 12, 10, 9, 4, 3, 2, or even 1 carbon atom. 1 The group may have up to 4, 3, 2, or even 1 oxygen atom, or even no oxygen atoms. In these perfluoropolyether structural formulas, the different repeat units may be randomly distributed along the chain. Such mono(meth)acrylate monomers include CH2=CHC(=O)O(CH2)2NHC(=O)CF(CF3)(OCF2CFCF3) n OC3F7 is one example.

[0023] The methacrylate copolymers of the present disclosure are made using a reversible addition-fragmentation chain transfer (i.e., RAFT) process. Such polymerization techniques are known in the art, and the polymerization is mediated by a RAFT agent. In one embodiment, the RAFT agent is of the formula ZC(=S)SR, where R comprises at least one of a nitrile or ester functional group, and Z is -CH, N-(4-pyridinyl)-N-methylamine, or -SR. 5 where R 5 is an alkyl group containing 1 to 12 carbon atoms. Exemplary RAFT agents include: [ka] [ka] [ka] [ka] and H 25 C 12 -SC(=S)SC(CH3)2C(=O)OH is an example.

[0024] In one embodiment, a methacrylate copolymer constructed from RAFT polymerization of monomers (a), (b), and (c) results in a random polymer.

[0025] In one embodiment, the methacrylate copolymer has the following formula: [ka] wherein: R 1 is a C1-C4 alkyl group, L 1 is a linking group containing 1 to 9 carbon atoms, Y is -L 2 -R 2 Or -L 3 -R 3 wherein L 2 is a linking group containing 1, 2, 3, 4, 5, 6, 7, 8, or 9 carbon atoms and, optionally, at least one catenated ether; R 2 contains a silicone group, L 3 is a linking group containing at least one of an ether, an ester, an amide, or a sulfonamide; R 3 contains a perfluorinated alkyl group or a perfluorinated polyether group, Each Q is independently selected from H or CH; X includes -C(CH3)2CN, -C(CH3)2C6H5, -CH(CN)C6H5, or -C(CH3)2C(=O)OC2H5; Z is -CH, -SR 5 where R 5 is an alkyl group containing 1 to 12 carbon atoms or a monovalent pyrrole; a is an integer from 50 to 1000; b is an integer from 5 to 200; and c is an integer from 1 to 50.

[0026] In one embodiment, a is at least 50, 75, 100, 150, or even 200, and up to 1000, 900, 800, 700, 600, 500, 400, 300, or even 250. In one embodiment, b is at least 5, 8, 10, 20, 25, or even 40, and up to 200, 150, 100, 90, 80, 70, 60, 50, or even 45. In one embodiment, c is at least 1, 2, 3, 5, 8, 10, 15, or even 20, and up to 50, 40, 30, 25, or even 20.

[0027] In one embodiment, the methacrylate copolymers of the present disclosure have a number average molecular weight of at least 10,000, 20,000, 30,000 or even 40,000 Daltons, and up to 100,000, 90,000, 80,000, 70,000 or even 60,000 Daltons. The molecular weight of a polymer can be determined using techniques known in the art, such as gel permeation chromatography.

[0028] In one embodiment, the methacrylate copolymer is derived from 0.5 to 30%, 5 to 20%, or even 8 to 15% by weight of a (meth)acrylate monomer comprising a second terminal olefinic group.

[0029] In one embodiment, the methacrylate copolymer is derived from 50 to 90 weight percent, or even 70 to 80 weight percent, of alkyl methacrylate monomers.

[0030] In one embodiment, the methacrylate copolymer is derived from 0.5 to 30%, 5 to 20%, or even 8 to 15% by weight of (meth)acrylate monomers comprising low surface energy groups.

[0031] In some embodiments, the methacrylate copolymer is derived from monomers other than monomers (a), (b), and (c).

[0032] In one embodiment, the methacrylate copolymers of the present disclosure have a glass transition temperature of at least 30, 40, 50, 60, 70, 80° C., or even 90° C., and up to 150, 140, 130, 120, 110° C., or even 100° C. Glass transition temperature can be determined using differential scanning calorimetry, as known in the art.

[0033] liquid composition

[0034] The methacrylate copolymers of the present disclosure can be mixed with a solvent and a crosslinker to form a liquid composition, which in some embodiments can be used as a replication medium, as described below.

[0035] The methacrylate copolymers disclosed herein can be crosslinked with a suitable crosslinker through the pendant terminal olefin. The crosslinker serves to control the glass transition temperature, allowing for low temperature lamination. The crosslinker also reacts to further harden the resin, creating a more durable patterned surface. In one embodiment, the crosslinker comprises a mono- or multi-functional (meth)acrylate, a multi-functional thiol, or a (meth)acrylamide. Such crosslinkers are known in the art. For example, monofunctional acrylates include 2-phenoxyethyl acrylate or tetrahydrofurfuryl acrylate, and difunctional acrylates include 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, or tricyclodecane dimethanol diacrylate, butanoic acid, 4-oxo-4-[[3-oxo-3-[2-[(1-oxo-2-propen-1-yl)oxy]ethoxy]propyl]thio]-, 2-[(1-oxo-2-propen-1-yl)oxy]ethyl ether (or TEDA), triacrylates such as trimethylolpropane triacrylate or ethoxylated trimethylolpropane triacrylate, tetraacrylates such as ethoxylated pentaerythritol tetraacrylate, or higher functional acrylates such as dipentaerythritol pentaacrylate. Multifunctional thiols include glycol di(3-mercaptopropionate), tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), and dipentaerythritol hexa(3-mercaptopropionate).

[0036] The crosslinker may be added in an amount of at least 5, 8, or even 10%, and up to 20, 18, 15, or even 12%, based on the weight of the liquid composition excluding the solvent (e.g., methacrylate copolymer, crosslinker, and optionally added photoinitiator, stabilizer, and filler, if used).

[0037] Generally, the solvent is selected so that the methacrylate copolymer is soluble in the solvent. Exemplary solvents include propylene glycol methyl ether, propylene glycol n-propyl ether, propylene glycol methyl ether acetate, ethylene glycol propyl ether, and ethylene glycol butyl ether.

