Resist underlayer composition and method of forming pattern using the same

Abstract

A resist underlayer composition and a method of forming a pattern using the same are disclosed. The resist underlayer composition includes: a polymer including a structural unit represented by Chemical Formula 1, a structural unit represented by Chemical Formula 2, a structural unit represented by Chemical Formula 3, or a combination thereof; a compound represented by one or more selected from Chemical Formulae 4 to 6; and a solvent. Definitions of Chemical Formulae 1 to 6 are as described in the specification. # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0142299 filed in the Korean Intellectual Property Office on October 23, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Embodiments of the present disclosure relate to a resist underlayer composition and a method of forming a pattern using the same. Background Art

[0004] Recently, the semiconductor industry has developed ultra-fine technology with patterns of several nanometers to tens of nanometers in size. This ultra-fine technology is due to the effective photolithography technology.

[0005] Photolithography is a processing method that includes coating a photoresist layer on a semiconductor substrate (such as a silicon wafer) to form a thin film, irradiating activating radiation (such as ultraviolet rays) through a mask pattern on which a device pattern is drawn, developing to obtain a photoresist pattern, and etching the substrate using the obtained photoresist pattern as a protective film to form a fine pattern corresponding to the pattern on the substrate surface.

[0006] As semiconductor patterns become more and more fine, the thickness of the photoresist layer should be thinner, and accordingly, the thickness of the resist bottom layer should also be thinner. Even if the resist bottom layer is thinned, the photoresist pattern should not collapse, it should have good adhesion to the photoresist, and should be formed with a uniform (or substantially uniform) thickness. The resist bottom layer should have a high refractive index and a low extinction coefficient for the light used for photolithography, and the etching rate should be faster than the photoresist layer. Summary of the invention

[0007] The resist underlayer composition according to some embodiments of the present disclosure provides a resist underlayer that does not cause resist pattern collapse even in a fine patterning process and has improved sensitivity to an exposure light source, thereby improving patterning performance and energy efficiency.

[0008] Some embodiments provide methods of forming patterns using a resist underlayer composition.

[0009] The resist underlayer composition according to some embodiments includes: a polymer including a structural unit represented by Chemical Formula 1, a structural unit represented by Chemical Formula 2, a structural unit represented by Chemical Formula 3, or a combination thereof; a compound represented by one or more selected from Chemical Formulas 4 to 6; and a solvent:

[0010] Chemical formula 1

[0011]

[0012] Chemical formula 2

[0013]

[0014] Chemical formula 3

[0015]

[0016] Among them, in Chemical Formula 1 to Chemical Formula 3,

[0017] A is a heterocyclic group containing a nitrogen atom in the ring,

[0018] L 1 To L 7 each is independently a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C1 to C20 heteroarylene group, or a combination thereof,

[0019] X 1 To X 8 Each is independently a single bond (e.g., a single covalent bond), -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -(C=O)O-, -O(C=O)O-, -C(=O)NH-, -NHC(=O)-, -NR a -(where R a is hydrogen, deuterium or C1 to C10 alkyl) or a combination thereof,

[0020] Y 1 To Y 4 each is independently hydroxy, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C2-C10 heteroalkenyl, substituted or unsubstituted C2-C10 heteroalkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, or a combination thereof,

[0021] R 1 and R 2 are each independently hydrogen, deuterium, a hydroxyl group, a halogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or a combination thereof, and

[0022] * is the connection point;

[0023] Chemical formula 4

[0024]

[0025] Among them, in chemical formula 4,

[0026] R 3 and R 4 are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group, or R 3 and R 4 They are linked to each other to form a tricyclic alkyl group;

[0027] Chemical formula 5

[0028]

[0029] Among them, in chemical formula 5,

[0030] R 5 is hydrogen, deuterium, hydroxyl, halogen atom, cyano, =O, -NCS, -OR b (where R b is substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, or a combination thereof), -OC(=O)R c (where R c is hydrogen, deuterium, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, or a combination thereof), -NHC(=O)R d (Among them, R d is a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group), -NR e R f (where R e and R f are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl) or -C(=O)OR g (where R g is hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl), and

[0031] R 6 To R 9each independently represents hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, or a combination thereof;

[0032] Chemical formula 6

[0033]

[0034] Among them, in chemical formula 6,

[0035] M is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C10 heterocycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group,

[0036] L 8 and L 9 are each independently a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof,

[0037] X 9 and X 10 each independently represents -O-, -C(=O)-, -C(=O)O-, -O(C=O)O-, -C(=O)NH-, -NHC(=O)-, or a combination thereof,

[0038] R 10 To R 13 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, or a combination thereof, and

[0039] n is an integer of 2 or more but smaller than the valence of M.

[0040] A in Chemical Formula 1 and Chemical Formula 2 may be represented by one or more selected from Chemical Formula A-1 to Chemical Formula A-4:

[0041] Chemical formula A-1

[0042]

[0043] Chemical formula A-2

[0044]

[0045] Chemical formula A-3

[0046]

[0047] Chemical formula A-4

[0048]

[0049] In Chemical Formulae A-1 to A-4, * is a connection point.

