Polymer, composition including the same, and method of forming pattern using the composition

Abstract

Provided are a polymer including a first repeating unit represented by Formula 1 and having a glass transition temperature of 50 DEG C or less, a polymer-containing composition including the polymer, and a method of forming a pattern by using the polymer-containing composition, in which, in Formula 1, the description of L11 to L13, a11 to a13, A11, R11, R12, b12, and p1 is provided in the present specification. Formula 1 # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on and claims the benefit of priority from Korean Patent Application No. 10-2023-0102277 filed on August 4, 2023 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference. Technical Field

[0003] The present disclosure relates to polymers, polymer-containing compositions including the same, and methods of forming patterns by using the compositions. Background Art

[0004] In recent years, with the rapid popularization of information media, the performance of semiconductor devices has also been rapidly improved. In the case of recent semiconductor products, high integration of products is required for low cost and high quality to ensure competitiveness.

[0005] Meanwhile, as the integration degree of semiconductor devices increases, the distance between wirings may decrease, and an etching process is required to effectively form a plurality of wirings spaced apart from each other.

[0006] Therefore, there is a need for materials that have improved gap-filling properties, thereby preventing and / or reducing voids and / or seams, and that can be removed quickly while still acting as a protective barrier during subsequent processing. Summary of the invention

[0007] Provided are a polymer having improved resistance to wet etching (wet etching resistance), improved etching speed of dry etching and / or improved gap filling properties, a polymer-containing composition including the polymer, and a method of forming a pattern by using the polymer-containing composition.

[0008] Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.

[0009] According to one aspect of the present disclosure, the polymer includes a first repeating unit represented by Formula 1 and has a glass transition temperature of 50° C. or less:

[0010] Formula 1

[0011]

[0012] Among them, in formula 1,

[0013] L 11 To L 13may each independently be a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or a linear, branched or cyclic C optionally including a heteroatom 1 -C 30 Divalent hydrocarbon groups,

[0014] a11 to a13 may each independently be an integer from 1 to 4,

[0015] A 11 It may be a linear, branched or cyclic C 1 -C 30 alkyl, or a linear, branched or cyclic C 2 -C 30 Alkenyl,

[0016] R 11 and R 12 Each of them may be independently hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a linear, branched or cyclic C optionally including heteroatoms. 1 -C 30 Monovalent hydrocarbon groups,

[0017] b12 can be an integer from 1 to 10,

[0018] p1 can be an integer from 1 to 5, and

[0019] * indicates the binding site with the adjacent atom

[0020] According to another aspect of the present disclosure, a polymer-containing composition includes the polymer, an acid generator (acid generator), and an organic solvent.

[0021] According to another aspect of the present disclosure, a method for forming a pattern includes: forming an insulating layer by applying the polymer-containing composition to a substrate provided with a first layer; forming an insulating pattern exposing a first surface of the first layer by selectively removing at least a portion of the insulating layer; and removing the first layer having the exposed first surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The above and other aspects, features, and advantages of some embodiments of the present disclosure will become more apparent from the following description considered in conjunction with the accompanying drawings, in which:

[0023] Figure 1 A flow chart showing a method for forming a pattern according to at least one embodiment;

[0024] FIG. 2A to FIG. 2CEach is a side cross-sectional view illustrating a pattern forming method according to at least one embodiment; and

[0025] FIG. 3A to FIG. 3D Each is a side cross-sectional view illustrating a method of preparing a semiconductor device according to at least one embodiment. DETAILED DESCRIPTION

[0026] Embodiments will now be described in detail, examples of which are shown in the accompanying drawings, wherein the same reference numerals refer to the same elements throughout. In this regard, the present embodiment may have different forms and should not be construed as being limited to the description set forth herein. Therefore, embodiments are described below only by reference to the accompanying drawings to illustrate aspects. As used herein, the term "and / or" includes any and all combinations of one or more of the related enumerated items. Statements such as "at least one (kind)" when before or after a list of elements modify the entire list of elements and do not modify the individual elements of the list.

[0027] The present disclosure may undergo a variety of changes and may have a variety of embodiments. Therefore, specific embodiments will be shown in the drawings and described in detail in the detailed description. However, this is not intended to limit the disclosure to specific embodiments, and should be understood to include all modifications, equivalents and substitutes included in the spirit and technical scope of the present disclosure. When describing the disclosure, when it is determined that the detailed description of the relevant known technology may make the subject of the present disclosure unclear, the detailed description will be omitted.

[0028] The terms “first”, “second”, “third”, etc. may be used to describe various elements, but are only used for the purpose of distinguishing one element from other elements, and do not limit the order or type of the elements.

[0029] Throughout the specification, a portion of a layer, film, region, panel, etc., that is described as being "on" or "over" another portion thereof can be directly above, below, to the left or to the right while in contact, as well as above, below, to the left or to the right while not in contact.

[0030] Singular expressions include plural expressions unless the context clearly dictates otherwise. Unless otherwise specified, terms such as "include" or "have" are intended to indicate the presence of features, numbers, steps, operations, elements, parts, components, materials, or combinations thereof described in the specification, and it should be understood that the terms do not exclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, elements, parts, components, materials, or combinations thereof.

[0031] In addition, when the term "about" or "substantially" is used in conjunction with numerical and / or geometric terms in the specification, it is intended that the relevant numerical value includes a manufacturing tolerance (e.g., ±10%) around the stated numerical value. In addition, whether or not the numerical value is modified as "about" or "substantially", it will be understood that these values ​​should be interpreted as including manufacturing or operating tolerances (e.g., ±10%) around the stated numerical value. Whenever a range of values ​​is listed, the range includes all values ​​falling within the range, as if explicitly written, and further includes the boundaries of the range. Therefore, the range of "X to Y" includes all values ​​between X and Y, and also includes X and Y.

[0032] As used herein, the term "C x -C y ” refers to the case where the number of carbon atoms constituting the substituent is from x to y. For example, “C 1 -C 6 " refers to the case where the number of carbon atoms constituting the substituent is 1 to 6, and "C 6 -C 20 ” refers to the case where the number of carbon atoms constituting the substituent is 6 to 20.

[0033] The term "monovalent hydrocarbon group" as used herein refers to a monovalent residue derived from an organic compound including carbon and hydrogen or a derivative of the organic compound, and examples thereof may include: a linear or branched alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, and nonyl); a monovalent saturated cyclic aliphatic hydrocarbon group (e.g., cycloalkyl) (e.g., cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecyl, tetradecyl ...hexylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylbutyl, The invention also includes cyclododecyl, tetracyclododecylmethyl, and dicyclohexylmethyl groups; monovalent unsaturated aliphatic hydrocarbon groups (e.g., alkenyl, alkynyl, and allyl groups); monovalent unsaturated cyclic aliphatic hydrocarbon groups (e.g., cycloalkenyl and 3-cyclohexenyl); aryl groups (e.g., phenyl, 1-naphthyl, and 2-naphthyl); arylalkyl groups (e.g., benzyl and diphenylmethyl); monovalent hydrocarbon groups containing heteroatoms (e.g., tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl); or any combination thereof. Some of the hydrogen atoms in these groups may be replaced by moieties containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, or some of the carbon atoms in these groups may be replaced by moieties containing heteroatoms such as oxygen, sulfur, or nitrogen. Thus, these groups may include hydroxyl, cyano, carbonyl, carboxyl, ether linkage, ester linkage, sulfate linkage, carbonate linkage, lactone ring, sultone ring, carboxylic anhydride moiety, or haloalkyl moiety.