[0038] Other additives, such as photoinitiators, stabilizers, surfactants, plasticizers, etc., may be included in the liquid composition to aid in the processing of the liquid composition and / or to modify its properties. The additives are added in an amount sufficient to obtain the desired final properties.

[0039] In some embodiments, a photoinitiator is added to the liquid composition. Exemplary photoinitiators include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (available under the trade name OMNIRAD TPO from IGM Resins USA Inc., St. Charles, IL), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (available under the trade name OMNIRAD 819 from IGM Resins USA Inc., St. Charles, IL), bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide (available under the trade name OMNIRAD 403 from IGM Resins USA Inc., St. Charles, IL), a 25:75 by weight mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (available under the trade name OMNIRAD 152 from IGM Resins USA Inc., St. Charles, IL), and mixtures of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (available under the trade name OMNIRAD 152 from IGM Resins USA Inc., St. Charles, IL). available under the trade designation OMNIRAD 1700), a 1:1 by weight mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (available under the trade designation OMNIRAD 4265 from IGM Resins USA Inc., St. Charles, Ill.), and ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (available under the trade designation OMNIRAD TPO-L from IGM Resins USA Inc., St. Charles, Ill.), and combinations thereof.

[0040] In some embodiments, stabilizers are added to prevent premature curing of the composition and / or inhibit free radical formation.Such stabilizers include antioxidants such as those known in the art (e.g., hindered phenols, phosphites, thioesters, and amines), and cure inhibitors or retarders such as butylated hydroxytoluene, quinones (e.g., hydroquinone, benzoquinone, etc.), nitrobenzene, 1,3,5-trinitrobenzene, sulfur, aniline, phenol, chloroaniline, etc.Exemplary stabilizers include 2,6-di-tert-butyl-4-methylphenol (BHT), 4-methoxyphenol, hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-hydroxy-TEMPO), and phenothiazene.

[0041] The liquid composition can be prepared by mixing the desired amounts of methacrylate copolymer, crosslinker, solvent, and optionally additional additives in conventional processing equipment. It is generally desirable to distribute the solid components uniformly during mixing. Mixing of the liquid composition is typically performed at ambient conditions.

[0042] The amount of solvent in the liquid composition can be adjusted depending on the application to obtain the desired viscosity of the liquid composition. In one embodiment, the liquid composition comprises at least 70, 75, 80, or even 85% by weight of solvent. In one embodiment, the liquid composition comprises up to 95, 90, or even 85% by weight of solvent.

[0043] use

[0044] In one embodiment, the methacrylate copolymers disclosed herein can be used in replicating the surface relief of a patterned template. Two different methods for patterning methacrylate copolymers are discussed below: imprint lithography and transfer lithography.

[0045] Transfer lithography, as used herein, refers to a method in which a patterned template having a predetermined relief structure is coated with a solution, which fills the surface relief and then solidifies. Imprint lithography refers to a method in which a solid layer comprising a methacrylate copolymer is thermomechanically deformed by a patterned template to replicate the relief structure in the solid layer comprising a methacrylate copolymer.

[0046] These techniques, imprint lithography and transfer lithography, allow for the duplication of nanostructures at high throughput. In general, a high-resolution master mold is used as the initial patterned template. These high-resolution master molds are typically fabricated using lithographic techniques on silicon wafers. These master molds tend to be expensive, fragile, and have small patterned areas limited by device size, limiting the pattern fabrication throughput for their fabrication. Thus, the high-resolution master mold can be used as the original template, and then other cheaper and / or more durable materials can be used to fabricate large-area patterned tiled replicas that can be used later to create tools.

[0047] Shown in Figure 1 is an exemplary process of using the disclosed methacrylate copolymers in a transfer process to create a finished nanostructured product from a patterned template. Figure 1 shows a cross-sectional view of the in-process structure, which is not drawn to scale. The patterned template 100 contains nano-sized features, in this case voids 105, which are reproduced as pillars 155 on the patterned resin 150. The patterned resin 150 is a negative image of the patterned template 100. The patterned template 100 can be a high-resolution master mold, or a temporary template. Since the process produces a negative of the patterned template, an intermediate template can be used to obtain the correct pattern of the final product, as is routine in the art.

[0048] 1, a liquid composition of the present disclosure is coated onto the surface of patterned template 100, filling voids 105. The coating is then solidified (e.g., a solvent drying process, a reactive partial curing process, etc.) to form replication medium 120. The solidification process results in a polymer resin that is substantially solid at room temperature (e.g., having a glass transition temperature of at least 0, 5, 10° C., or even 20° C.). The solid layer of replication medium substantially conforms to the structured surface of patterned template 100.

[0049] The liquid composition is deposited on the patterned template 100 and solidified thereon to form a replication medium 120 that is a negative image of the template. The replication medium conforms to the patterned surface along a first side thereof and forms a planar surface on a second side opposite the first side.

[0050] The second side of the replication medium 120 may be placed on a receiving substrate 160 as shown in FIG. 1. The receiving substrate 160 may aid in handling of the thin replication medium. The receiving substrate 160 may include a flexible polymer substrate (polyethylene terephthalate, polycarbonate, cyclic olefin copolymer, etc.), glass, quartz, silicon wafer, polished metal, rigid polymer substrate, etc. In one embodiment, an adhesive may be used to adhere the replication medium 120 to the receiving substrate 160.

[0051] Typically, the replication medium is placed along its planar surface on a receiving substrate, still in contact with the patterned template. This structure is then treated to crosslink (or further crosslink) the replication medium. The treatment for crosslinking the replication medium depends on its composition. For example, actinic radiation is used with a photoinitiator. Crosslinking of the replication medium forms a patterned resin 150. Crosslinking of the methacrylate copolymer-containing replication medium improves its mechanical properties and allows separation / peeling of the patterned resin 150 from the patterned template 100, preserving the relief structure, especially for nanostructures with high aspect ratios. Once the patterned template is removed, the patterned resin 150, including a relief surface that is the negative of the template, is placed on a receiving substrate 160.

