Solvent system for selective removal of polymer materials

Abstract

A solution and related method are provided for the selective removal of polymer chains from a layer of block copolymer. The layer of block copolymer comprises a plurality of polymer domains, each polymer domain comprising a first region and a second region. The first region comprises a first polymer chain. The second region comprises a second polymer chain. The solution is configured to remove the second polymer chain at a higher rate than the first polymer chain and is sufficient to increase or modify the dimensions of at least one of the plurality of polymer domains.

Description

Technical Field

[0001] The present disclosure relates to solvent systems and related methods for the selective removal of polymer materials.

Background Art

[0002] Conventional methods of patterning microchips do not effectively remove polymer materials. The inability to remove the polymer layer hinders further progress and scaling of patterning.

Summary of the Invention

[0003] Some embodiments include obtaining a layer of a polystyrene-b-polymethylmethacrylate block copolymer, the layer including a plurality of polymer domains, each of the plurality of polymer domains including a first region including polystyrene chains; and a second region including polymethylmethacrylate chains; obtaining a layer of a polystyrene-b-polymethylmethacrylate block copolymer; contacting the layer with a solution to form a porous layer or a layer having a surface morphology, and removing at least a portion of the polymethylmethacrylate chains from the second region, wherein the solution removes the polymethylmethacrylate chains at a higher rate than the polystyrene chains, and relates to a method including removing at least a portion of the polymethylmethacrylate chains from the second region.

[0004] Some embodiments of the method involve obtaining a layer of polystyrene-b-polymethyl methacrylate block copolymer, wherein the layer comprises a plurality of polymer domains, each of which comprises a first region comprising polystyrene chains; a second region comprising polymethyl methacrylate chains;; exposing the layer to ultraviolet light, wherein at least a portion of the polymethyl methacrylate chains present in the second region are cleaved by the ultraviolet light; and removing at least a portion of the polymethyl methacrylate chains from the second region by contacting the layer with a solution to form a porous layer or a layer having surface morphology, wherein the solution removes the polymethyl methacrylate chains at a higher rate than the polystyrene chains.

[0005] Some embodiments relate to obtaining a layer of polystyrene-b-polymethyl methacrylate block copolymer, wherein the layer comprises a plurality of polymer domains, each of which comprises: a first region comprising polystyrene chains; a second region comprising polymethyl methacrylate chains; and a third region between the first and second regions, comprising unseparated portions of polystyrene and polymethyl methacrylate chains; and a method relating to removing at least a portion of polymethyl methacrylate chains from the second and third regions by contacting the layer with a solution to form a porous layer or a layer having surface morphology, wherein the solution removes polymethyl methacrylate chains in a higher proportion than polystyrene chains.

[0006] Several embodiments of the present disclosure are described herein merely as examples with reference to the accompanying drawings. With further detailed and specific reference to the drawings, it will be emphasized that the embodiments shown are illustrative and for illustrative purposes only. In this regard, the description in conjunction with the drawings will make it clear to those skilled in the art how embodiments of the present disclosure may be carried out. [Brief explanation of the drawing]

[0007] [Figure 1] This is a schematic diagram of the domains of a phase-separated block copolymer according to several embodiments. [Figure 2] This is a flowchart of a method for selective removal of polymer chains according to several embodiments. [Modes for carrying out the invention]

[0008] Among these disclosed benefits and improvements, other purposes and advantages of this disclosure will become apparent from the following description in conjunction with the accompanying drawings. Detailed embodiments of this disclosure are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative examples of the various forms in which this disclosure may be embodied. Furthermore, each example shown with respect to the various embodiments of this disclosure is intended to be illustrative, not limiting.

[0009] Any prior patents and publications referenced herein are incorporated in their entirety by reference.

[0010] Throughout this specification and the claims, the following terms have the meanings expressly associated herein unless otherwise explicitly indicated by the context. Where used herein, the phrases “in one embodiment,” “in one embodiment,” and “in several embodiments” may refer to the same embodiment, but not necessarily the same (one or more) embodiments. Furthermore, where used herein, the phrases “in another embodiment” and “in several other embodiments” may refer to different embodiments, but not necessarily different embodiments. All embodiments of this disclosure are intended to be combinatorial without departing from the scope or spirit of this disclosure.

[0011] As used herein, the term “based on” is not exclusive and may be based on additional factors not listed unless otherwise explicitly indicated by the context. Furthermore, throughout this specification, the meanings of “a,” “an,” and “the” include multiple references. The meaning of “in” includes “in” and “on.”

[0012] Several embodiments relate to solvent systems and related methods for the selective removal of polymer materials. In some embodiments, solvent systems are provided for modifying the limit dimensions of patterned layers useful for semiconductor fabrication, including microchip fabrication. The solvent systems can be combined with directed phase separation techniques of block copolymers to increase the limit dimensions of patterned layers. Directed phase separation of block copolymers allows for the formation of layers of polystyrene-β-polymethyl methacrylate block copolymers by coating and annealing onto the inducing patterned layer to obtain a structural pattern. The solvent systems disclosed herein may be used for the selective removal of polymethyl methacrylate chains in various regions of each polymer domain of the phase-separated block copolymer layer.

[0013] Unlike conventional solvent systems, the solvent systems disclosed herein can be used for the selective removal of polymethyl methacrylate chains from polystyrene chains. The selective removal of polymethyl methacrylate chains may include regions containing only polymethyl methacrylate chains, as well as regions containing both polymethyl methacrylate chains and polystyrene chains. The solvent systems disclosed herein can also be used, for example, to increase or modify the limiting dimensions of layers (e.g., the diameter of holes in each polymer domain) or patterns compared to conventional methods. The solvent systems disclosed herein can be used to improve pattern uniformity after wet chemical development. The solvent systems disclosed herein can be used to remove impurities. These and other benefits will be apparent to those skilled in the art in view of this disclosure.

[0014] Figure 1 is a schematic diagram of domain 100 of a layer of phase-separated block copolymer according to several embodiments. As shown in Figure 1, in some embodiments, domain 100 includes at least one of a first region 110, a second region 120, a third region 130, or any combination thereof. In some embodiments, the first region 110 includes, consists of, or is essentially composed of polystyrene chains. In some embodiments, the second region 120 includes, consists of, or is essentially composed of polymethyl methacrylate chains. In some embodiments, the third region lies between the first region 110 and the second region 120. In some embodiments, the third region 130 includes a mixed region. In some embodiments, the third region 130 includes, consists of, or is essentially composed of unseparated portions of polystyrene chains and polymethyl methacrylate chains. In some embodiments, the second region does not contain polystyrene chains. In some embodiments, the first region does not contain polymethyl methacrylate chains.

[0015] As used herein, the term “cleaved” refers to any form of damage to or breakdown of a bond. In some embodiments, the term “cleaved” refers to the breakdown of a chemical bond. In some embodiments, a cleaved polymer chain results in a breakdown of a chemical bond such that the polymer chain has a cleaved portion and an uncleaved portion. In some embodiments, the polymethyl methacrylate chain present in the second region 120 is not cleaved. In some embodiments, the polymethyl methacrylate chain present in the second region 120 is at least partially cleaved. In some embodiments, the polymethyl methacrylate chain present in the second region 120 is cleaved. In some embodiments, the polymethyl methacrylate chain present in the second region 120 includes an uncleaved polymethyl methacrylate chain 140 and a cleaved polymethyl methacrylate chain 150.