[0034] As used herein, the term "divalent hydrocarbon group" refers to a divalent residue in which one hydrogen of a monovalent hydrocarbon group is replaced by a bonding site with an adjacent atom. Examples of divalent hydrocarbon groups may include linear or branched alkylene, cycloalkylene, alkenylene, alkynylene, cycloalkenylene, arylene, or a group in which some carbon atoms are replaced by heteroatoms.

[0035] The term "alkyl" as used herein refers to a linear or branched saturated aliphatic hydrocarbon monovalent group, and examples thereof may include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, and / or the like. The term "alkylene" as used herein refers to a linear or branched saturated aliphatic divalent hydrocarbon group, and examples thereof may include methylene, ethylene, propylene, butylene, isobutylene, and / or the like.

[0036] The term "haloalkyl" as used herein refers to a group in which one or more hydrogen atoms of an alkyl group are replaced by a halogen, and examples may include CF 3and / or similar.

[0037] As used herein, the term "alkoxy" refers to a 101 A is a monovalent group represented by 101 is an alkyl group and O is oxygen. Examples thereof may include methoxy, ethoxy, isopropoxy and the like.

[0038] As used herein, the term "alkylthio" refers to a group consisting of the formula -SA 101 A is a monovalent group represented by 101 is an alkyl group and S is sulfur.

[0039] The term "haloalkoxy" as used herein refers to a group in which one or more hydrogen atoms of an alkoxy group are replaced by a halogen, and examples thereof may include -OCF 3 and / or similar.

[0040] The term "haloalkylthio" as used herein refers to a group in which one or more hydrogen atoms of an alkylthio group are replaced by halogen, and examples thereof may include -SCF 3 and / or similar.

[0041] The term "cycloalkyl" as used herein refers to a monovalent saturated hydrocarbon cyclic group, and examples thereof may include monocyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and / or the like, and polycyclic condensed cyclic groups such as norbornyl and adamantyl. The term "cycloalkylene" as used herein refers to a divalent saturated hydrocarbon cyclic group, and examples thereof include cyclopentylene, cyclohexylene, adamantylene, adamantylenemethyl, norbornylene, norbornylenemethyl, tricyclodecylene, tetracyclododecylene, tetracyclododecylenemethyl, dicyclohexylenemethyl and / or the like.

[0042] As used herein, the term "cycloalkoxy" refers to a cycloalkyloxy group having the formula -OA 102 A is a monovalent group represented by 102 is a cycloalkyl group. Examples thereof may include cyclopropyloxy, cyclobutyloxy, and the like.

[0043] As used herein, the term "cycloalkylthio" refers to a group consisting of the formula -SA 102 A is a monovalent group represented by 102 It is a cycloalkyl group.

[0044] The term "heterocycloalkyl" used herein refers to a group in which some carbon atoms of cycloalkyl are replaced by a portion including heteroatoms such as oxygen, sulphur or nitrogen, and the example of heterocycloalkyl includes an ether linking group, an ester linking group, a sulfonate linking group, a carbonate linking group, a lactone ring, a sultone ring or a carboxylic anhydride moiety. The term "heterocycloalkylene" used herein refers to a group in which some carbon atoms of cycloalkylene are replaced by a portion including heteroatoms such as oxygen, sulphur or nitrogen.

[0045] As used herein, the term "heterocycloalkoxy" refers to a 103 A is a monovalent group represented by 103 It is a heterocycloalkyl group.

[0046] As used herein, the term "alkenyl" refers to a linear or branched unsaturated aliphatic monovalent hydrocarbon group including one or more carbon-carbon double bonds. As used herein, the term "alkenylene" refers to a linear or branched unsaturated aliphatic divalent hydrocarbon group including one or more carbon-carbon double bonds.

[0047] As used herein, the term "alkenyloxy" refers to a 104 A is a monovalent group represented by 104 It is an alkenyl group.

[0048] The term "cycloalkenyl" as used herein refers to a monovalent unsaturated cyclic hydrocarbon group including one or more carbon-carbon double bonds and not having aromaticity. The term "cycloalkenylene" as used herein refers to a divalent unsaturated cyclic hydrocarbon group including one or more carbon-carbon double bonds.

[0049] As used herein, the term "cycloalkenyloxy" refers to a cycloalkenyloxy group of the formula -OA 105 A is a monovalent group represented by 105 It is a cycloalkenyl group.

[0050] As used herein, the term "heterocycloalkenyl" refers to a group in which some of the carbon atoms of a cycloalkenyl group are replaced by a moiety that includes a heteroatom such as oxygen, sulfur, or nitrogen. As used herein, the term "heterocycloalkenylene" refers to a group in which some of the carbon atoms of a cycloalkenylene group are replaced by a moiety that includes a heteroatom such as oxygen, sulfur, or nitrogen.

[0051] As used herein, the term "heterocycloalkenyloxy" refers to a heterocycloalkyleneoxy group of the formula -OA 106 A is a monovalent group represented by 106 It is a heterocycloalkenyl group.

[0052] The term "alkynyl" as used herein refers to a linear or branched unsaturated aliphatic monovalent hydrocarbon group including one or more carbon-carbon triple bonds.

[0053] As used herein, the term "alkynyloxy" refers to a 107 A is a monovalent group represented by 107 It is an alkynyl group.

[0054] The term "aryl" as used herein refers to a monovalent group having a carbocyclic aromatic system, and examples may include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, and base.

[0055] As used herein, the term "aryloxy" refers to a 108 A is a monovalent group represented by 108 It is an aromatic group.

[0056] The term "heteroaryl" as used herein refers to a monovalent group having a heterocyclic aromatic system, and examples thereof include pyridyl, pyrimidyl, pyrazinyl and / or the like. The term "heteroarylene" as used herein refers to a divalent group having a heterocyclic aromatic system.

[0057] As used herein, the term "heteroaryloxy" refers to a 109 A is a monovalent group represented by 109 It is a heteroaryl group.

[0058] The term "substituent" as used herein may include: deuterium, halogen, hydroxyl, cyano, nitro, carbonyl, carboxylic acid group, amino, ether moiety, ester moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C1 -C 20 Heteroaryloxy, or C 1 -C 20 heteroarylthio;

[0059] Each of the following is deuterated, halogenated, hydroxyl, cyano, nitro, carbonyl, carboxylic acid group, amino group, ether moiety, ester moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C 1 -C 20 Heteroaryloxy, C 1 -C 20 C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C20 Aryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C 1 -C 20 Heteroaryloxy, or C 1 -C 20 heteroarylthio; and any combination thereof.

[0060] Hereinafter, at least one embodiment will be described in detail with reference to the accompanying drawings, and in the description with reference to the accompanying drawings, substantially the same or corresponding elements are represented by the same reference numerals, and their repeated descriptions will be omitted. With respect to the accompanying drawings, the thickness is enlarged to clearly indicate each layer and region. In addition, in the accompanying drawings, the thickness of some layers and regions is exaggerated for ease of description. On the other hand, the embodiments described below are merely illustrative, and various changes may be made to these embodiments.