[0052] In one embodiment, a multi-layer structure including patterned template 100 and replication medium 120 is cut to a desired size and a planar surface of replication medium 120 is placed on a larger receiving substrate. The structure is at least partially cross-linked and then patterned template 100 is removed leaving tiles of patterned resin on the receiving substrate. This process can be repeated to result in many patterned resins on the receiving substrate. Shown in Figure 2 is a top view displaying a receiving substrate 260 with four tiles of patterned resin 250 thereon.

[0053] FIG. 1 is a simplified process and shows only one transfer process of the resin containing the methacrylate copolymer of the present disclosure. Those skilled in the art will recognize that other molding techniques can be used to obtain the correct molded form. Other techniques such as coating with a release agent and / or coating with a metal to facilitate separation of the patterned template from the patterned resin may also be used. Such techniques are illustrated in the Examples section.

[0054] In the imprinting method, the liquid composition described above can be coated on a substrate and solidified to form a replication medium, for example by removing a volatile solvent. Methods of solvent removal from the liquid composition can include at least partial evaporation at ambient conditions, or application of heat, reduced pressure, etc. to increase the rate of solvent evaporation. The patterned template is then contacted with the replication medium and thermally embossed or thermally imprinted with respect to each other, such that the negative image from the patterned template is transferred to the surface of the replication medium. Such methods of imprinting are known in the art. The replication medium can then be placed on a receiving substrate in a transfer process and crosslinked as described above. The patterned template is then removed, leaving the patterned resin placed on the receiving substrate, similar to that described for the transfer method above.

[0055] The patterned template has a structured surface including an array of pattern elements extending away from a base surface with voids formed between the pattern elements. The pattern elements or the voids between them accommodate microscale and / or nanoscale features in a regular or random arrangement. In one embodiment, the patterned template includes a structured surface including an array of pattern elements extending away from its base surface. In one embodiment, the pattern elements may have an average lateral dimension of at least 1, 5, 10, 20, 25 nm, or even 50 nm. In one embodiment, the pattern elements may have an average lateral dimension of up to 1000, 500, 250, 200, 100, 50 micrometers, or even 30 micrometers. In one embodiment, the pattern elements may have an aspect ratio of height to lateral dimension of 0, 0.5, 1, 1.5, or even greater than 2 and up to 20, 10, 5. The patterned template may accommodate microscale and / or nanoscale features in a regular or random arrangement. The patterned template may be a precisely fabricated structure, such as a silicon wafer master mold created using lithographic techniques, or a replica made from a master mold, referred to herein as a temporary mold. These temporary molds often use a replication medium that includes a curable polymer resin, such as a reactive thermoplastic polymer plasticized with a reactive crosslinker. Exemplary UV-curable resins include at least one of (meth)acrylate monomers, (meth)acrylate oligomers, epoxies, silicones, or silicone acrylates. Thus, the methacrylate copolymers disclosed herein may be used to fabricate replicas from a mold master, such as a silicon master, or from a temporary mold, as illustrated in the following examples.

[0056] In some embodiments, an adhesion promoter may be included as an additive in the replication medium, or may be provided on the planar surface of the replication medium (120) prior to contact with the receiving substrate (160), or the adhesion promoter may be provided on the receiving substrate (160) prior to contact with the replication medium. Exemplary adhesion promoters include silane coupling agents such as 3-(trimethoxysilyl)propyl methacrylate or (3-trimethoxysilylpropylcarbamoyloxy)ethyl prop-2-enoate, as described in Example 7 of U.S. Pat. No. 9,790,396, which is incorporated herein by reference.

[0057] The liquid composition of the present disclosure comprising a methacrylic copolymer is a particularly useful precursor to the replication medium (120). Due to the glass transition temperature of the methacrylate copolymer, the liquid composition comprising the methacrylate copolymer of the present disclosure can be at least partially solidified, and then the replication medium comprising the methacrylate copolymer can be crosslinked to increase its durability and allow the resulting patterned resin to be removed from the patterned template without damaging the pattern. For example, in one embodiment, the liquid composition of the present disclosure can be first dried to remove the solvent to form a methacrylate copolymer solid, which can then be crosslinked by actinic radiation. Prior to the application of actinic radiation, the replication medium comprising the methacrylate copolymer has a lower glass transition temperature, which allows the solidified methacrylate copolymer composition to be laminated onto a receiving substrate at a lower temperature. In one embodiment, the planar side of the solidified replication medium comprising the methacrylate copolymer of the present disclosure can be laminated onto a receiving substrate at a temperature of 80, 70, 60, 50°C, or even 40°C or less. Lamination of the replication medium comprising the methacrylate copolymer and the receiving substrate can be accomplished by roller lamination, by hand lamination, by precision roll lamination across the width of the substrate, by deformable (membrane or compliant) lamination devices, and the like.

[0058] In one embodiment, the thickness of patterned resin 150 has a remaining thickness T excluding the height of the pattern elements of patterned resin 150. The remaining thickness T may be on the order of the nanostructured depth or height, for example, in the range of 10 nm to 1000 micrometers, or even greater than 1000 micrometers.

[0059] To make large quantities of copies using the patterned resin 150 as described above, in one embodiment, the patterned resin 150 is cut into "tiles." A plurality of nanofeature tiles are placed on a receiving support to form a tool that can be used to make a large area coverage nanostructured tool for pattern replication. Such a structure is shown in FIG. 2, which is a top view displaying a receiving substrate 260 having four nanostructured tiles 250 thereon. Although FIG. 2 shows a 2 tile by 2 tile array, any reasonable number of tiles can be used. Typically, each tile is approximately 1 mm in size, for example. 2 ~2000000mm 2 In many cases, there will be gaps between adjacent tiles, ranging, for example, from about 0 mm to 100 mm. In the illustrated embodiment, each tile in the pattern array has a square shape, although any shape (e.g., rectangular, circular, etc.) can be envisioned.