[0016] Figure 2 is a flowchart of Method 200 for selective removal of polymer chains according to several embodiments. As shown in Figure 2, in some embodiments, Method 200 includes one or more of the following steps: a step 202 to obtain a block copolymer; a step 204 to expose the layer to ultraviolet light; and a step 206 to contact the layer with a solution to form a porous layer or a layer having surface morphology.

[0017] In step 202, in some embodiments, a layer of block copolymer is obtained. In some embodiments, the layer of block copolymer includes a layer of phase-separated block copolymer. In some embodiments, the layer of block copolymer includes a layer of polystyrene-b-polymethyl methacrylate block copolymer. In some embodiments, the layer of polystyrene-b-polymethyl methacrylate block copolymer includes a plurality of polymer domains. In some embodiments, the plurality of polymer domains are formed as a result of phase separation of the polystyrene-b-polymethyl methacrylate block copolymer. In some embodiments, the plurality of polymer domains are formed as a result of induced phase separation of the polystyrene-b-polymethyl methacrylate block copolymer.

[0018] Each of the multiple polymer domains may contain, consist of, or be essentially of at least one of a first region, a second region, a third region, or any combination thereof. In some embodiments, the first region contains, consists of, or is essentially of polystyrene chains. In some embodiments, the second region contains, consists of, or is essentially of polymethyl methacrylate chains. In some embodiments, the third region is a region located between the first and second regions. In some embodiments, the third region includes a mixed region. In some embodiments, the third region includes a region in which the polystyrene chain and the polymethyl methacrylate chain are not completely separated. In some embodiments, the third region contains, consists of, or is essentially of unseparated portions of polystyrene chains and polymethyl methacrylate chains.

[0019] The polystyrene-β-polymethyl methacrylate block copolymer layer may contain at least one impurity. In some embodiments, the impurity is located in a first region. In some embodiments, the impurity is located in a second region. In some embodiments, the impurity is located in a third region. In some embodiments, the impurity includes styrene impurities. In some embodiments, the impurity includes methyl methacrylate impurities. In some embodiments, the impurity includes at least one of the following: at least one additive, at least one by-product, at least one residue (e.g., from a third region or mixed region), or any combination thereof.

[0020] In step 204, in some embodiments, the layer is exposed to ultraviolet light. In some embodiments, the ultraviolet light includes light having wavelengths in the range of 10 nm to 400 nm, or any range or partial range in that range. In some embodiments, the ultraviolet light includes extreme ultraviolet (EUV) light. As used herein, the term “extreme ultraviolet light” refers to the light used in extreme ultraviolet lithography. In some embodiments, the ultraviolet light utilizes photons to expose the photoresist. In some embodiments, the ultraviolet light includes 13.5 nm photons to expose the photoresist. In some embodiments, ultraviolet light is defined as 10nm-375nm, 10nm-350nm, 10nm-325nm, 10nm-300nm, 10nm-275nm, 10nm-250nm, 10nm-225nm, 10nm-200nm, 10nm-175nm, 10nm-150nm, 10nm-125nm, 10nm-100nm, 10nm-75nm, 10nm-50nm, 10nm-25nm, 25nm-4 Includes light having wavelengths in the range of 00nm, 50nm-400nm, 75nm-400nm, 100nm-400nm, 125nm-400nm, 150nm-400nm, 175nm-400nm, 200nm-400nm, 225nm-400nm, 250nm-400nm, 275nm-400nm, 300nm-400nm, 325nm-400nm, 350nm-400nm, or 375nm-400nm.

[0021] Exposure of a layer to ultraviolet light may be sufficient to damage, decompose, or otherwise break the chemical bonds of polymer chains. Exposure may selectively cleave polymethyl methacrylate chains relative to polystyrene chains. In some embodiments, exposure cleaves polymethyl methacrylate chains present in the second region at a higher rate than polystyrene chains present in the first region. In some embodiments, exposure cleaves polymethyl methacrylate chains present in the third region at a higher rate than polystyrene chains present in the third region. In some embodiments, exposure cleaves polymethyl methacrylate chains present in the third region at a higher rate than polystyrene chains present in the first region. In some embodiments, exposure cleaves polymethyl methacrylate chains present in the second region at a higher rate than polystyrene chains present in the third region. In some embodiments, exposure does not cleave any polystyrene chains present in the first region, the third region, or at least one of any combination thereof.

[0022] Exposure can cause cleavage of at least a portion of polymethyl methacrylate chains present in at least one of the regions of a plurality of polymer domains. In some embodiments, exposure causes cleavage of at least a portion of polymethyl methacrylate chains present in a second region. In some embodiments, as a result of cleavage, the second region includes polymethyl methacrylate chains, which consist of cleaved portions and uncleaved portions. In some embodiments, exposure causes cleavage of at least a portion of polymethyl methacrylate chains present in a third region. In some embodiments, as a result of cleavage, the third region includes polymethyl methacrylate chains, which consist of cleaved portions and uncleaved portions.

[0023] In some embodiments, no polymer chains are removed, but at least one dimension (e.g., critical dimension, e.g., without limitation, pore diameter, etc.) of at least one of the plurality of polymer domains is increased or modified by cleavage upon exposure to ultraviolet light.

[0024] In step 206, in some embodiments, the layer is contacted with a liquid. The solution may be configured to remove at least a portion of the polymethylmethacrylate chains from the layer to increase or modify at least one dimension (e.g., critical dimension, e.g., without limitation, pore diameter, etc.) of at least one of the plurality of polymer domains. In some embodiments, the term "remove" also means cleave as defined herein. In some embodiments, upon contact, at least a portion of the polymethylmethacrylate chains present in at least one of the regions of the plurality of polymer domains is removed. In some embodiments, upon contact, at least a portion of the polymethylmethacrylate chains present in a second region is removed. In some embodiments, upon contact, at least a portion of the non-cleaved polymethylmethacrylate chains present in the second region is removed. In some embodiments, upon contact, at least a portion of the polymethylmethacrylate chains present in a third region is removed. In some embodiments, upon contact, at least a portion of the non-cleaved polymethylmethacrylate chains present in the third region is removed.

[0025] A solution can selectively remove polymethyl methacrylate chains relative to polystyrene chains such that it is sufficient to increase or modify at least one dimension (e.g., a critical dimension, e.g., without limitation, pore diameter, etc.) of at least one of a plurality of polymer domains. In some embodiments, upon contact, the polymethyl methacrylate chains present in the second region are removed at a higher rate than the polystyrene chains present in the first region. In some embodiments, upon contact, the polymethyl methacrylate chains present in the second region are removed at a higher rate than the polystyrene chains present in the third region. In some embodiments, upon contact, the polymethyl methacrylate chains present in the third region are removed at a higher rate than the polystyrene chains present in the third region. In some embodiments, upon contact, the polymethyl methacrylate chains present in the third region are removed at a higher rate than the polystyrene chains present in the first region.

[0026] The solution can be formulated or configured to remove polymethyl methacrylate chains at a higher rate (portion) than a conventional solution, e.g., a conventional solution comprising or consisting of isopropyl alcohol (IPA), from at least one of the second region, the third region, or any combination thereof. In some embodiments, the solution comprises, consists of, or consists essentially of at least one of: at least one organic solvent, at least one aqueous solution, at least one alcohol solvent, at least one pH adjuster, or any combination thereof. In some embodiments, the solution comprises, consists of, or consists essentially of at least one organic solvent. In some embodiments, the solution comprises, consists of, or consists essentially of at least one aqueous solution. In some embodiments, the solution comprises, consists of, or consists essentially of at least one alcohol solvent. In some embodiments, the solution comprises, consists of, or consists essentially of at least one pH adjuster.