[0061] [polymer]

[0062] The polymer according to some embodiments includes a first repeating unit represented by Formula 1 and has a glass transition temperature of 50° C. or less:

[0063] Formula 1

[0064]

[0065] Wherein, in formula 1:

[0066] L 11 To L 13 may each independently be a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or a linear, branched or cyclic C optionally including a heteroatom 1 -C 30 Divalent hydrocarbon groups,

[0067] a11 to a13 may each independently be an integer from 1 to 4,

[0068] A 11 It may be a linear, branched or cyclic C 1 -C 30 Alkyl; or a linear, branched or cyclic C optionally including heteroatoms 2 -C 30 Alkenyl,

[0069] R 11 and R 12Each of them may be independently hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a linear, branched or cyclic C optionally including heteroatoms. 1 -C 30 Monovalent hydrocarbon groups,

[0070] b12 can be an integer from 1 to 10,

[0071] p1 can be an integer from 1 to 5, and

[0072] * indicates the binding site with the adjacent atom.

[0073] In at least one embodiment, the glass transition temperature of the polymer may be 25° C. or less. Here, the glass transition temperature is a value obtained by measurement, and an example measurement method is as described in further detail in the following examples.

[0074] In at least one embodiment, L in Formula 1 11 To L 13 may be independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); substituted or unsubstituted C 1 -C 30 Alkylene; substituted or unsubstituted C 3 -C 30 Cycloalkylene; substituted or unsubstituted C 3 -C 30 Heterocycloalkylene; substituted or unsubstituted C 2 -C 30 Alkenylene; substituted or unsubstituted C 3 -C 30 Cycloalkenylene; substituted or unsubstituted C 3 -C 30 Heterocycloalkenylene; substituted or unsubstituted C 6 -C 30 Arylene; or substituted or unsubstituted C 1 -C 30 Heteroarylene.

[0075] In at least one embodiment, L in Formula 1 11 To L 13 may be independently selected from a single bond; O; C(=O); C(=O)O; OC(=O); or C 1 -C 20 Alkylene, C 3 -C 20 Cycloalkylene, C 3 -C 20Heterocycloalkylene, C 2 -C 20 Alkenylene, C 3 -C 20 Cycloalkenylene, C 3 -C 20 Heterocycloalkenylene, C 6 -C 20 Arylene, or C 1 -C 20 Heteroarylene: deuterium, halogen, cyano, hydroxyl, amino, carboxylic acid group, thiol group, ester moiety, sulfonate moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 6 -C 20 aryl, or any combination thereof.

[0076] In at least one embodiment, L in Formula 1 11 To L 13 may be independently selected from a single bond; O; C(=O); C(=O)O; OC(=O); or C 1 -C 20 Alkylene, C 3 -C 20 Cycloalkylene, C 3 -C 20 Heterocycloalkylene, phenylene, or naphthylene: deuterium, halogen, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 alkoxy, phenyl, naphthyl, or any combination thereof.

[0077] In at least one embodiment, L in Formula 1 11 It may be selected from a single bond; O; C(=O); C(=O)O; or OC(=O).

[0078] In at least one embodiment, L in Formula 1 12 and L 13 may be independently selected from: a single bond; O; C(=O); C(=O)O; OC(=O); or C 1 -C20 Alkylene: deuterium, halogen, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 alkoxy, phenyl, naphthyl, or any combination thereof.

[0079] In Formula 1, a11 to a13 represent L 11 The number of repetitions to L 13 The number of repetitions.

[0080] In at least one embodiment, a11 to a13 in Formula 1 may each independently be an integer of 1 to 3.

[0081] In at least one embodiment, a11 to a13 in Formula 1 may each independently be 1.

[0082] In at least one embodiment, A in Formula 1 11 It may be a linear, branched or cyclic C 1 -C 30 alkyl.

[0083] In at least one embodiment, A in Formula 1 11 Can be selected from: groups represented by formulae 9-1 to 9-37 and 10-1 to 10-48; groups in which at least one carbon of one of the groups represented by formulae 9-1 to 9-37 and 10-2 to 10-48 is replaced by oxygen; and groups in which at least one carbon of one of the groups represented by formulae 9-1 to 9-37 and 10-2 to 10-48 is replaced by a carbonyl group:

[0084]

[0085]

[0086] Among them, in formulas 9-1 to 9-37 and 10-1 to 10-48,

[0087] *Indicates the same as L 11 binding site.

[0088] In Formulas 9-1 to 9-37 and 10-1 to 10-48, a number (e.g., p1) of hydrogens may each be replaced by OH, and the remaining hydrogens may each be replaced by R 12 replace.

[0089] In at least one embodiment, A in Formula 1 11 The groups represented by free formulas 10-1 to 10-48 may be selected.

[0090] In at least one embodiment, R in Formula 1 11 and R 12 may be independently selected from hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; or C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, or C 6 -C 20 Aryl: deuterium, halogen, cyano, hydroxyl, amino, carboxylic acid group, thiol group, ester moiety, sulfonate moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 6 -C 20 aryl, or any combination thereof.

[0091] In at least one embodiment, R in Formula 1 11 Can be hydrogen, deuterium, halogen, CH 3 , CH 2 F. CHF 2 CF 3 , CH 2 CH 3 , CHFCH 3 , CHFCH 2 F. CHFCHF 2 , CHFCF 3 CF 2 CH 3 CF 2 CH 2 F. CF 2 CHF 2 , or CF 2 CF 3 .

[0092] In at least one embodiment, R in Formula 1 12 It can be hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; C 1 -C 20 Alkyl; C 1 -C 20 Haloalkyl; C 3 -C 20Cycloalkyl; or C 6 -C 20 Aryl.

[0093] In at least one embodiment, the first repeating unit can be represented by Formula 1-1:

[0094] Formula 1-1

[0095]

[0096] Among them, in formula 1-1,

[0097] L 11 To L 13 , a11 to a13, and R 11 can each be defined as in Formula 1,

[0098] r1 can be an integer from 1 to 3,

[0099] R 12a To R 12d can be respectively compared with R in formula 1 12 Defined similarly, and

[0100] *Indicates the binding site with the adjacent atom.

[0101] In at least one embodiment, the first repeating unit may be selected from Group I:

[0102] Group I

[0103]

[0104] In one or more embodiments, the polymer may further include at least one of a second repeating unit represented by Formula 2 and a third repeating unit represented by Formula 3:

[0105] Formula 2

[0106]

[0107] Formula 3

[0108]

[0109] Among them, in formulas 2 and 3,

[0110] L 21 To L 23 and L 31 To L 33 may each independently be a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or a linear, branched or cyclic C optionally including a heteroatom 1 -C 30Divalent hydrocarbon groups,

[0111] a21 to a23 and a31 to a33 may each independently be an integer of 1 to 4,

[0112] A 21 and A 31 may be each independently a linear, branched or cyclic C 1 -C 30 Alkyl; linear, branched or cyclic C optionally including heteroatoms 2 -C 30 or optionally including heteroatoms C 1 -C 30 Aromatic groups,

[0113] n2 can be 0 or 1,

[0114] R 21 , R 22 , R 31 and R 32 Each of them may be independently hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a linear, branched or cyclic C optionally including heteroatoms. 1 -C 30 Monovalent hydrocarbon groups,

[0115] b22 and b32 may each independently be an integer from 1 to 10,

[0116] p2 can be an integer from 1 to 5, and

[0117] *Indicates the binding site with the adjacent atom.