[0060] The patterned resin can be fixed to the receiving substrate via a variety of mechanisms including, for example, thermal exposure, thermal lamination, UV exposure or curing, In one embodiment, an additional adhesive layer (such as an optically clear adhesive or OCA), coupling agents, surface treatments, decomposition agents, etc. are used to help fix the patterned resin to the receiving substrate.

[0061] In an embodiment, the liquid composition comprising the methacrylate copolymer disclosed herein can be hardened by curing. One or more energy sources can be positioned such that the emitted energy can cure the methacrylate copolymer. The energy source can be capable of emitting energy, for example, actinic radiation, electron beam radiation, or heat. If the energy source emits radiation, the liquid composition and / or the patterned template can be substantially transparent to the radiation to allow the hardening of the replication medium. The term "substantially" with respect to a property or characteristic means that the property or characteristic is exhibited to a greater extent than the opposite of the property or characteristic is exhibited. For example, a "substantially" transparent substrate refers to a substrate that transmits more radiation (e.g., visible light) than it does not transmit (e.g., absorbs and reflects). Thus, a substrate that transmits more than 50% of the visible light incident on the surface is substantially transparent, while a substrate that transmits 50% or less of the visible light incident on the surface is not substantially transparent.

[0062] The source of actinic radiation is selected so that the actinic radiation is of suitable wavelength that is absorbed by photoinitiator and organic photoactivatable reducing agent precursor.Exemplary actinic radiation sources can include laser (ultraviolet or visible light), broad-area flash lamp (e.g., xenon flash lamp), and low-, medium-, and high-pressure mercury arc lamps, microwave-driven mercury lamps (e.g., using H-type, V-type, or D-type bulbs), and light-emitting diodes (LEDs).Further details regarding radiation curing are within the capabilities of those skilled in the art.

[0063] Advantageously, the methacrylate copolymers disclosed herein have a glass transition temperature of greater than 0, 5, 10, 15, or even 20° C., allowing the replication resin to be solid at room temperature while also allowing low temperature lamination (e.g., less than 70° C.) of the solidified replication medium laminated onto a solid support. In one embodiment, the glass transition temperature of the replication medium (i.e., the methacrylate copolymer and any additives) is at least 30, 35, 40, or even 45° C., and up to 70, 65, 60, 55, or even 50° C. Exemplary embodiments of the present disclosure provide a replication medium formed on a patterned template that is substantially solid at room temperature. The processes described herein can facilitate handling and storage during intermediate processing steps, such as, for example, during coating or transferring the replication medium onto other patterned templates for other subregions on the same substrate. Embodiments of the present disclosure further provide a curable polymeric resin replication medium having a planar surface that contacts the subregions of the substrate. The replication medium should have a reduced glass transition temperature to allow the material to become substantially flowable in order to bring the planar surface into intimate contact with the substrate. The embodiments described herein are advantageous because they reduce the process temperature and thus the possibility of distortion of the relief structure of the patterned template due to mismatches in the thermal expansion coefficients of the patterned template, the replication medium, and the receiving substrate. EXAMPLES

[0064] Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight and all reagents used in the examples were obtained from EMD Millipore (Burlington, MA) and used as received, or are available from general chemical suppliers such as VWR, Radnor, PA, or can be synthesized by conventional methods. Table 1 (below) lists the materials used in the examples and their suppliers. [Table 1]

[0065] Test Method

[0066] Methods for collecting scanning electron microscope (SEM) images

[0067] Samples were mounted on aluminum test stubs and coated with AuPd by sputtering to ensure conductivity. Sputtering was performed for 30 seconds at a current of 20 milliamps using direct current mode using a Desk V Sample Preparation System (Denton Vacuum). Examination was performed with a Hitachi S4700 field emission scanning electron microscope (Hitachi, Tokyo, Japan).

[0068] Preparation Example 1

[0069] Resin A was prepared by combining PHOTOMER 6210, SR238, SR351, and TPO in a weight ratio of 60 / 20 / 20 / 0.5. After all ingredients were added, the resin mixture was blended by heating to approximately 50° C. and mixing on a roller mixer for 12 hours. The mixture was blended until it appeared homogenous.

[0070] Preparation Example 2

[0071] Glass was prepared by rinsing 2 x 3 inch (5.1 cm (centimeter) x 7.6 cm) borosilicate microscope slides (Fisher Scientific, Hampton, NH) with acetone and isopropyl alcohol and wiping with a Vectra TX1010 cleanroom wipe (Texwipe, Kernersville, NC). The cleaned glass was dip coated in a solution containing 0.5 wt% K90 in methyl ethyl ketone. The coated slides were baked at 140°C for 15 minutes and then cooled to room temperature.

[0072] Preparation Example 3

[0073] Synthesis of TEDA [ka]

[0074] To a 500 mL (milliliter) round bottom flask equipped with a stir bar was added TE1 (20 g, 97 mmol, 1.0 equiv), BHT (2.14 g, 9.70 mmol, 0.100 equiv), and dichloromethane (DCM, 324 mL). To the heterogeneous mixture was added DPTS (1.43 g, 8.85 mmol, 0.05 equiv) and 2-hydroxyethyl acrylate (20.05 mL, 174.6 mmol, 1.8 equiv). The mixture was stirred at rt (room temperature) for 5 min, then DIC (33.04 mL, 213.4 mmol, 2.2 equiv) was added via syringe. The reaction was stirred at room temperature for 18 h, after which the solids were filtered, washed with ethyl acetate (3×10 mL), and the organic layer was collected and partially concentrated under reduced pressure. When approximately 1 / 3 of the liquid remained, the heterogeneous mixture (white solids in a pale yellow viscous liquid) was filtered and washed with ethyl acetate (3 x 3 mL). This process was repeated once more and then concentrated overnight in a fume hood by blowing room air over the liquid. The resulting material was a viscous yellow oil, which was purified by automated column chromatography using a Biotage Isolara One (Biotage, Uppsala, Sweden) and a suitable Biotage Sfaer Flash purification column. The eluent was a hexane / ethyl acetate gradient from 80 / 20 to 20 / 80 v / v. The desired product was collected and concentrated by blowing room air overnight to give a clear viscous oil (37.2 g, 95.3% yield).