[0027] The solution may also be formulated or configured to remove at least one impurity from a layer of polystyrene-β-polymethyl methacrylate block copolymer. In some embodiments, the solution removes impurities present in a first region. In some embodiments, the solution removes impurities present in a second region. In some embodiments, the solution removes impurities present in a third region. In some embodiments, the solution removes styrene impurities. In some embodiments, the solution removes methyl methacrylate impurities. In some embodiments, the solution removes at least one of the following: at least one additive, at least one by-product, at least one residue (e.g., from a third region or mixed region), or any combination thereof.

[0028] Solutions may be formulated using any combination of solution types disclosed herein. As used herein, the term “solution type” refers to any substance present in a solution. Non-limiting examples of solution types include solvents in general, e.g., organic solvents, water, alcohol solvents, non-alcohol solvents, etc.; swelling control agents; pH adjusters; etc. In some embodiments, solvent refers to a solution type present in an amount sufficient to remove PMMA (e.g., alcohol solvent). In some embodiments, swelling control agent refers to a solution type present in an amount sufficient to control (e.g., at least reduce) the swelling of PS. In some embodiments, swelling control agent is a solution type present in an amount less than the amount of solvent. In some embodiments, swelling control agent is a solution type that improves CD and / or LCDU. In some embodiments, swelling control agent is C5~C 10This includes alcohol solvents and their isomers. In some embodiments, the swelling control agent is an alcohol solvent, and the solvent is an alcohol solvent, both of which are combined in the solvent system. In some embodiments, the CD is improved by a non-alcohol solvent. In some embodiments, a particular solution species may act as a solvent when present in the solution at a first concentration, and may act as a swelling control agent when present in the solution at a second concentration different from the first concentration. In some embodiments, a pH adjuster refers to a solution species present in an amount sufficient to adjust the pH of the solution. As one non-limiting example, an alcohol solvent may act as a solvent at a first concentration; the same alcohol solvent may act as a swelling control agent at a second concentration which is less than the first concentration.

[0029] In some embodiments, the solution contains, consists of, or is essentially composed of, a first organic solvent and a second organic solvent different from the first organic solvent. In some embodiments, the solution contains, consists of, or is essentially composed of, a first organic solvent, a second organic solvent different from the first organic solvent, and a pH adjuster. In some embodiments, the solution contains, consists of, or is essentially composed of, an organic solvent and an alcohol solvent. In some embodiments, the solution contains, consists of, or is essentially composed of, an alcohol solvent and a pH adjuster. In some embodiments, the solution contains, consists of, or is essentially composed of, an organic solvent, an alcohol solvent, and a pH adjuster. In some embodiments, the solution contains, consists of, or is essentially composed of, water and a water-miscible alcohol solvent. In some embodiments, the solution contains, consists of, or is essentially composed of, at least one solvent, at least one pH adjuster, or at least one of any combination thereof. In some embodiments, the solution comprises, consists of, or is essentially composed of at least one of the following: at least one alcoholic solvent, at least one non-alcoholic solvent, at least one pH adjuster, or any combination thereof. In some embodiments, the solution comprises, consists of, or is essentially composed of at least one of the following: at least one solvent, at least one swelling control agent, at least one pH adjuster, or any combination thereof. In some embodiments, the solution comprises, consists of, or is essentially composed of at least one of the following: at least one organic solvent, at least one water-miscible organic solvent, at least one water, or any combination thereof.

[0030] In some embodiments, the solution comprises at least one of the following: acetone, acetic acid, diethylene glycol dibutyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, cyclohexanone, toluene, dichloromethane, tetrahydrofurfuryl alcohol, 2-phenoxyethanol, ethylene glycol butyl ether, 1-butanol, 2-ethoxyethyl acetate, n-butyl acetate, ethyl acetate, 1-heptanol, 1-butoxy-2-propanol, triethylamine, benzyl benzoate, bromobenzene, propylene glycol monobutyl ether, propylene glycol methyl ether (PGME), ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 1-(2-hydroxyethyl)-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, hexylene glycol, triethylene glycol, or at least one of any combination thereof.

[0031] In some embodiments, the solution comprises at least one of the following: acetic acid, acetone, acetonitrile, benzene, 1-butanol, 2-butanol, 2-butanone, carbon tetrachloride, chlorobenzene, chloroform, cyclohexane, 1,2-dichloroethane, diethylene glycol, diethyl ether, diethylene glycol dimethyl ether, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, ethanol, ethyl acetate, ethylene glycol, glycerin, methanol, ethanol, isopropanol, ethyl lactate, ethylene glycol, propylene glycol monomethyl ether, cyclohexanol, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, polyaryl ether, hexamethyldisilazane, or any combination thereof.

[0032] In some embodiments, the solution comprises at least one of the following: pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, 2,2,4-trimethylpentane, cyclohexane, cyclohexane, ethylbenzene, ketone, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, N-methyl-2-pyrrolidone, diethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, 1,4-dioxane, tetrahydrofuran, ester, methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, glycol ether, propylene glycol, methyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, trichloroethylene, perchloroethylene, monochlorobenzene, dimethylformamide, dimethylacetamide, acetic acid, aniline, nitrobenzene, pyridine, phenol, or any combination thereof.

[0033] In some embodiments, if the solution contains an alcohol solvent, the organic solvent does not contain an alcohol solvent. In some embodiments, the alcohol solvent includes at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, 2-butanol, 1-pentanol, 1-hexanol, heptanol, amyl alcohol, cyclohexanol, n-octanol, ethanediol, diethylene glycol, 1,2-propanediol, or any combination thereof. In some embodiments, the alcohol solvent includes any one or more of the alcohols disclosed herein.

[0034] In some embodiments, the pH adjuster includes at least one of the following: methanesulfonic acid, acetic acid, octanoic acid, formic acid, phosphoric acid, choline hydroxide, diethylamine, methanolamine, N-(3-aminopropyl)diethanolamine, 2-(butylamino)ethanol, 2-(tert-butylamino)ethanol, 2-(2-aminoethoxy)ethanol, 3-amino-1-propanol, tetrabutylammonium hydroxide (TBAH), tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), (ETAMH), triethylamine (TEA), triethanolamine, ethanolamine (ETA), or at least one of any combination thereof.

[0035] In some embodiments, the solution comprises at least one of at least one solvent, at least one pH adjuster, or any combination thereof. In some embodiments, the at least one solvent comprises at least one of 1-butanol, propylene glycol methyl ether (PGME), 1-heptanol, or any combination thereof. In some embodiments, the at least one pH adjuster comprises at least one of 70% methanesulfonic acid (MSA), acetic acid, octanoic acid, triethanolamine, 2-(2-aminoethoxy)ethanol, 40% tetrabutylammonium hydroxide (TBAH), or any combination thereof.

[0036] In some embodiments, the solution comprises at least one of the following: at least one alcoholic solvent, at least one non-alcoholic solvent, at least one pH adjuster, or any combination thereof. In some embodiments, the alcoholic solvent comprises 1-butanol. In some embodiments, the at least one non-alcoholic solvent comprises at least one of the following: cyclohexanone, methyl isobutyl ketone (MIBK), butyl acetate, 1-heptanol, or any combination thereof. In some embodiments, the pH adjuster comprises 3-amino-1-propanol.