[0118] In at least one embodiment, L in Formulas 2 and 3 21 To L 23 and L 31 To L 33 Can be independently as L 11 For example, L 21 To L 23 and L 31 To L 33 The group selected from L 11 The groups selected are identical and / or substantially similar.

[0119] In at least one embodiment, a21 to a23 and a31 to a33 in Formulae 2 and 3 may each independently be as defined for a11. For example, a21 to a23 and a31 to a33 may each independently be an integer of 1 to 3.

[0120] A 21 and A 31 The selected group can be 11 The groups selected from are identical and / or substantially similar. For example, in at least one embodiment, in Formulas 2 and 3, A 21 and A 31 may be independently: a linear, branched or cyclic C optionally including heteroatoms 1 -C 30 or optionally including heteroatoms C 1 -C 30 Aromatic groups.

[0121] In at least one embodiment, in Formulas 2 and 3, A 21 and A 31 Each independently may be selected from the groups represented by formulae 9-1 to 9-37 and 10-1 to 10-48; the group in which at least one carbon of one of the groups represented by formulae 9-1 to 9-37 and 10-2 to 10-48 is replaced by oxygen; the group in which at least one carbon of one of the groups represented by formulae 9-1 to 9-37 and 10-2 to 10-48 is replaced by a carbonyl group; a benzene group; a naphthalene group; a phenanthrene group; and an anthracene group:

[0122]

[0123]

[0124] Among them, in formulas 9-1 to 9-37 and 10-1 to 10-48,

[0125] *Indicates the same as L 21 or L 31 binding site.

[0126] In Formulas 9-1 to 9-37 and 10-1 to 10-48 of Formula 2, a number (eg, p2) of hydrogens may each be replaced by COOH, and the remaining hydrogens may each be replaced by R 22 replace.

[0127] In at least one embodiment, R in Formulas 2 and 3 21 , R 22 , R 31 and R 32 Can be independently as R 11 As defined in .

[0128] In at least one embodiment, R in Formula 3 32 It may be a linear, branched or cyclic C 1 -C 30 A monovalent hydrocarbon group.

[0129] In at least one embodiment, the second repeating unit may be represented by one or two or more selected from Group II:

[0130] Group II

[0131]

[0132] In at least one embodiment, the third repeating unit may be represented by one or two or more selected from Group III:

[0133] Group III

[0134]

[0135] In at least one embodiment, the polymer may include the first repeating unit in an amount ranging from about 1 mol % to about 100 mol %, from about 5 mol % to about 100 mol %, and from about 10 mol % to about 100 mol %.

[0136] In one or more embodiments, the polymer chain may consist of the first repeating unit.

[0137] In one or more embodiments, the polymer may include the second repeating unit in an amount ranging from about 0 mol % to about 99 mol %, from about 1 mol % to about 99 mol %, and from about 10 mol % to about 90 mol %.

[0138] In one or more embodiments, the polymer may include the third repeating unit in an amount ranging from about 0 mol % to about 99 mol %, from about 1 mol % to about 99 mol %, and from about 10 mol % to about 90 mol %.

[0139] In one or more embodiments, the polymer may include a polymer chain consisting of the first repeating unit and the second repeating unit. For example, in at least one embodiment, the polymer chain of the polymer may consist of a copolymer of the first repeating unit and the second repeating unit. In one or more embodiments, the polymer may include the first repeating unit in an amount ranging from about 1 mol % to about 99 mol % or from about 10 mol % to about 90 mol %, and include the second repeating unit in an amount ranging from about 1 mol % to about 99 mol % or from about 10 mol % to about 90 mol %.

[0140] In one or more embodiments, the polymer may include a polymer chain consisting of the first repeating unit and the third repeating unit. For example, in at least one embodiment, the polymer chain of the polymer may consist of a copolymer of the first repeating unit and the third repeating unit. In one or more embodiments, the polymer may include the first repeating unit in an amount ranging from about 1 mol % to about 99 mol % or from about 10 mol % to about 90 mol %, and include the third repeating unit in an amount ranging from about 1 mol % to about 99 mol % or from about 10 mol % to about 90 mol %.

[0141] In one or more embodiments, the polymer may include a polymer chain consisting of the first repeating unit, the second repeating unit, and the third repeating unit. For example, in at least one embodiment, the polymer chain of the polymer may be composed of a copolymer of the first repeating unit, the second repeating unit, and the third repeating unit. In one or more embodiments, the polymer may include the first repeating unit in an amount ranging from about 1 mol % to about 98 mol % or from about 5 mol % to about 90 mol %, include the second repeating unit in an amount ranging from about 1 mol % to about 98 mol % or from about 5 mol % to about 90 mol %, and include the third repeating unit in an amount ranging from about 1 mol % to about 98 mol % or from about 5 mol % to about 90 mol %.

[0142] The polymer may have a weight average molecular weight (Mw) ranging from about 1,000 to 100,000, for example, from about 2,000 to about 80,000 and / or from about 3,000 to about 50,000, wherein the weight average molecular weight Mw is measured by gel permeation chromatography using tetrahydrofuran as a solvent and polystyrene as a standard material.

[0143] In at least one embodiment, the polymer may consist of: the first repeating unit; or the first repeating unit and the second repeating unit, wherein the polymer may have a weight average molecular weight Mw in the range of about 3,000 to about 10,000.

[0144] The polymer may have a polydispersity index (PDI: Mw / Mn) in the range of about 1.0 to about 3.0, for example, about 1.0 to about 2.5. Within these ranges, the possibility of foreign matters remaining on the pattern may be reduced, or the deterioration of the pattern profile may be minimized. Therefore, the polymer-containing composition may be suitable for forming a fine pattern.

[0145] The structure (composition) of the polymer can be confirmed by performing Fourier transform infrared (FT-IR) analysis, nuclear magnetic resonance (NMR) analysis, X-ray fluorescence (XRF) analysis, mass spectrometry, ultraviolet UV analysis, single crystal X-ray structure analysis, powder X-ray diffraction (PXRD) analysis, liquid chromatography (LC) analysis, size exclusion chromatography (SEC) analysis, thermal analysis and / or the like. Example confirmation methods are described in detail in the following examples.

[0146] Since the polymer including the first repeating unit represented by Formula 1 includes one or more OH groups, adhesion to a lower film, for example, a lower film including an inorganic material, may be improved.

[0147] Also, when forming a film, the polymer including the first repeating unit represented by Formula 1 may undergo a cross-linking reaction, for example, an esterification reaction and / or an etherification reaction, and such a cross-linked product may have relatively high resistance to a wet etching process.

[0148] In addition, since the polymer including the first repeating unit represented by Formula 1 has a relatively low glass transition temperature, the polymer may have improved gap-filling properties.