[0075] Example 1: Preparation of copolymers of MMA, AMA, and MCR-M07 [ka]

[0076] The reagents shown in Table 2 were added to a 1000 milliliter (mL) three-neck round-bottom flask. A stir bar was added and the flask was connected to a nitrogen manifold and fitted with a thermocouple, condenser, and rubber septum. The solution was deoxygenated by bubbling nitrogen gas through a needle placed through the septum for 10 minutes. The flask was immersed in an oil bath and heated with stirring to maintain a reaction temperature of 65-67 °C for 16 hours. An increase in viscosity was observed during this time. 1 Analysis of an aliquot by H NMR indicated that 59% of the MMA monomer was converted to polymer. The reaction was then cooled and exposed to air. The solution was diluted with acetonitrile (200 mL) and isopropanol (60 grams (g)) and the resulting solution was transferred to a separatory funnel. The polymer solution was washed twice with heptane (360 g). The solution was then transferred to a 2 liter (L) round bottom flask and DOWANOL PM (260 g) was added. The solvent was distilled under reduced pressure using a rotary evaporator until the total solution mass was equal to 300 g. A second portion of DOWANOL PM (260 g) was added and the solvent was distilled under reduced pressure using a rotary evaporator until the total solution mass was equal to 260.3 g. A small aliquot was evaporated to dryness (e.g., a small aliquot was heated at 150° C. for at least 1 hour) and the change in mass was used to determine a polymer concentration of 22.8%. This means a yield of 59.4 g of polymer. [Table 2]

[0077] Example 2: Preparation of copolymers of MMA, AMA, and HFPO-MA [ka]

[0078] The reagents shown in Table 3 were added to a 1000 mL three-neck round bottom flask. A stir bar was added to the solution and the flask was connected to a nitrogen manifold and fitted with a thermocouple, condenser, and rubber septum. The solution was deoxygenated by bubbling nitrogen gas through a needle placed through the septum for 10 minutes. The solution was heated using a heating mantle with stirring to maintain a reaction temperature of 72° C. for 5 hours. An increase in viscosity was observed during this time. 1 Analysis of an aliquot by H NMR (nuclear magnetic resonance) showed that 60% of the MMA monomer was converted to polymer. The solution was exposed to air and then allowed to cool. The polymerization solution was then poured into a beaker containing NOVEC 7100 (750 g) with stirring, resulting in precipitation of the polymer. The polymer was isolated by filtration and washed with NOVEC 7100 (200 g). The solid polymer + DOWANOL PM (400 g) was then transferred to a 1000 mL round bottom flask. The polymer was dissolved by spinning the flask on a rotary evaporator. The solvent was then distilled using a rotary evaporator until the total solution mass was 250 g. A small aliquot was evaporated to dryness and the change in mass was used to determine a polymer concentration of 23.0%. This implies a yield of 57.5 g of polymer. [Table 3]

[0079] Example 3: Preparation of liquid compositions

[0080] A liquid composition was prepared by mixing the copolymer of Example 1 (10 g), TEDA (250 milligrams (mg)), TPO (253 mg of a 10% solution in DOWANOL PM), and DOWANOL PM (14.8 g).

[0081] Example 4: Preparation of patterned resin containing the copolymer of Example 1

[0082] Resin A patterned template

[0083] A nanofeature template was prepared by die coating Resin A onto Multilayer Film A. Multilayer Film A was prepared using the method described in WO 2019 / 032635(A1) (Johnson et al.). The resulting multilayer film had a 43 micron polyethylene terephthalate (PET) layer, a 6-7 micron linear BES triblock copolymer layer ("KRATON G1645"), a 6-7 micron layer comprising a blend of 60 parts by weight of polypropylene random copolymer ("PP9074MED") and 40 parts by weight of BES triblock copolymer ("KRATON G1645"), and a 15 micron PETG copolymer layer ("EASTAR GN071"). The Resin A side of the coated film was pressed onto a nanostructured nickel surface attached to a steel roller controlled at 60°C using a rubber-covered roller at a speed of 15.2 meters / min. The nanostructured nickel tool consisted of one 5 cm x 7.5 cm patterned area with hole features. The features were cylinders 150 nm in diameter and 450 nanometers (nm) tall in a random array with repeat unit squares of approximately 25 μm by 25 μm. The coating thickness of Resin A on Multilayer Film A was sufficient to completely wet the nickel surface forming a rolling bead of resin as the coated film was pressed against the nanostructured nickel surface. The Resin A coating was exposed to radiation from two Fusion UV lamp systems (obtained under the trade designation "F600" from Fusion UV Systems, Gaithersburg, MD) fitted with D bulbs, both operating at 142 watts per centimeter (142 W / cm), while in contact with the nanostructured nickel surface. The nanostructured features were obtained in Resin A by peeling the coated film from the nanostructured nickel surface. The nanostructured side of the coated film was again exposed to radiation from the Fusion UV lamp system to form a patterned template comprising Resin A with nanostructured features on top of Multilayer Film A.