[0037] In some embodiments, the solution comprises at least one of the following: at least one solvent, at least one swelling control agent, at least one pH adjuster, or any combination thereof. In some embodiments, the at least one solvent comprises at least one of the following: 1-butanol, propylene glycol methyl ether (PGME), or any combination thereof. In some embodiments, the at least one swelling control agent comprises at least one of the following: 1-pentanol, 2-pentanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,4-dimethyl-3-pentanol, 1-octanol, methanol, ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, 2-butanol, pentanol, amyl alcohol, cyclohexanol, n-octanol, ethanediol, diethylene glycol, 1,2-propanediol, or any combination thereof. In some embodiments, the pH adjuster includes tetrabutylammonium hydroxide (TBAH). In some embodiments, the swelling control agent is linear C1-C 20 Contains alcohol. In some embodiments, the swelling control agent is branched C2-C 20 Contains alcohol.

[0038] In some embodiments, the solution comprises at least one solvent in any range or partial range between 5% and 90% by weight, or between 5% and 90%, based on the total weight of the solution. In some embodiments, the solution is divided into 5%-85% by weight, 5%-80% by weight, 5%-75% by weight, 5%-70% by weight, 5%-65% by weight, 5%-60% by weight, 5%-55% by weight, 5%-50% by weight, 5%-45% by weight, 5%-40% by weight, 5%-35% by weight, 5%-30% by weight, 5%-25% by weight, 5%-20% by weight, 5%-15% by weight, 5%-10% by weight, 10%-90% by weight, 15%-90% by weight, 20%-90% by weight, 30%-90% by weight, 35%-90% by weight, and 40%-90% by weight. It contains at least one solvent in the following amounts: 0% by weight, 45% to 90% by weight, 50% to 90% by weight, 55% to 90% by weight, 60% to 90% by weight, 65% to 90% by weight, 70% to 90% by weight, 75% to 90% by weight, 80% to 90% by weight, 85% to 90% by weight, 45% to 65% by weight, 45% to 60% by weight, 45% to 55% by weight, 45% to 50% by weight, 50% to 65% by weight, 55% to 65% by weight, 60% to 65% by weight, 15% to 30% by weight, 20% to 30% by weight, 25% to 30% by weight, 15% to 25% by weight, or 15% to 20% by weight.

[0039] In some embodiments, the solution contains at least one pH adjusting agent in an amount of 0.1% to 20% by weight, or any range or partial range between 0.1% and 20%, based on the total weight of the solution. In some embodiments, the solution contains 0.1% to 19% by weight, 0.1% to 18% by weight, 0.1% to 17% by weight, 0.1% to 16% by weight, 0.1% to 15% by weight, 0.1% to 14% by weight, 0.1% to 13% by weight, 0.1% to 12% by weight, 0.1% to 11% by weight, or 0.1% to 10% by weight, based on the total weight of the solution. %, 0.1% to 9% by weight, 0.1% to 8% by weight, 0.1% to 7% by weight, 0.1% to 6% by weight, 0.1% to 5% by weight, 0.1% to 4% by weight, 0.1% by weight %~3wt%, 0.1wt%~2wt%, 0.1wt%~1wt%, 0.1wt%~0.9wt%, 0.1wt%~0.8wt%, 0.1wt%~0.7wt%, 0.1wt% ~0.6wt%, 0.1wt%~0.5wt%, 0.1wt%~0.4wt%, 0.1wt%~0.3wt%, 0.1wt%~0.2wt%, 0.5wt%~20wt%, 1wt Amount%~20wt%, 2wt%~20wt%, 3wt%~20wt%, 4wt%~20wt%, 5wt%~20wt%, 6wt%~20wt%, 7wt%~20wt%, 8wt% It contains at least one pH adjuster in the following amounts: ~20% by weight, 9%~20% by weight, 10%~20% by weight, 11%~20% by weight, 12%~20% by weight, 13%~20% by weight, 14%~20% by weight, 15%~20% by weight, 16%~20% by weight, 17%~20% by weight, 18%~20% by weight, or 19%~20% by weight.

[0040] In some embodiments, the solution contains at least one alcoholic solvent in any range or partial range between 50% and 99% by weight, or between 50% and 99%, based on the total weight of the solution. In some embodiments, the solution contains at least one alcoholic solvent in any range between 50% and 95% by weight, or between 50% and 99% by weight, based on the total weight of the solution.

[0041] In some embodiments, the solution contains at least one non-alcoholic solvent in any range or partial range between 1% and 50% by weight, or between 1% and 50%, based on the total weight of the solution. In some embodiments, the solution contains at least one non-alcoholic solvent in any range between 1% and 45% by weight, 1% and 40% by weight, 1% and 35% by weight, 1% and 30% by weight, 1% and 25% by weight, 1% and 20% by weight, 1% and 15% by weight, 1% and 10% by weight, 1% and 5% by weight, 5% and 50% by weight, 10% and 50% by weight, 15% and 50% by weight, 20% and 50% by weight, 25% and 50% by weight, 30% and 50% by weight, 35% and 50% by weight, 40% and 50% by weight, or 45% and 50% by weight.

[0042] In some embodiments, the solution contains at least one swelling control agent in any range or partial range between 1% to 25% by weight, or between 1% and 25%, based on the total weight of the solution. In some embodiments, the solution contains, based on the total weight of the solution, 1% to 24% by weight, 1% to 22% by weight, 1% to 20% by weight, 1% to 18% by weight, 1% to 16% by weight, 1% to 15% by weight, 1% to 14% by weight, 1% to 12% by weight, 1% to 10% by weight, 1% to 8% by weight, 1% to 6% by weight, 1% to 5% by weight, 1% to 4% by weight, 1% to 2% by weight, and double It contains at least one swelling control agent in amounts of % to 25% by weight, 4% to 25% by weight, 5% to 25% by weight, 6% to 25% by weight, 8% to 25% by weight, 10% to 25% by weight, 12% to 25% by weight, 14% to 25% by weight, 15% to 25% by weight, 16% to 25% by weight, 18% to 25% by weight, 20% to 25% by weight, 22% to 25% by weight, or 24% to 25% by weight.

[0043] In some embodiments, the solution contains at least one organic solvent in an amount of 5% to 90% by weight, or any range or partial range between 5% and 90%, based on the total weight of the solution. In some embodiments, the solution is divided into 5%-85% by weight, 5%-80% by weight, 5%-75% by weight, 5%-70% by weight, 5%-65% by weight, 5%-60% by weight, 5%-55% by weight, 5%-50% by weight, 5%-45% by weight, 5%-40% by weight, 5%-35% by weight, 5%-30% by weight, 5%-25% by weight, 5%-20% by weight, 5%-15% by weight, 5%-10% by weight, 10%-90% by weight, 15%-90% by weight, 20%-90% by weight, 30%-90% by weight, 35%-90% by weight, and 40%-90% by weight. It contains at least one organic solvent in the following amounts: weight %, 45% to 90% by weight, 50% to 90% by weight, 55% to 90% by weight, 60% to 90% by weight, 65% to 90% by weight, 70% to 90% by weight, 75% to 90% by weight, 80% to 90% by weight, 85% to 90% by weight, 45% to 65% by weight, 45% to 60% by weight, 45% to 55% by weight, 45% to 50% by weight, 50% to 65% by weight, 55% to 65% by weight, 60% to 65% by weight, 15% to 30% by weight, 20% to 30% by weight, 25% to 30% by weight, 15% to 25% by weight, or 15% to 20% by weight.