[0149] When the polymer including the first repeating unit represented by Formula 1 further includes the second repeating unit represented by Formula 2, adhesion to a lower film including an inorganic material may be improved and / or an etching rate in a dry etching process may be accelerated.

[0150] When the polymer including the first repeating unit represented by Formula 1 further includes the second repeating unit represented by Formula 3, the density of the polymer may be increased, and thus, swelling of a film formed of the polymer to an etchant may be reduced.

[0151] [Polymer-containing composition]

[0152] Another aspect of the present disclosure provides a polymer-containing composition including the polymer, an acid generator, and an organic solvent.

[0153] As the polymer including the repeating unit represented by Formula 1 and used in the polymer-containing composition, one type of polymer or a combination of two or more different types of polymers may be used.

[0154] The polymer may be included in an amount of about 0.1 parts by weight to about 50 parts by weight based on 100 parts by weight of the polymer-containing composition. Specifically, the polymer may be included in an amount of about 0.5 parts by weight to about 30 parts by weight based on 100 parts by weight of the polymer-containing composition. When the amount of the polymer is satisfied within the above range, any performance loss, such as the formation of foreign particles due to lack of solubility and / or degradation of film-forming properties, may be reduced.

[0155] The polymer-containing composition may not include a crosslinking agent. Even if the polymer-containing composition does not include a crosslinking agent, when the polymer-containing composition is applied and heated or exposed, a crosslinking reaction, such as an esterification reaction and / or an etherification reaction, in which the acid generator may act as a catalyst, may occur.

[0156] The polymer is as defined above, and the acid generator, the organic solvent, and additional components such as a surfactant included as necessary will be described below.

[0157] <Acid Generator>

[0158] The acid generator may be selected to promote the cross-linking reaction of the polymer-containing composition.

[0159] The acid generator may be configured to generate acid via light and / or heat.

[0160] The acid generator may be, for example, a photoacid generator and / or a thermal acid generator. In at least one embodiment, the acid generator may include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, pyridinium trifluoromethanesulfonate, salicylic acid, 5-sulfosalicylic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, 4-phenolsulfonic acid, 4-phenolsulfonic acid methyl ester, benzene disulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, or any combination thereof.

[0161] The acid generator may be included in an amount ranging from about 0.01 parts by weight to about 40 parts by weight, from about 0.1 parts by weight to about 40 parts by weight, or from about 0.1 parts by weight to about 20 parts by weight, based on 100 parts by weight of the polymer.

[0162] One type of acid generator may be used, or a combination of two or more different types of acid generators may be used.

[0163] <Organic Solvents>

[0164] The organic solvent included in the polymer-containing composition may be selected based on the ability of the organic solvent to dissolve and / or disperse the polymer, the acid generator, and additional components contained as needed.

[0165] Examples of the organic solvent may include an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an amide-based solvent, an ester-based solvent, a sulfoxide-based solvent, a hydrocarbon-based solvent, and / or the like.

[0166] Examples of the alcohol-based solvent may include monohydric alcohol-based solvents (e.g., methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, 4-methyl-2-pentanol (MIBC), sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol and / or the like; polyol solvents (e.g. ethylene glycol, 1,2-propylene glycol, 1,3-Butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol); and ether solvents containing polyols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and / or the like.

[0167] Examples of the ether-based solvent may include dialkyl ether-based solvents (e.g., diethyl ether, dipropyl ether, dibutyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and / or the like); cyclic ether-based solvents (e.g., tetrahydrofuran, tetrahydropyran, and / or the like); and aromatic ring-containing ether-based solvents (e.g., diphenyl ether, anisole, and / or the like).

[0168] Examples of the ketone-based solvent may include linear ketone solvents (e.g., acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-amyl ketone, diethyl ketone, methyl isobutyl ketone, 2-heptanone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonanone, and / or the like); cyclic ketone-based solvents (e.g., cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, and / or the like); 2,4-pentanedione; acetonylacetone; acetophenone; and / or the like.

[0169] Examples of the amide-based solvent may include cyclic amide-based solvents (e.g., N,N'-dimethylimidazolidinone, N-methyl-2-pyrrolidone, and / or the like); chain amide-based solvents (e.g., N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and / or the like); and / or the like.

[0170] Examples of the ester-based solvent may include acetate solvents (e.g., methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-amyl acetate, isoamyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methylamyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, and / or the like); ether carboxylate solvents containing polyols (e.g., ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ...methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate and / or the like); lactone solvents (e.g., γ-butyrolactone and δ-valerolactone); carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; lactate solvents such as methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate and / or the like; glycol diacetate; methoxytriglycol acetate; ethyl propionate; n-butyl propionate; isoamyl propionate; diethyl oxalate; di-n-butyl oxalate; methyl acetoacetate; ethyl acetoacetate; diethyl malonate; dimethyl phthalate; diethyl phthalate; and / or the like.

[0171] Examples of the sulfoxide-based solvent may include dimethyl sulfoxide, diethyl sulfoxide, and / or the like.

[0172] Examples of the hydrocarbon-based solvent may include aliphatic or alicyclic hydrocarbon-based solvents (e.g., n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, methylcyclohexane, and / or the like); and aromatic hydrocarbon-based solvents (e.g., benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, and / or the like).

[0173] In at least one embodiment, the organic solvent may be selected from an alcohol-based solvent, an amide-based solvent, an ester-based solvent, a sulfoxide-based solvent, and / or any combination thereof. In one or more embodiments, the organic solvent may be selected from propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, ethyl lactate, dimethyl sulfoxide, and / or any combination thereof.

[0174] In at least one embodiment, when an acid-labile group (e.g., in the form of acetal) is used, the organic solvent may further include a high boiling point alcohol (e.g., diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, 1,3-butanediol, and / or the like) to accelerate the deprotection reaction of the acetal.

[0175] One type of organic solvent may be used, or a combination of two or more different types of organic solvents may be used.

[0176] The organic solvent may be used in an amount ranging from about 200 parts by weight to about 20,000 parts by weight, for example, from about 2,000 to about 10,000 parts by weight, based on 100 parts by weight of the polymer.

[0177] <Additional Components>

[0178] The polymer-containing composition may further include a surfactant, an additive, or any combination thereof as required.

[0179] The polymer-containing composition may further include a surfactant to improve coating properties and / or the like. Examples of the surfactant may include a nonionic surfactant (e.g., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and / or the like); and / or the like. For use as a surfactant, a commercially available product may be used, or a synthetic product may be used. Examples of commercially available products may include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75 and POLYFLOW No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), FTOP EF301, FTOP EF303, and FTOP EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE F171 (registered trademark), MEGAFACE F173, R40, R41, and R43 (manufactured by DIC Corporation), Fluorad FC430 (registered trademark) and Fluorad FC431 (manufactured by 3M Company), AsahiGuard AG710 (product of AGC Corporation), Surflon S-382 (registered trademark), Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105 and Surflon SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.), and / or the like.

[0180] The surfactant may be included in an amount of about 0 parts by weight to about 20 parts by weight, based on 100 parts by weight of the polymer.