[0084] Peeling treatment of resin A patterned template

[0085] A silicon-containing release film layer, assembled according to the methods described in U.S. Pat. Nos. 6,696,157 (David et al.) and 8,664,323 (Iyer et al.) and U.S. Patent Application Publication No. 2013 / 0229378 (Iyer et al.), was applied to the Resin A patterned template from above in a parallel plate capacitively coupled plasma reactor to form a silicon-containing release surface on top of the nanostructured Resin A. The chamber had a volume of 1.7 m. 2 (18.3ft 2 The reactor had a central cylindrical powered electrode with a surface area of ​​1.3 Pascals (Pa) (2 millitorr (mTorr)). After the resin A patterned template was placed on the powered electrode, the reactor chamber was pumped down to a base pressure of less than 1.3 Pascals (Pa) (2 millitorr (mTorr)). O2 gas was flowed into the chamber at a flow rate of 1000 standard cubic centimeters per minute (SCCM). The treatment was carried out using a plasma-enhanced CVD method by coupling radio frequency (RF) power into the reactor at a frequency of 13.56 megahertz (MHz) and an applied power of 2000 watts (W). The treatment time was controlled by moving the polymer nanostructured template through the reaction zone at a speed of 9.1 meters / minute (30 feet / minute), resulting in an approximate exposure time of 10 seconds. After the deposition was completed, the RF (radio frequency) power was turned off and the gases were evacuated from the reactor. Following the first treatment, a second plasma treatment was carried out in the same reactor without returning the chamber to atmospheric pressure. HMDSO gas was flowed into the chamber at approximately 1750 SCCM to achieve a pressure of 9 mTorr. Subsequently, 13.56 MHz RF power was coupled into the reactor with an applied power of 1000 W. The patterned template was then transported through the reaction zone at a speed of 9.1 meters / minute (feet / minute), resulting in an approximate exposure time of 10 seconds and a coating thickness of approximately 5-10 nm. At the end of this treatment time, the RF power and gas supply were turned off and the chamber was returned to atmospheric pressure. This resulted in a release-treated Resin A patterned template.

[0086] Patterning resins containing methacrylate copolymers

[0087] The liquid composition of Example 3 was used to spin coat a layer of the liquid composition onto the release treated resin A patterned template. The spin coating conditions were 500 revolutions per minute (rpm) for 5 seconds and 1000 rpm for 30 seconds, after which 1 mL of solution was statically applied to cover the nanofeature area, coating the patterned template with the methacrylate copolymer resin. The planar surface of the replication media was laminated to the treated glass using a hot roll laminator at a temperature of 175°F (79.4°C) and the lowest speed setting. A nip of 60 pounds per square inch (psi) (0.41 megapascals (MPa)) was used to conform the replication media to the treated glass. The resulting structure was crosslinked using a Fusion D-bulb (Fusion Light Hammer 10, Heraeus, Hanau, Germany) at 100% strength and a belt speed of 50 feet per minute (fpm) (15.2 meters per minute). The structure was then peeled away to separate the release treated Resin A patterned template from the patterned resin made from the liquid composition of Example 3. A scanning electron microscope (SEM) was used to obtain an image of the patterned resin obtained according to this test method (see FIG. 3), which shows good fidelity to the original nanostructured nickel tool.

[0088] Example 5: Preparation of a liquid composition

[0089] A liquid composition was prepared by mixing the polymer of Example 1 (100 g), PETMP (2.53 g), TPO (2.53 g of a 10% solution in DOWANOL PM), and DOWANOL PM (148 g).

[0090] Example 6: Preparation of a nanofeature patterning tool comprising the liquid composition of Example 5

[0091] Resin A patterned template

[0092] A nanofeature template was prepared as described in Example 4, except that a 3 mil thick (0.08 millimeters (mm)) by 12.0 inch wide (30 cm) PET film was used, resulting in Resin A having nanostructured features on the PET film.

[0093] Peeling treatment of resin A patterned template

[0094] Resin A patterned templates were treated with silicon using the procedure described in Example 4. SEM was used to obtain images of Resin A patterned templates that had been peel treated according to this test method.

[0095] Patterning resins containing methacrylate copolymers

[0096] The liquid composition of Example 5 was die coated from above onto the release treated resin A patterned template in a roll-to-roll process using a slot die at a speed of 10 feet / minute (0.051 meters / second (m / s)). The solution was coated at a width of 5.0 inches (13 cm) with a slot height of 3.0 mils (0.0076 cm) and pumped at a rate of 3.5 SCCM using a PHD 2000 Syringe Infuse / Withdraw Syringe Pump (Harvard Apparatus, Holliston, MA). The coating was allowed to dry at room temperature for 2 minutes to produce a replication medium on the patterned template. A LD-K1010-75 (Showa Denko Materials Co. LTD, Tokyo, Japan) liner was temporarily laminated onto the planar surface of the replication medium. Prior to attachment to the receiving substrate, the LD-K1010-75 was removed, the planar surface of the replication medium was transferred to treated glass, and the sample was cured as described in Example 4, except that the sample was cured for 3 minutes at 100% intensity with a JL3-series LED (Clearstone Technologies, Hopkins, MN) at a wavelength of 455 nm. The light was controlled with a Clearstone Technologies CF 2000 standard benchtop UV LED power supply. The patterned template was removed from the patterned resin. An SEM was used to obtain an image of the patterned resin (see FIG. 4) according to the test method, which showed good fidelity to the original nanostructured nickel tool.

[0097] Example 7: Preparation of patterned resin containing the methacrylate copolymer of Example 1

[0098] Resin A patterned template

[0099] Nanostructured templates of Resin A were prepared as described in Example 4, except that a 5.0 mil thick (0.13 mm) by 9.0 inch wide (23 cm) polycarbonate film was used in place of multilayer film A, and a nickel tool consisting of a single approximately 5 cm by 5 cm patch of regularly spaced 200 nm diameter holes was used and maintained at 66°C.

[0100] Peeling treatment of resin A patterned template

[0101] Resin A patterned templates were coated with silicone using the procedure described in Example 4. SEM was used to obtain images of the release treated Resin A patterned templates according to this test method, see Figures 5A and 5B.

[0102] Patterned templates comprising methacrylate copolymers - Patent Application 20070123633

[0103] The liquid composition of Example 3 was used to spin coat a layer of liquid onto the release-treated Resin A patterned template. The spin-coating conditions were 500 revolutions per minute (rpm) for 5 seconds and 1000 rpm for 30 seconds after static application of 1 mL of the liquid composition to cover the nanofeature area of ​​the release-treated Resin A patterned template. The replication medium was then transferred onto glass and cured as described in Example 4. Images of the resulting patterned resin made from Example 3 according to the test method were obtained using SEM. See Figures 6A and 6B. Comparison of the release-treated Resin A patterned template shown in Figures 5A (top view) and 5B (side view) with the resulting patterned resin containing methacrylate copolymer shown in Figures 6A (top view) and 6B (side view) shows good fidelity.