[0044] In some embodiments, the solution contains water in any range or partial range between 5% and 90% by weight, or between 5% and 90%, based on the total weight of the solution. In some embodiments, the solution is divided into 5%-85% by weight, 5%-80% by weight, 5%-75% by weight, 5%-70% by weight, 5%-65% by weight, 5%-60% by weight, 5%-55% by weight, 5%-50% by weight, 5%-45% by weight, 5%-40% by weight, 5%-35% by weight, 5%-30% by weight, 5%-25% by weight, 5%-20% by weight, 5%-15% by weight, 5%-10% by weight, 10%-90% by weight, 15%-90% by weight, 20%-90% by weight, 30%-90% by weight, 35%-90% by weight, 40%-90% by weight, and 4 Contains at least one type of water in the following proportions: 5% to 90% by weight, 50% to 90% by weight, 55% to 90% by weight, 60% to 90% by weight, 65% to 90% by weight, 70% to 90% by weight, 75% to 90% by weight, 80% to 90% by weight, 85% to 90% by weight, 45% to 65% by weight, 45% to 60% by weight, 45% to 55% by weight, 45% to 50% by weight, 50% to 65% by weight, 55% to 65% by weight, 60% to 65% by weight, 15% to 30% by weight, 20% to 30% by weight, 25% to 30% by weight, 15% to 25% by weight, 10% to 95% by weight, or 15% to 20% by weight.

[0045] In some embodiments, the solution has a pH in the range of 0 to 14, or any range or partial range in that range. In some embodiments, the solution has a neutral pH (e.g., pH of about 7). In some embodiments, the solution has a pH in the range of 0 to 6, 1 to 6, 2 to 6, 3 to 6, 4 to 6, 5 to 6, 0 to 5, 0 to 4, 0 to 3, 0 to 2, 0 to 1, or any range or partial range in that range. In some embodiments, the solution has a pH in the range of 8 to 14, 8 to 13, 8 to 12, 8 to 11, 8 to 10, 8 to 9, 9 to 14, 10 to 14, 11 to 14, 12 to 14, 13 to 14, or any range or partial range in that range.

[0046] In some embodiments, a porous layer is formed as a result of contact. In some embodiments, the porous layer contains a plurality of pores. In some embodiments, the porous layer contains a plurality of nanopores. In some embodiments, the porous layer contains a plurality of isopores. In some embodiments, the pores of the porous layer have an average pore diameter of 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less, 10 nm or less, or 5 nm or less. In some embodiments, the pores of the porous layer have an average pore diameter of 1 nm to 100 nm, or any range or partial range in that range. For example, the pores in a porous layer may have an average pore diameter of 1nm-90nm, 1nm-80nm, 1nm-70nm, 1nm-60nm, 1nm-50nm, 1nm-40nm, 1nm-30nm, 1nm-20nm, 1nm-10nm, 1nm-5nm, 5nm-100nm, 10nm-100nm, 20nm-100nm, 30nm-100nm, 40nm-100nm, 50nm-100nm, 60nm-100nm, 70nm-100nm, 80nm-100nm, or 90nm-100nm. In some embodiments, the pores of the porous layer have average pore diameters of 10nm-70nm, 10nm-60nm, 10nm-50nm, 10nm-40nm, 10nm-30nm, 10nm-20nm, 20nm-70nm, 30nm-70nm, 40nm-70nm, 50nm-70nm, and 60nm-70nm.

[0047] In some embodiments, contact results in the formation of a layer having surface morphology. For example, in some embodiments, contact results in a layer having a patterned surface. The patterned surface may have at least one of lines, spaces, ridges, columns, valleys, or any combination thereof.

[0048] Some embodiments relate to porous layers or layers having surface morphology. In some embodiments, the porous layer includes any porous layer formed according to any of the methods disclosed herein. In some embodiments, the porous layer is useful as a mask for pattern transfer. In some embodiments, the layer has any of the surface morphologies disclosed herein.

[0049] Some embodiments relate to obtaining a layer of polystyrene-b-polymethyl methacrylate block copolymer, wherein the layer comprises a plurality of polymer domains, each of which comprises a first region comprising polystyrene chains; a second region comprising polymethyl methacrylate chains; and a method comprising contacting the layer with a solution to remove at least a portion of the polymethyl methacrylate chains from the second region so as to form a porous layer or a layer having surface morphology, wherein the solution removes the polymethyl methacrylate chains in a higher proportion than the polystyrene chains.

[0050] In some embodiments, the solution includes an organic solvent.

[0051] In some embodiments, the solution includes an aqueous solution.

[0052] In some embodiments, the solution contains an alcoholic solvent.

[0053] In some embodiments, the solution includes a pH adjuster.

[0054] In some embodiments, the solution comprises a first organic solvent and a second organic solvent different from the first organic solvent.

[0055] In some embodiments, the solution comprises a first organic solvent, a second organic solvent different from the first organic solvent, and a pH adjuster.

[0056] In some embodiments, the solution comprises an organic solvent and an alcoholic solvent.

[0057] In some embodiments, the solution comprises an alcohol solvent and a pH adjuster.

[0058] In some embodiments, the solution comprises an organic solvent, an alcoholic solvent, and a pH adjuster.

[0059] In some embodiments, the solvent includes water and a water-miscible alcohol solvent.

[0060] In some embodiments, the solution contains at least one of the following organic solvents: acetone, acetic acid, diethylene glycol dibutyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, cyclohexanone, toluene, dichloromethane, tetrahydrofurfuryl alcohol, 2-phenoxyethanol, ethylene glycol butyl ether, 1-butanol, 2-ethoxyethyl acetate, n-butyl acetate, ethyl acetate, 1-heptanol, 1-butoxy-2-propanol, triethylamine, benzyl benzoate, bromobenzene, propylene glycol monobutyl ether, propylene glycol methyl ether (PGME), ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-(2-hydroxyethyl)-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, hexylene glycol, triethylene glycol, or at least one of any combination thereof.

[0061] In some embodiments, the solution contains at least one of the following pH adjusters: methanesulfonic acid, acetic acid, octanoic acid, formic acid, phosphoric acid, choline hydroxide, diethylamine, methanolamine, N-(3-aminopropyl)diethanolamine, 2-(butylamino)ethanol, 2-(tert-butylamino)ethanol, 2-(2-aminoethoxy)ethanol, 3-amino-1-propanol, tetrabutylammonium hydroxide (TBAH), tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), (ETAMH), triethylamine (TEA), triethanolamine, or at least one of any combination thereof.

[0062] In some embodiments, the solution removes polymethyl methacrylate chains present in the second region at a higher rate than polystyrene chains present in the first region.

[0063] In some embodiments, each of the plurality of polymer domains further comprises a third region, which is a mixed region between a first region and a second region, and which includes unseparated portions of polystyrene chains and polymethyl methacrylate chains.

[0064] In some embodiments, the solution removes at least a portion of the polymethyl methacrylate chain from the third region.

[0065] In some embodiments, the solution removes polymethyl methacrylate chains present in the third region at a higher rate than polystyrene chains present in the third region.

[0066] In some embodiments, the solution removes polymethyl methacrylate chains present in the third region at a higher rate than polystyrene chains present in the first region.