[0181] One type of surfactant may be used, or a combination of two or more different types of surfactants may be used.

[0182] The polymer-containing composition may further include an additive to improve the adhesion of the substrate to which the polymer-containing composition is applied, and to prevent the stripping of the film formed by the polymer-containing composition when it is not desired. Examples of the additive may include aromatic hydroxy compounds, such as phenol, cresol, xylenol, catechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicyl alcohol, p-hydroxybenzyl alcohol, p-hydroxyphenylethanol, p-aminophenol, m-aminophenol, diaminophenol, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid and / or the like. In at least some embodiments, the additive for improving adhesion may be selected as an additive for supporting the adhesion of -OH of Formula 1.

[0183] The additive may be included in an amount ranging from about 0 parts by weight to about 20 parts by weight, based on 100 parts by weight of the polymer.

[0184] One type of additive may be used, or a combination of two or more different types of additives may be used.

[0185] The method for preparing the polymer-containing composition is not particularly limited, and for example, a method of mixing a polymer, an acid generator, and optional components added as needed in an organic solvent may be used. The temperature or time during mixing is not particularly limited. If necessary, filtering may be performed after mixing.

[0186] [Pattern Formation Method]

[0187] In the following, reference will be made to Figure 1 and 2A 2C describe the pattern forming method according to the embodiment in more detail. Figure 1 is a flow chart showing a pattern forming method according to at least one embodiment, and Figures 2A to 2C Each is a side cross-sectional view illustrating a pattern forming method according to at least one embodiment.

[0188] Reference Figure 1 and 2A To 2C, the method of forming a pattern includes: forming an insulating layer by applying the polymer-containing composition to a substrate provided with a first layer S100; forming an insulating pattern exposing a first surface of the first layer by selectively removing at least a portion of the insulating layer S200; and removing the first layer having the exposed first surface S300.

[0189] First, prepare a substrate (e.g., Figure 3A100). The substrate may be, for example, a semiconductor substrate such as a silicon substrate, a germanium substrate, and / or the like, and / or may include glass, quartz, ceramic, copper, and / or the like. In at least one embodiment, the substrate may include a III-V compound such as GaP, GaAs, GaSb, and / or the like.

[0190] The first layer 10 may be disposed on a substrate. The first layer 10 may include, for example, a conductive metal oxide, a conductive metal oxynitride, a conductive metal nitride, or any combination thereof. In at least one embodiment, the first layer 10 may include titanium nitride, titanium oxynitride, or any combination thereof. The first layer 10 may further include an organic polymer. The first layer 10 may be formed by, for example, atomic layer deposition (ALD), chemical vapor deposition (CVD), reactive sputtering, ion plating, vacuum deposition, spin coating (e.g., spin on glass (SOG)).

[0191] Next, on the substrate provided with the first layer 10, the aforementioned polymer-containing composition may be applied to a desired thickness according to an appropriate coating method to form the insulating layer 20. The insulating layer 20 may be a dry etching resist layer and / or a wet etching resist layer, but the embodiment is not limited thereto.

[0192] The thickness of the insulating layer 20 may be, for example, in a range of about 0.001 μm to about 10 μm, for example, about 0.002 μm to about 1 μm, and for example, about 0.005 μm to about 0.5 μm.

[0193] Since the polymer-containing composition includes the acid generator, an acid may be generated when a stimulus such as light and / or heat is applied, and thus a cross-linking reaction of the polymer-containing composition may be promoted.

[0194] Therefore, when forming the insulating layer 20, the substrate 100 to which the polymer-containing composition is applied may be optionally baked using a heating device such as a hot plate. The lower limit of the baking temperature may be 60°C or higher, such as 80°C or higher. In addition, the upper limit of the baking temperature may be 150°C or lower, such as 140°C or lower. When the baking temperature is lower than the above range, crosslinking may not be fully formed, so that the insulating layer 20 formed thereby may not have sufficient resistance to etchants. When the baking temperature is higher than the above range, the insulating layer 20 may be thermally decomposed. The lower limit of the baking time may be 5 seconds or longer, such as 10 seconds or longer. The upper limit of the baking time may be 600 seconds or less, such as 300 seconds or less.

[0195] Next, a resist pattern (not shown) may be additionally formed on the insulating layer 20. The resist pattern may be formed by a conventional method, such as a resist pattern forming method including applying a resist composition, exposing and developing. The resist pattern thus formed may be used as a mask in forming an insulating pattern.

[0196] Next, at least a portion of the insulating layer 20 may be selectively removed to form an insulating pattern 21 or 22 exposing the first surface 10US of the first layer 10 .

[0197] The insulating pattern 21 or 22 may be formed by using a dry etching process, and for example, may be formed by a dry etching process using the aforementioned resist pattern as a mask. The type of gas used in the dry etching process is not particularly limited, but a freon-based gas, an oxygen-based gas (oxygen-based gas), and / or a nitrogen-based gas (nitrogen-based gas) may be used.

[0198] Next, the first layer 10 having the exposed first surface 10US may be removed by using a wet etching process. Here, the insulating pattern 21 or 22 may be used as a mask. The etchant used in the wet etching process may include hydrogen peroxide. The etchant may further include: an alkaline substance (e.g., ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, etc.); an organic amine (e.g., triethanolamine); and / or an acidic substance (e.g., an inorganic acid, such as hydrochloric acid, sulfuric acid, and / or the like).

[0199] Next, the insulating pattern 21 or 22 may be removed. The insulating pattern 21 or 22 may be removed by using a wet etching process, an ashing process, or any combination thereof.

[0200] If desired, the steps may be omitted, or the steps may be performed in reverse order.

[0201] [Method for producing a semiconductor device]

[0202] In the following, reference will be made to Figure 3A and 3D A method of fabricating a semiconductor device according to some embodiments is described in detail.

[0203] In the drawings of semiconductor devices to be described below, at least one embodiment depicts a semiconductor device having a gate-all-around transistor, but the embodiments are not limited thereto.

[0204] In one or more embodiments, the semiconductor device may include a field effect transistor (FET), a planar FET, a fin FET, a tunnel FET, or a 3D transistor. In one or more embodiments, the semiconductor device may include a planar transistor without difficulty. In addition, the technical concept of the present disclosure can be applied to FETs based on 2D materials and their heterostructures.

[0205] Furthermore, in one or more implementations, the semiconductor device may include a bipolar junction (bipolar) transistor, a lateral double diffused metal oxide transistor, or the like.

[0206] Reference Figure 3A , providing a substrate 100. The substrate 100 may include a first region I and a second region II. The first region I and the second region II may be adjacent to each other, or may be separated from each other.

[0207] The first active pattern AP1 may be formed in the first region I of the substrate 100. The second active pattern AP2 may be formed in the second region II of the substrate 100. A portion in which the first active pattern AP1 and the second active pattern AP2 exist may be an active region.

[0208] The first active pattern AP1 may have a first bottom pattern BP1 and a plurality of first sheet patterns UP1. The second active pattern AP2 may have a second bottom pattern BP2 and a plurality of second sheet patterns UP2. The first sheet pattern UP1 and the second sheet pattern UP2 are shown as having three each, but are shown only for convenience of explanation and are not limited thereto.