[0104] Example 8: Preparation of a liquid composition

[0105] A liquid composition was prepared by mixing the polymer of Example 1 (10 g), TEDA (253 mg), TPO (253 mg of a 10% solution in DOWANOL PM), and DOWANOL PM (6.4 g).

[0106] Example 9: Preparation of 2x2 tiled arrays

[0107] The polymer patterned templates were fabricated from a lithographically mastered 100 mm diameter silicon master containing a relief structure of line grading with a pitch of 400 nm, a depth of 200 nm, and a duty cycle of 50 percent, as well as a 10 mm wide area without line grading 30 mm from the edge of the silicon that runs the length of the template in a direction parallel to the line grading. The polymer template was fabricated after a release process of the silicon master. The relief surface of the silicon master was treated with a thin layer (e.g., monolayer) of a low surface energy fluorinated silane after O2 plasma activation of the surface to aid in release. The O2 plasma activation was performed at 50 W RF power for 5 minutes and a steady state pressure of 1.0 Pa (Pascal, 75 mTorr).

[0108] Polymer patterned templates were made by depositing 0.5 mL of MR-UVCur26SF onto the relief surface of the peel-treated silicon master, and the ST504 film was laminated with a rubber roller to spread the MR-UVCur26SF material over the entire relief structure. The MR-UVCur26SF was cured through the ST504 PET film using a custom low-power UV-LED unit with a wavelength of 385 nanometers (nm) at 40 volts (V), 8 amps (A) for 2 minutes. The ST504 PET film and MR-UVCur26SF material were peeled off the silicon master to expose the reverse relief structure in the MR-UVCur26SF material. This was repeated four times using the same silicon master to make each polymer template.

[0109] The ST504 PET used to fabricate the polymer patterned templates was modified to improve adhesion by using plasma etching with an in-house built parallel plate capacitively coupled plasma reactor as described in U.S. Pat. No. 6,696,157 (David et al.). The chamber had a volume of 1.7 square meters (m 2 , 18.3ft 2 The reactor has a central cylindrical powered electrode with a surface area of ​​1.3 Pa (2 mTorr). After the film was placed on the powered electrode, the reactor chamber was pumped down to a base pressure of less than 1.3 Pa (2 mTorr). O2 and HMDSO gases were flowed into the chamber at rates of 20 SCCM and 750 SCCM, respectively. Processing was carried out using a reactive ion etching method by coupling RF power to the reactor at a frequency of 13.56 MHz and an applied power of 7500 Watts. Processing time was controlled by moving the film through the reaction zone at a speed of 3 meters / min (10 feet / min), resulting in an approximate exposure time of 30 seconds. At the end of this processing time, the RF power and gas supply were turned off and the chamber was returned to atmospheric pressure.

[0110] A silicon-containing release layer, constructed according to the "Method for Release Processing" described in WO 2020 / 095258 (Van Lengerich et al.), was applied to the polymer patterned template.

[0111] The liquid composition of Example 8 was spin-coated onto the release-treated patterned template. The spin-coating conditions were 500 rpm for 5 seconds and 1000 rpm for 60 seconds, after which 6 mL of solution was statically applied to cover the nanofeature area of ​​the template. The coating was allowed to dry for 60 seconds to form the replication medium, after which an oversized LD-K1010-75 liner was applied to the planar surface. The liner, replication medium, and patterned template were cut into circles with a diameter of 85 mm. This process was repeated to create four circles (or tiles).

[0112] The circle was placed in the film lamination unit, with the LD-K1010-75 surface of the circle in contact with the bottom of the unit. The film lamination unit contained an upper and lower compartment separated by a silicone membrane. Vacuum could be applied to each chamber separately, and pressure could be applied to the top. Both units were evacuated at a rate that avoided contact of the membranes until 200 mtorr was reached. The top was then vented to atmosphere, followed by the bottom. The LD-K1010-75 was removed from the circle, and the prepared glass was placed at the bottom of the unit. The glass was prepared as in Example 4, except that Corning EAGLE XG 200.0 x 200.0 x 0.70 mm glass (Precision Glass & Optics, Santa Ana, CA) was used. The upper and lower chambers were evacuated at a rate that avoided contact of the replication medium to the receiving substrate (or glass) until a vacuum was reached. The top chamber was then pressurized to 0.41 MPa (60 psi) to allow contact between the replication medium and the receiving substrate. The unit was heated on a hot plate until the internal temperature of the bottom platen reached 45° C. The top chamber was vented to atmosphere. While still in the lamination unit and bottom chamber under vacuum, a custom low power UV-LED unit with a wavelength of 385 nm at 40 volts (V), 8 amps (A) was directed at the patterned template and applied for 5 minutes to cure the replication medium. The bottom chamber was then vented to atmosphere and the glass / patterned resin / patterned template structure was removed. The patterned template was removed from each of the circles (or tiles) to expose the patterned resin. Four tiles of patterned resin made from methacrylate copolymer resin according to the present disclosure are shown in FIG. 7.

[0113] Foreseeable modifications and variations of the present invention will become apparent to those skilled in the art without departing from the scope and spirit of the present invention. The present invention is not limited to the embodiments described in this application for illustrative purposes. All references, patents, and patent applications cited in the above patent application for Letters Patent are incorporated herein by reference in their entirety in a consistent manner. In the event of any inconsistency or discrepancy between the description in this specification and the disclosure in any document set forth in this specification or incorporated by reference, the description in this specification shall control.

Claims

1. (a) a (meth)acrylate monomer comprising a second terminal olefin group; and (b) an alkyl methacrylate monomer, the alkyl group of which contains 1 to 4 carbon atoms; (c) a mono(meth)acrylate monomer containing a low surface energy group including a perfluorinated alkyl group, a perfluorinated polyether group, or a silicone group; (d) a reversible addition-cleavage (RAFT) agent; and A polymer derived from

2. The (meth)acrylate monomer comprising the second terminal olefin group has the formula CH ２ =CQC(=O)L １ CH=CH ２ wherein Q is H or CH ３ and L １ The polymer of claim 1, wherein L 1 is a linking group containing 1 to 9 carbon atoms, and optionally L 1 is CH 2 .