[0067] In some embodiments, the solution removes polymethyl methacrylate chains present in the second region at a higher rate than polystyrene chains present in the third region.

[0068] In some embodiments, the porous layer includes a plurality of nanopores.

[0069] In some embodiments, the porous layer contains pores having an average pore diameter of 100 nm or less.

[0070] Some embodiments relate to a method for obtaining a layer of polystyrene-b-polymethyl methacrylate block copolymer, wherein the layer comprises a plurality of polymer domains, each of which comprises a first region comprising polystyrene chains; a second region comprising polymethyl methacrylate chains;; exposing the layer to ultraviolet light, wherein the ultraviolet light cleaves at least a portion of the polymethyl methacrylate chains present in the second region; and contacting the layer with a solution to remove at least a portion of the polymethyl methacrylate chains from the second region, wherein the solution removes the polymethyl methacrylate chains at a higher rate than the polystyrene chains.

[0071] In some embodiments, the solution includes an organic solvent.

[0072] In some embodiments, the solution includes an aqueous solution.

[0073] In some embodiments, the solution contains an alcoholic solvent.

[0074] In some embodiments, the solution includes a swelling control agent.

[0075] In some embodiments, the solution includes a pH adjuster.

[0076] In some embodiments, the solution comprises a first organic solvent and a second organic solvent different from the first organic solvent.

[0077] In some embodiments, the solution comprises a first organic solvent, a second organic solvent different from the first organic solvent, and a pH adjuster.

[0078] In some embodiments, the solution comprises an organic solvent and an alcoholic solvent.

[0079] In some embodiments, the solution comprises an alcohol solvent and a pH adjuster.

[0080] In some embodiments, the solution comprises an organic solvent, an alcoholic solvent, and a pH adjuster.

[0081] In some embodiments, the solution comprises water and a water-miscible alcohol solvent.

[0082] In some embodiments, the solution contains at least one of the following organic solvents: acetone, acetic acid, diethylene glycol dibutyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, cyclohexanone, toluene, dichloromethane, tetrahydrofurfuryl alcohol, 2-phenoxyethanol, ethylene glycol butyl ether, 1-butanol, 2-ethoxyethyl acetate, n-butyl acetate, ethyl acetate, 1-heptanol, 1-butoxy-2-propanol, triethylamine, benzyl benzoate, bromobenzene, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-(2-hydroxyethyl)-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, hexylene glycol, triethylene glycol, or at least one of any combination thereof.

[0083] In some embodiments, the solution contains at least one of the following pH adjusters: methanesulfonic acid, acetic acid, formic acid, phosphoric acid, choline hydroxide, diethylamine, methanolamine, N-(3-aminopropyl)diethanolamine, 2-(butylamino)ethanol, 2-(tert-butylamino)ethanol, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), ethyltrimethylammonium hydroxide (ETAMH), triethylamine (TEA), triethanolamine, or at least one of any combination thereof.

[0084] In some embodiments, the solution removes polymethyl methacrylate chains present in the second region at a higher rate than polystyrene chains present in the first region.

[0085] In some embodiments, each of the multiple polymer domains further comprises a third region between a first region and a second region, which is a mixed region containing unseparated portions of polystyrene chains and polymethyl methacrylate chains.

[0086] In some embodiments, the solution removes at least a portion of the polymethyl methacrylate chain from the third region.

[0087] In some embodiments, the solution removes polymethyl methacrylate chains present in the third region at a higher rate than polystyrene chains present in the third region.

[0088] In some embodiments, the solution removes polymethyl methacrylate chains present in the third region at a higher rate than polystyrene chains present in the first region.

[0089] In some embodiments, the solution removes polymethyl methacrylate chains present in the second region at a higher rate than polystyrene chains present in the third region.

[0090] In some embodiments, the porous layer includes a plurality of nanopores.

[0091] In some embodiments, the porous layer contains pores having an average pore diameter of 100 nm or less.

[0092] Some embodiments relate to obtaining a layer of polystyrene-b-polymethyl methacrylate block copolymer, wherein the layer comprises a plurality of polymer domains, each of which comprises: a first region comprising polystyrene chains; a second region comprising polymethyl methacrylate chains; and a third region between the first and second regions, comprising an unseparated portion of the polystyrene chains and the polymethyl methacrylate chains; and a method relating to removing at least a portion of the polymethyl methacrylate chains from the second and third regions by contacting the layer with a solution to form a porous layer or a layer having surface morphology, wherein the solution removes the polymethyl methacrylate chains in a higher proportion than the polystyrene chains, and the method relates to removing at least a portion of the polymethyl methacrylate chains from the second region.

[0093] In some embodiments, the solution includes an organic solvent.

[0094] In some embodiments, the solution includes an aqueous solution.

[0095] In some embodiments, the solution contains an alcoholic solvent.

[0096] In some embodiments, the solution includes a pH adjuster.

[0097] In some embodiments, the solution comprises a first organic solvent and a second organic solvent different from the first organic solvent.

[0098] In some embodiments, the solution comprises a first organic solvent, a second organic solvent different from the first organic solvent, and a pH adjuster.

[0099] In some embodiments, the solution comprises an organic solvent and an alcoholic solvent.

[0100] In some embodiments, the solution comprises an alcohol solvent and a pH adjuster.

[0101] In some embodiments, the solution comprises an organic solvent, an alcoholic solvent, and a pH adjuster.

[0102] In some embodiments, the solution comprises water and a water-miscible alcohol solvent.

[0103] In some embodiments, the solution contains at least one of the following organic solvents: acetone, acetic acid, diethylene glycol dibutyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, cyclohexanone, toluene, dichloromethane, tetrahydrofurfuryl alcohol, 2-phenoxyethanol, ethylene glycol butyl ether, 1-butanol, 2-ethoxyethyl acetate, n-butyl acetate, ethyl acetate, 1-heptanol, 1-butoxy-2-propanol, triethylamine, benzyl benzoate, bromobenzene, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-(2-hydroxyethyl)-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, hexylene glycol, triethylene glycol, or at least one of any combination thereof.

[0104] In some embodiments, the solution contains at least one of the following pH adjusters: methanesulfonic acid, acetic acid, formic acid, phosphoric acid, choline hydroxide, diethylamine, methanolamine, N-(3-aminopropyl)diethanolamine, 2-(butylamino)ethanol, 2-(tert-butylamino)ethanol, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), ethyltrimethylammonium hydroxide (ETAMH), triethylamine (TEA), triethanolamine, or at least one of any combination thereof.

[0105] In some embodiments, the solution removes polymethyl methacrylate chains present in the second region at a higher rate than polystyrene chains present in the first region.

[0106] In some embodiments, the solution removes at least a portion of the polymethyl methacrylate chain from the third region.

[0107] In some embodiments, the solution removes polymethyl methacrylate chains present in the third region at a higher rate than polystyrene chains present in the third region.

[0108] In some embodiments, the solution removes polymethyl methacrylate chains present in the third region at a higher rate than polystyrene chains present in the first region.

[0109] In some embodiments, the solution removes polymethyl methacrylate chains present in the second region at a higher rate than polystyrene chains present in the third region.

[0110] In some embodiments, the porous layer includes a plurality of nanopores.