[0209] The first bottom pattern BP1 and the second bottom pattern BP2 may protrude from the substrate 100 in the second direction D2 and be elongated (extended long) in the third direction D3. The first bottom pattern BP1 and the second bottom pattern BP2 may be spaced apart from each other in the first direction (D1). The first direction D1, the second direction D2, and the third direction D3 may intersect each other. The first direction D1, the second direction D2, and the third direction D3 may be substantially perpendicular to each other.

[0210] The field insulating film 105 may be formed between the first bottom pattern BP1 and the second bottom pattern BP2. The field insulating film 105 may include, for example, an oxide film, a nitride film, an oxynitride film, or any combination thereof.

[0211] Then, a gate insulating film 130 may be formed. The gate insulating film 130 may be formed on the upper surface of the field insulating film 105, a portion of the side surface and the upper surface of the first bottom pattern BP1, a portion of the side surface and the upper surface of the second bottom pattern BP2, the first sheet pattern UP1 and the second sheet pattern UP2. The gate insulating film 130 may surround the periphery of the first sheet pattern UP1 and the second sheet pattern UP2. The gate insulating film 130 may include a high dielectric constant material.

[0212] The work function metal layer 140 may be formed on the substrate 100. The work function metal layer 140 may be formed on the gate insulating film 130. The work function metal layer 140 may surround the periphery of the first pattern UP1 and the second pattern UP2. The work function metal layer 140 may include a conductive metal oxide, a conductive metal oxynitride, a conductive metal nitride, or any combination thereof. In at least one embodiment, the work function metal layer 140 may include titanium nitride, titanium oxynitride, or any combination thereof.

[0213] The protective layer 150 may be formed on the work function metal layer 140. The protective layer 150 may cover the work function metal layer 140. Materials included in the protective layer 150 may be the same as or similar to those included in the work function metal layer 140. For example, the protective layer 150 may include titanium nitride, but embodiments are not limited thereto.

[0214] Reference Figure 3B , an insulating layer may be formed on the protective layer 150 by using the aforementioned polymer-containing composition. The protective layer 150 and the insulating layer may then be combined to form a sacrificial layer 160.

[0215] Reference Figure 3C , a resist pattern PR1 may be formed on the sacrificial layer 160. The resist pattern PR1 may cover a portion of the sacrificial layer 160 on the first region I and the sacrificial layer 160 on the second region II.

[0216] Next, the insulating layer in the sacrificial layer 160 may be removed by using the resist pattern PR1 as a mask. By removing the insulating layer in the sacrificial layer 160, the surface of the protective layer 150 may be exposed. The removal of the insulating layer in the sacrificial layer 160 may be performed by a dry etching process, but the embodiment is not limited thereto.

[0217] Reference Figure 3D , in the first region I, the protective layer 150 and the work function metal layer 140 may be removed. The protective layer 150 of only the first region I may be selectively removed. The removal of the protective layer 150 and the work function metal layer 140 in the first region I may be performed by a wet etching process. When the wet etching process is performed, the protective layer 150 and the work function metal layer 140 may be removed, but the sacrificial layer 160 may not be removed. The etchant used in the wet etching process may not penetrate (penetrate) the insulating layer. Therefore, the etchant may not reach the sacrificial layer 160 of the second region II, and therefore the sacrificial layer 160 of the second region II may not be removed.

[0218] Next, the insulating layer within the sacrificial layer 160 of the second region II may be removed to form the protection layer 150. The insulating layer may be removed by using a wet etching process, an ashing process, or any combination thereof, but the embodiment is not limited thereto.

[0219] The present disclosure will be described in more detail using Examples and Comparative Examples, but the technical scope of the present disclosure is not limited to the following Examples.

[0220] [Example]

[0221] Synthesis Example 1: Synthesis of polymer pHEA

[0222] V601(C 10 H 18 N 2 O2 Azo initiator (0.99 g, 0.0043 mol) and hydroxyethyl acrylate (HEA) (5 g, 0.043 mol) as monomer 1 were dissolved in propylene glycol monomethyl ether (PGME) (9.3 g), and the mixed solution was allowed to react at 80° C. for 4 hours. Next, precipitation was performed using diethyl ether, and the precipitate was dried to form a polymer HEA (pHEA).

[0223] Synthesis Examples 2 to 7

[0224] The polymers were obtained in the same manner as in Synthesis Example 1, except that Monomers 1 and 2 of Table 1 were used instead of Monomer 1 alone. The polymers obtained by Synthesis Examples 1 to 7 were obtained by 1 H-NMR and gel permeation chromatography (GPC) analysis, and the weight average molecular weight, PDI and glass transition temperature (Tg) thereof were measured, and the results thereof are shown in Table 2. Here, thermal analysis (N 2 Atmosphere, temperature interval: at room temperature and up to 600°C (10°C / min, disposable Al pan) to obtain the glass transition temperature Tg.

[0225] [Table 1]

[0226]

[0227]

[0228] [Table 2]

[0229]

[0230]

[0231] Comparative Synthesis Example 1: Synthesis of Polymer NPs

[0232] Referring to KR2019-0057281A, a polymer NP (pNP) having the following structure was synthesized. The weight average molecular weight of the pNP may be 1,360, and the PDI of the pNP is 1.2.

[0233]

[0234] Evaluation example

[0235] The polymers shown in Tables 3 and 4, pyridinium trifluoromethanesulfonate (acid generator), gallic acid monohydrate (additive) and R-43 (source: DIC, surfactant) were each dissolved in propylene glycol methyl ether (PGME) to a concentration of 10% by weight to prepare a stock solution. The prepared stock solution was mixed in the amounts shown in Tables 3 and 4, and then 1.5 mL of PGME was added thereto to prepare a coating solution. The prepared coating solution was spin-coated at 1,500 rpm for 60 seconds on a silicon wafer on which TiN was deposited to a thickness of 7 nm. After spin coating, the silicon wafer was baked at 220° C. for 1 minute to form a film having a thickness of about 150 nm.

[0236] (1) Evaluation of etching rate

[0237] Next, a dry etching device Plasmalab 100RIE (source: Oxford Instruments Plasma Technology) was used with H 2 / N 2 The plasma etched the film for 0 to 6 seconds. Then, the change in film thickness was observed. The etching rate was calculated from the change in film thickness and is shown in Table 3.

[0238] Table 3

[0239]

[0240]

[0241] Referring to Table 3, it was confirmed that the polymers of Examples 1-1 to 1-9 had faster etching speeds than the polymer of Comparative Example 1-1. In addition, it was confirmed that the etching speed of the polymer can be adjusted depending on the amount of the monomer 2 including COOH.

[0242] (2) Evaluation of wet etching resistance

[0243] Next, the film was immersed in a 20 wt % aqueous hydrogen peroxide solution at 70° C. for 2 minutes and 30 seconds. Then, wet etching resistance was evaluated by confirming whether the film peeled off from the TiN surface. In Table 4, the case where peeling did not occur was indicated as pass, and the case where peeling occurred was indicated as fail.