3. The alkyl methacrylate monomer has the formula CH ２ =C(CH ３ ) C(=O) OR １ wherein R １ The polymer of claim 1, wherein is a C1 to C4 alkyl group.

4. R １ But -CH ３ , -CH ２ CH ３ , -CH(CH ３ ) CH ３ , -CH ２ CH ２ CH ３ , -CH(CH ３ ) CH ２ CH ３ , -CH ２ CH (CH ３ ) CH ３ , or -C(CH ３ ) ３ 4. The polymer of claim 3, wherein:

5. The mono(meth)acrylate monomer has the following formula: CH ２ =CQC(=O)OL ２ R ２ (wherein Q is H or CH ３ and L ２ is a linking group containing 1 to 9 carbon atoms and optionally an ether group linked in a chain; R ２ contains said silicone group), or CH ２ =CQC(=O)OL ３ R ３ (wherein Q is H or CH ３ and L ３ is a linking group containing at least one of an ether, an ester, an amide, or a sulfonamide; R ３ includes the perfluorinated alkyl group or the perfluorinated polyether group) 10. The polymer of claim 1, wherein the polymer is at least one of:

6. The perfluorinated polyether group is -(C ｐ F ２ｐ ) -, -(C ｐ F ２ｐ O)-,-(CF(Q １ )) -, -(CF(Q １ )O)-,-(CF(Q １ ) C ｐ F ２ｐ O)-, -(C ｐ F ２ｐ CF (Q １ ) O) - or -(CF ２ CF (Q １ )O)—, wherein p is an integer from 1 to 10, Q １ The polymer of claim 1 , wherein is a fluorine atom, a perfluoroalkyl group, a perfluoroether group, a nitrogen-containing perfluoroalkyl group, a perfluoropolyether, or a perfluoroalkoxy group.

7. The silicone group is —[Si(CH ３ ) ２ -O] ｒ -Si(CH ３ ) ２ R ４ where r is an integer from 1 to 200, and R ４ The polymer of claim 1, wherein is an alkyl group containing 1 to 8 carbon atoms.

8. The RAFT agent is of the formula ZC(=S)SR, where R contains at least one of a nitrile or ester functionality, and Z is -C ６ H ５ , N-(4-pyridinyl)-N-methylamine, or -SR ５ wherein R ５ The polymer of claim 1, wherein is an alkyl group containing 1 to 12 carbon atoms.

9. The following formula: 【Chemistry 1】 wherein R １ is an alkyl group containing 1 to 4 carbon atoms, L １ is a linking group containing 1 to 9 carbon atoms, optionally L 1 is CH 2 ; Y is -L ２ -R ２ or -L ３ -R ３ wherein L is a releasable group selected from ２ is a linking group containing 1 to 9 carbon atoms and optionally at least one catenated ether; R ２ contains a silicone group, and L ３ is a linking group containing at least one of an ether, an ester, an amide, or a sulfonamide; R ３ contains a perfluorinated alkyl group or a perfluorinated polyether group, Each Q is independently H or CH ３ is selected from X is -C(CH ３ ) ２ CN, -C(CH ３ ) ２ C ６ H ５ , -CH(CN)C ６ H ５ , or -C(CH ３ ) ２ C(=O)OC ２ H ５ Including, Z is -C ６ H ５ , -SR ５ wherein R ５ is an alkyl group containing 1 to 12 carbon atoms or a monovalent pyrrole; a is an integer from 50 to 1000, b is an integer from 5 to 200, A polymer wherein c is an integer from 1 to 50.

10. R １ But -CH ３ , -CH ２ CH ３ , -CH(CH ３ ) CH ３ , -CH ２ CH ２ CH ３ , CH(CH ３ ) CH ２ CH ３ , -CH ２ CH (CH ３ ) CH ３ , or -C(CH ３ ) ３ 10. The polymer of claim 9, wherein:

11. 10. The polymer of claim 9, wherein the perfluorinated alkyl group is a straight-chain, branched-chain, or cyclic alkyl group containing from 1 to 10 carbon atoms.

12. The perfluorinated polyether group is -(C ｐ F ２ｐ ) -, -(C ｐ F ２ｐ O)-,-(CF(Q １ )) -, -(CF(Q １ )O)-,-(CF(Q １ ) C ｐ F ２ｐ O)-, -(C ｐ F ２ｐ CF (Q １ ) O) - or -(CF ２ CF (Q １ )O)—, During the ceremony, p is an integer from 1 to 10, Q １ is a fluorine atom, a perfluoroalkyl group, a perfluoroether group, a nitrogen-containing perfluoroalkyl group, a perfluoropolyether, or a perfluoroalkoxy group.

13. The silicone group is —[Si(CH ３ ) ２ -O] ｒ -Si(CH ３ ) ２ R ４ where r is an integer from 1 to 200, and R ４ 10. The polymer of claim 9, wherein is an alkyl group containing 1 to 8 carbon atoms.

14. 1. A liquid composition comprising: (a) the polymer of claim 1; (b) a crosslinking agent, optionally comprising a (meth)acrylate, a multifunctional thiol, a (meth)acrylamide, or a combination thereof; (c) a solvent, and (d) an optional photoinitiator, and (e) an optional stabilizer, optionally comprising at least one of 2,6,di-tert-butyl-4-methylphenol (BHT), 4-methoxyphenol, hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-)oxyl (4-hydroxy-TEMPO), or phenothiazene; A liquid composition comprising:

15. 10. A method of making a patterned resin comprising contacting a layer comprising the polymer of claim 1 with a patterned template, wherein the patterned template comprises a relief structure, and optionally the relief structure has at least one dimension less than 100 micrometers.

Images