[0111] In some embodiments, the porous layer contains pores having an average pore diameter of 100 nm or less. [Examples]

[0112] General method Immersion method in beaker: A 50 ml test solution prepared by weight percentage was placed in a 100 ml glass beaker. While gently stirring at 120 rpm at room temperature, a wafer coupon was picked up with PP tweezers and completely immersed in the solution, then immersed for 10 to 180 seconds depending on the test conditions. Subsequently, the coupon was lifted and placed directly into another beaker, rinsed with DIW for 1 minute, and then dried with N2 air. Film thickness measurements were performed before and after the immersion process by using coupon pieces of homo-PS or homo-PMMA coated film samples, particularly for etching rate studies and expansion inhibition studies.

[0113] Spin-on-Paddle Method: A wafer coupon was placed on the flat stage of a spin coater (MIKASA MS-B300) and pulled down and secured using a vacuum pump. 0.5 ml of the test solution was dropped onto the surface of the coupon, which immediately covered the surface completely. After the coupon was left to stand for the required processing time for paddle drying, the coupon was spin-dried at 1500 rpm to uniformly dry the surface.

[0114] Functionality testing with patterned wafer coupons: 1 x 1 cm² wafer coupons were processed for the required processing time either by immersion in a beaker or by spin-on. A scanning electron microscope (Hitachi SU-8220) was used for pattern observation with a Pt coating. Image data was processed for metropolitan analysis, and LCDU and twisting were analyzed using measurement algorithms and statistical processing applied to CD-SEM.

[0115] Example 1 A mixture of solvent and pH adjuster Several formulations (Samples A-F) were prepared at various pH levels, and the PMMA removal performance of each formulation was evaluated. A mixture of 1-butanol, propylene glycol methyl ether (PGME), and 1-heptanol was blended with a pH adjuster by stirring at room temperature. The formulations of Samples A-F and their corresponding PMMA removal performance are summarized in Tables 1 and 2 below. TIFF2026512038000002.tif61170

[0116] The pKa values ​​of each pH adjuster included 70% MSA (-1.9 pKa), acetic acid (4.6 pKa), octanoic acid (4.9 pKa), triethanolamine (7.9 pKa), 2-(2-aminoethoxy)ethanol (9.6 pKa), and 40% TBAH (14 pKa). TIFF2026512038000003.tif63170

[0117] As shown in Tables 1 and 2, the alkaline system performed unexpectedly better than the acidic system.

[0118] Example 2 A mixture of alcoholic solvent, non-alcoholic solvent, and pH adjuster. Several formulations (Samples G-I) were prepared, and the PMMA removal performance of each formulation was evaluated. Alcoholic and non-alcoholic solvents were blended with a pH adjuster by stirring at room temperature. The formulations of Samples G-I and their corresponding PMMA removal performance are summarized in Tables 3 and 4 below. TIFF2026512038000004.tif71170TIFF2026512038000005.tif42170

[0119] Example 3 A mixture of solvent, swelling control agent, and pH adjuster. Several formulations (Samples J-Q) were prepared, and the PMMA removal performance of each formulation was evaluated. The solvent and swelling control agent were combined with a pH adjuster and blended by stirring at room temperature. The formulations of Samples J-Q and their corresponding PMMA removal performance are summarized in Tables 5 and 6 below. TIFF2026512038000006.tif112170TIFF2026512038000007.tif76170

[0120] Example 4 A mixture of water and organic solvents Several formulations (Samples R-U) were prepared, and the PMMA removal performance of each formulation was evaluated. Water and an organic solvent were combined and blended by stirring at room temperature. Table 7 below summarizes the formulations of Samples R-U and the corresponding PMMA removal performance for each formulation. TIFF2026512038000008.tif51170

[0121] manner Various embodiments are described below. It should be understood that one or more of the features described in the following embodiments may be combined with one or more of the other embodiments. Appearance 1. The objective is to obtain a layer of polystyrene-β-polymethyl methacrylate block copolymer, The layer contains multiple polymer domains, and each of the multiple polymer domains is The first region containing polystyrene chains; A second region containing a polymethyl methacrylate chain; To obtain a layer of polystyrene-β-polymethyl methacrylate block copolymer containing; The method involves bringing the layer into contact with a solution to remove at least a portion of the polymethyl methacrylate chains from the second region. The solution removes polymethyl methacrylate chains at a higher rate than polystyrene chains, thereby removing at least a portion of the polymethyl methacrylate chains from a second region. Methods that include... Apparatus 2. The solution is At least one solvent in an amount of 5% to 90% by weight based on the total weight of the solution; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to embodiment 1, including the method described in embodiment 1. Embodiment 3. The method according to Embodiment 2, wherein the solution has a pH of less than 7. Apparatus 4. The solution is 50% to 99% by weight of at least one alcoholic solvent based on the total weight of the solution; Based on the total weight of the solution, at least one non-alcoholic solvent in an amount of 1% to 50% by weight; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to any one of embodiments 1 to 3, including the method described above. Apparatus 5. The solution is A first alcoholic solvent in an amount of 5% to 90% by weight, based on the total weight of the solution; At least one swelling control agent in an amount of 1% to 25% by weight based on the total weight of the solution, wherein at least one swelling control agent is a second alcohol solvent different from at least one first alcohol solvent; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to any one of embodiments 1 to 4, including the method described above. Apparatus 6. The solution is At least one organic solvent in an amount of 5% to 90% by weight based on the total weight of the solution; and Based on the total weight of the solution, 10% to 95% by weight of water. The method according to any one of embodiments 1 to 5, including the method described above. Embodiment 7. The method according to any one of Embodiments 1 to 6, wherein the solution removes polymethyl methacrylate chains present in the second region at a higher rate than polystyrene chains present in the first region. Appearance 8. The objective is to obtain a layer of polystyrene-β-polymethyl methacrylate block copolymer, The layer contains multiple polymer domains, and each of the multiple polymer domains is The first region containing polystyrene chains; A second region containing a polymethyl methacrylate chain; To obtain a layer of polystyrene-β-polymethyl methacrylate block copolymer containing; This involves exposing the layer to ultraviolet light. Exposing the layer to ultraviolet light causes at least some of the polymethyl methacrylate chains present in the second region to be cleaved. The method involves bringing the layer into contact with a solution to remove at least a portion of the polymethyl methacrylate chains from a second region, so as to form a porous layer or a layer having surface morphology. The solution removes polymethyl methacrylate chains at a higher rate than polystyrene chains, thereby removing at least a portion of the polymethyl methacrylate chains from the second region. Methods that include... Apparatus 9. The solution is At least one solvent in an amount of 5% to 90% by weight based on the total weight of the solution; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to embodiment 8, including the method described in embodiment 8. Embodiment 10. The method according to Embodiment 9, wherein the solution has a pH of less than 7. Apparatus 11. The solution is 50% to 99% by weight of at least one alcoholic solvent based on the total weight of the solution; Based on the total weight of the solution, at least one non-alcoholic solvent in an amount of 1% to 50% by weight; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to any one of embodiments 8 to 10, including the method described above. Apparatus 12. The solution is At least one solvent in an amount of 5% to 90% by weight based on the total weight of the solution; At least one swelling control agent in an amount of 1% to 25% by weight based on the total weight of the solution; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to any one of embodiments 8 to 11, including the method described above. Apparatus 13. The solution is At least one organic solvent in an amount of 5% to 90% by weight based on the total weight of the solution; and Based on the total weight of the solution, 10% to 95% by weight of water. The method according to any one of embodiments 8 to 12, including the method described above. Embodiment 14. The method according to any one of Embodiments 8 to 13, wherein the solution removes polymethyl methacrylate chains present in the second region at a higher rate than polystyrene chains present in the first region. Appearance 15. The objective is to obtain a layer of polystyrene-β-polymethyl methacrylate block copolymer, The layer contains multiple polymer domains, and each of the multiple polymer domains is The first region containing polystyrene chains; A second region containing a polymethyl methacrylate chain; A third region between the first region and the second region, A third region comprising the unseparated portions of the polystyrene chain and the polymethyl methacrylate chain; To obtain a layer of polystyrene-β-polymethyl methacrylate block copolymer containing; The method involves bringing the layer into contact with a solution to remove at least a portion of the polymethyl methacrylate chains from the second and third regions, so as to form a porous layer or a layer having surface morphology. The solution removes polymethyl methacrylate chains at a higher rate than polystyrene chains, thereby removing at least a portion of the polymethyl methacrylate chains from the second and third regions. Methods that include... Apparatus 16. The solution is At least one solvent in an amount of 5% to 90% by weight based on the total weight of the solution; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to embodiment 15, including the method described in embodiment 15. Embodiment 17. The method according to Embodiment 16, wherein the solution has a pH of less than 7. Apparatus 18. The solution is 50% to 99% by weight of at least one alcoholic solvent based on the total weight of the solution; Based on the total weight of the solution, at least one non-alcoholic solvent in an amount of 1% to 50% by weight; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to any one of embodiments 15 to 17, including the method described above. Apparatus 19. The solution is At least one solvent in an amount of 5% to 90% by weight based on the total weight of the solution; At least one swelling control agent in an amount of 1% to 25% by weight based on the total weight of the solution; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to any one of embodiments 15 to 18, including the method described above. Apparatus 20. The solution is At least one organic solvent in an amount of 5% to 90% by weight based on the total weight of the solution; and Based on the total weight of the solution, 10% to 95% by weight of water. The method according to any one of embodiments 15 to 19, including the method described above. In particular, it should be understood that detailed modifications may be made to the construction materials used, as well as the shape, size, and arrangement of components, without departing from the scope of this disclosure. This specification and the embodiments described herein are examples, and the true scope and spirit of this disclosure are indicated by the subsequent claims.