[0244] [Table 4]

[0245]

[0246]

[0247] With reference to Table 4, it was confirmed that Examples 2-1 to 2-28 were all able to provide a thin film having etching resistance to an aqueous hydrogen peroxide solution. In particular, with reference to Examples 2-1, 2-5, 2-9, 2-13, 2-17, 2-21, and 2-25, it was confirmed that the use of the polymer of the present disclosure was able to provide a thin film having etching resistance to an aqueous hydrogen peroxide solution even without using an additive.

[0248] According to one or more embodiments, provided are a polymer having improved resistance to wet etching, improved etching speed of dry etching, and / or improved gap filling properties, a polymer-containing composition including the polymer, and a method of forming a pattern by using the polymer-containing composition.

[0249] It should be understood that the example embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. The description of features or aspects in each embodiment should typically be considered to be applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and detail may be made therein without departing from the spirit and scope as defined by the appended claims.

Claims

1. A polymer comprising a first repeating unit represented by Formula 1 and having a glass transition temperature of 50° C. or less: (Formula 1) in, In formula 1, L 11 To L 13 each independently represents a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or a linear, branched or cyclic C1-C ... 30 Divalent hydrocarbon groups, a11 to a13 are each independently an integer of 1 to 4, A 11 is a linear, branched or cyclic C1-C 30 or a linear, branched or cyclic C2-C 30 Alkenyl, R 11 and R 12 each independently hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a linear, branched or cyclic C1-C ... 30 Monovalent hydrocarbon groups, b12 is an integer from 1 to 10, p1 is an integer from 1 to 5, and *Indicates the binding site with the adjacent atom.

2. The polymer of claim 1, wherein the polymer has a glass transition temperature of 25°C or less.

3. The polymer of claim 1, wherein L 11 To L 13 each independently represents a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); substituted or unsubstituted C1-C 30 Alkylene; substituted or unsubstituted C3-C 30 Cycloalkylene; substituted or unsubstituted C3-C 30 Heterocycloalkylene; substituted or unsubstituted C2-C 30 Alkenylene; substituted or unsubstituted C3-C 30 Cycloalkenylene; substituted or unsubstituted C3-C 30 Heterocycloalkenylene; substituted or unsubstituted C6-C 30 Arylene; or substituted or unsubstituted C1-C 30 Heteroarylene.

4. The polymer according to claim 1, wherein L 11 is a single bond; O; C(=O); C(=O)O; or OC(=O), and L 12 and L 13 are each independently a single bond; O; C(=O); C(=O)O; OC(=O); and C1-C 20 Alkylene: deuterium, halogen, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 alkoxy, phenyl, naphthyl, or a combination thereof.

5. The polymer according to claim 1, wherein A 11 is a linear, branched or cyclic C1-C 30 alkyl.

6. The polymer of claim 1, wherein A 11 A group selected from the group represented by formulae 9-1 to 9-37 and 10-1 to 10-48, a group in which at least one carbon of one of the groups represented by formulae 9-1 to 9-37 and 10-2 to 10-48 is replaced by oxygen, or a group in which at least one carbon of one of the groups represented by formulae 9-1 to 9-37 and 10-2 to 10-48 is replaced by a carbonyl group in, In formulas 9-1 to 9-37 and 10-1 to 10-48, * indicates 11 binding site.

7. The polymer of claim 1, wherein A 11 A group selected from the group represented by formulae 10-1 to 10-48: in, In formulas 10-1 to 10-48, * represents 11 binding site.

8. The polymer of claim 1, wherein R 11 and R 12 are each independently hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; and C1-C 20 Alkyl, C3-C 20 Cycloalkyl, or C6-C 20 Aryl: deuterium, halogen, cyano, hydroxyl, amino, carboxylic acid group, thiol group, ester moiety, sulfonate moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C3-C 20 Cycloalkyl, C3-C 20 Cycloalkoxy, C6-C 20 aryl, or a combination thereof.

9. The polymer of claim 1, wherein the first repeating unit is represented by Formula 1-1: (Formula 1-1) in, In formula 1-1, r1 is an integer from 1 to 3, R 12a To R 12d each independently hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a linear, branched or cyclic C1-C ... 30 a monovalent hydrocarbon group, and *Indicates the binding site with the adjacent atom.

10. The polymer of claim 1, wherein the first repeating unit is selected from Group I: (Group I) 11. The polymer of claim 1, further comprising at least one of a second repeating unit represented by Formula 2 or a third repeating unit represented by Formula 3: (Formula 2) (Formula 3) in, In equations 2 and 3, L 21 To L 23 and L 31 To L 33 each independently represents a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or a linear, branched or cyclic C1-C ... 30 Divalent hydrocarbon groups, a21 to a23 and a31 to a33 are each independently an integer of 1 to 4, A 21 and A 31 are each independently a linear, branched or cyclic C1-C 30 Alkyl; linear, branched or cyclic C2-C 30 or optionally including heteroatoms C1-C 30 Aromatic groups, n2 is 0 or 1, R 21 , R 22 , R 31 and R 32 each independently hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a linear, branched or cyclic C1-C ... 30 Monovalent hydrocarbon groups, b22 and b32 are each independently an integer from 1 to 10, p2 is an integer from 1 to 5, and *Indicates the binding site with the adjacent atom.

12. The polymer of claim 11, wherein A 21 and A 31 are each independently a linear, branched or cyclic C1-C 30 or a C1-C 30 Aromatic groups.

13. The polymer of claim 11, wherein A 21 and A 31 Each independently selected from the groups represented by formulae 9-1 to 9-37 and 10-1 to 10-48, a group in which at least one carbon of one of the groups represented by formulae 9-1 to 9-37 and 10-2 to 10-48 is replaced by oxygen, a group in which at least one carbon of one of the groups represented by formulae 9-1 to 9-37 and 10-2 to 10-48 is replaced by a carbonyl group, a benzene group, a naphthalene group, a phenanthrene group and an anthracene group in, In formulas 9-1 to 9-37 and 10-1 to 10-48, *Indicates the same as L 21 or L 31 binding site.

14. The polymer of claim 11, wherein R 32 is a linear, branched or cyclic C1-C 30 A monovalent hydrocarbon group.

15. The polymer of claim 11, wherein The second repeating unit is at least one of Group II, and The third repeating unit is at least one of Group III, and (Group II) (Group III) 16. A polymer-containing composition comprising: A polymer as described in any one of claims 1 to 15; Acid generators; and Organic solvents.

17. The polymer-containing composition of claim 16, wherein the acid generator comprises p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, pyridinium trifluoromethanesulfonate, salicylic acid, 5-sulfosalicylic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, 4-phenolsulfonic acid, methyl 4-phenolsulfonate, benzene disulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, or a combination thereof.

18. A method for forming a pattern, the method comprising: Forming an insulating layer by applying the polymer-containing composition according to claim 16 or 17 to a substrate provided with a first layer; forming an insulating pattern by selectively removing one or more portions of the insulating layer so that a first surface of the first layer is exposed; and The first layer having the exposed first surface is removed.

19. The method of claim 18, wherein the first layer comprises a conductive metal oxide, a conductive metal oxynitride, a conductive metal nitride, or a combination thereof.

20. The method of claim 18, wherein removing the first layer having the exposed first surface comprises a wet etching process, and The wet etching process uses an etchant containing hydrogen peroxide.

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