Claims

1. The objective is to obtain a layer of polystyrene-b-polymethyl methacrylate block copolymer, wherein the layer comprises a plurality of polymer domains, and each of the plurality of polymer domains is The first region containing polystyrene chains; Second region containing polymethyl methacrylate chain To obtain a layer of polystyrene-b-polymethyl methacrylate block copolymer containing, Removing at least a portion of the polymethyl methacrylate chains from a second region by bringing the layer into contact with a solution, wherein the polymethyl methacrylate chains are removed by the solution at a higher rate than the polystyrene chains. Methods that include...

2. The solution, At least one solvent in an amount of 5% to 90% by weight based on the total weight of the solution; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to claim 1, including the method described in claim 1.

3. The method according to claim 2, wherein the solution has a pH of less than 7.

4. The solution, 50% to 99% by weight of at least one alcoholic solvent based on the total weight of the solution; Based on the total weight of the solution, at least one non-alcoholic solvent in an amount of 1% to 50% by weight; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to claim 1, including the method described in claim 1.

5. The solution, A first alcohol solvent in an amount of 5% to 90% by weight, based on the total weight of the solution, of at least one such first alcohol solvent; At least one swelling control agent in an amount of 1% to 25% by weight based on the total weight of the solution, wherein at least one swelling control agent is a second alcohol solvent different from at least one first alcohol solvent; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to claim 1, including the method described in claim 1.

6. The solution, 5% to 90% by weight of at least one organic solvent based on the total weight of the solution; and 10% to 95% by weight of water based on the total weight of the solution The method according to claim 1, including the method described in claim 1.

7. The method according to claim 1, wherein the solution removes polymethyl methacrylate chains present in the second region at a higher rate than polystyrene chains present in the first region.

8. The objective is to obtain a layer of polystyrene-b-polymethyl methacrylate block copolymer, wherein the layer comprises a plurality of polymer domains, and each of the plurality of polymer domains is The first region containing polystyrene chains; Second region containing polymethyl methacrylate chain To obtain a layer of polystyrene-b-polymethyl methacrylate block copolymer containing, Exposing the layer to ultraviolet light, wherein at least a portion of the polymethyl methacrylate chains present in the second region are cleaved by the ultraviolet light, Removing at least a portion of polymethyl methacrylate chains from a second region by contacting the layer with a solution to form a porous layer or a layer having surface morphology, wherein the solution removes polymethyl methacrylate chains at a higher rate than polystyrene chains. Methods that include...

9. The solution, At least one solvent in an amount of 5% to 90% by weight based on the total weight of the solution; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to claim 8, including the method described in claim 8.

10. The method according to claim 9, wherein the solution has a pH of less than 7.

11. The solution, 50% to 99% by weight of at least one alcoholic solvent based on the total weight of the solution; Based on the total weight of the solution, at least one non-alcoholic solvent in an amount of 1% to 50% by weight; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to claim 8, including the method described in claim 8.

12. The solution, At least one solvent in an amount of 5% to 90% by weight based on the total weight of the solution; Based on the total weight of the solution, at least one swelling control agent in an amount of 1% to 25% by weight; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to claim 8, including the method described in claim 8.

13. The solution, 5% to 90% by weight of at least one organic solvent based on the total weight of the solution; and 10% to 95% by weight of water based on the total weight of the solution The method according to claim 8, including the method described in claim 8.

14. The method according to claim 8, wherein the solution removes polymethyl methacrylate chains present in the second region at a higher rate than polystyrene chains present in the first region.

15. The objective is to obtain a layer of polystyrene-b-polymethyl methacrylate block copolymer, wherein the layer comprises a plurality of polymer domains, and each of the plurality of polymer domains is The first region containing polystyrene chains; A second region containing a polymethyl methacrylate chain; A third region between the first and second regions, comprising the non-separated portions of the polystyrene chain and the polymethyl methacrylate chain. To obtain a layer of polystyrene-b-polymethyl methacrylate block copolymer containing, Removing at least a portion of polymethyl methacrylate chains from a second and a third region by contacting the layer with a solution to form a porous layer or a layer having surface morphology, wherein the solution removes polymethyl methacrylate chains at a higher rate than polystyrene chains. Methods that include...

16. The solution, At least one solvent in an amount of 5% to 90% by weight based on the total weight of the solution; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to claim 15, including the method described in claim 15.

17. The method according to claim 16, wherein the solution has a pH of less than 7.

18. The solution, 50% to 99% by weight of at least one alcoholic solvent based on the total weight of the solution; Based on the total weight of the solution, at least one non-alcoholic solvent in an amount of 1% to 50% by weight; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to claim 15, including the method described in claim 15.

19. The solution, At least one solvent in an amount of 5% to 90% by weight based on the total weight of the solution; Based on the total weight of the solution, at least one swelling control agent in an amount of 1% to 25% by weight; and A pH adjusting agent in an amount of 0.1% to 20% by weight, based on the total weight of the solution. The method according to claim 15, including the method described in claim 15.

20. The solution, 5% to 90% by weight of at least one organic solvent based on the total weight of the solution; and 10% to 95% by weight of water based on the total weight of the solution The method according to claim 15, including the method described in claim 15.

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