[0050] In some embodiments, L 1 To L 7 are each independently a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof, X 1 To X 8 are each independently a single bond (eg, a single covalent bond), -O-, -S-, -C(=O)-, -(CO)O-, -O(CO)O-, or a combination thereof, Y 1 To Y 4 are each independently hydroxy, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, or a combination thereof, and R 1 and R 2 Each is independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof.

[0051] The composition may further include a compound represented by Chemical Formula 7:

[0052] Chemical formula 7

[0053]

[0054] In chemical formula 7, R 13 is deuterium, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, or a combination thereof, p and q are each independently an integer of 1 or greater, and p+q is less than or equal to 6.

[0055] R in Formula 4 3 and R 4 Each independently may be a substituted or unsubstituted C1 to C30 alkyl group, or R 3 and R 4 May be linked to each other to form a tricycloalkyl group.

[0056] R in Formula 5 5 Can be hydrogen, hydroxyl, cyano, -NCS, -NH2, -COOH, -OR b (Among them, R b is substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, or a combination thereof), -OC(=O)R c (Among them, R cis hydrogen, deuterium, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C10 aryl, or a combination thereof), or -NHC(=O)R d (Among them, R d is a substituted or unsubstituted C1 to C10 alkyl group), and R 6 To R 9 Each is independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof.

[0057] In Chemical Formula 6, M may be a substituted or unsubstituted C3 to C10 heterocycloalkylene group, L 8 and L 9 are each independently a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof, X 9 and X 10 Each is independently -O-, -C(=O)-, -C(=O)O- or a combination thereof, R 10 To R 13 Each is independently hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof, and n may be 2 or 3.

[0058] The compound represented by Chemical Formula 4 may be represented by any one selected from Chemical Formula 4-1 to Chemical Formula 4-3:

[0059] Chemical formula 4-1

[0060]

[0061] Chemical formula 4-2

[0062]

[0063] Chemical formula 4-3

[0064]

[0065] The compound represented by Chemical Formula 5 may be represented by any one selected from Chemical Formula 5-1 to Chemical Formula 5-14:

[0066] Chemical formula 5-1

[0067]

[0068] Chemical formula 5-2

[0069]

[0070] Chemical formula 5-3

[0071]

[0072] Chemical formula 5-4

[0073]

[0074] Chemical formula 5-5

[0075]

[0076] Chemical formula 5-6

[0077]

[0078] Chemical formula 5-7

[0079]

[0080] Chemical formula 5-8

[0081]

[0082] Chemical formula 5-9

[0083]

[0084] Chemical formula 5-10

[0085]

[0086] Chemical formula 5-11

[0087]

[0088] Chemical formula 5-12

[0089]

[0090] Chemical formula 5-13

[0091]

[0092] Chemical formula 5-14

[0093]

[0094] The compound represented by Chemical Formula 6 can be represented by Chemical Formula 6-1 or Chemical Formula 6-2: Chemical Formula 6-1

[0095]

[0096] Chemical formula 6-2

[0097]

[0098] The compound represented by Chemical Formula 7 can be represented by any one selected from Chemical Formula 7-1 to Chemical Formula 7-5: Chemical Formula 7-1

[0099]

[0100] Chemical formula 7-2

[0101]

[0102] Chemical formula 7-3

[0103]

[0104] Chemical formula 7-4

[0105]

[0106] Chemical formula 7-5

[0107]

[0108] The weight average molecular weight of the polymer may be from about 1,000 g / mole to about 300,000 g / mole.

[0109] The polymer may be included in an amount of about 0.1 wt % to about 50 wt % based on the total weight of the resist underlayer composition.

[0110] The compound may be included in an amount of about 0.1 wt % to about 30 wt % based on the total weight of the resist underlayer composition.

[0111] The resist underlying composition may further include one or more polymers selected from acrylic resins, epoxy resins, novolac-based resins, glycoluril-based resins, and melamine-based resins.

[0112] The resist underlayer composition may further include additives such as a surfactant, a thermal acid generator, a photoacid generator, a plasticizer, or a combination thereof.

[0113] According to some embodiments, a method of forming a pattern includes forming a film to be etched on a substrate, coating an anti-etching base layer composition according to some embodiments on the film to be etched to form an anti-etching base layer, forming a photoresist pattern on the anti-etching base layer, and using the photoresist pattern as an etching mask to sequentially etch the anti-etching base layer and the film to be etched.

[0114] The resist underlayer composition according to some embodiments may provide a resist underlayer that does not cause collapse of a resist pattern even in a fine patterning process.

[0115] The resist underlayer composition according to some embodiments may provide a resist underlayer having improved sensitivity to an exposure light source, thereby improving patterning performance and energy efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0116] The drawings, together with the specification, illustrate embodiments of the presently disclosed subject matter, and, together with the description, serve to explain principles of the embodiments of the presently disclosed subject matter.

[0117] Figure 1-Figure 6 is a cross-sectional view illustrating a method of forming a pattern using a resist underlayer composition according to some embodiments.

[0118] Description of Reference Numerals

[0119] 100: substrate

[0120] 102:Film

[0121] 104: resist bottom layer

[0122] 106: Photoresist layer

[0123] 106a: Unexposed area

[0124] 106b: Exposure area

[0125] 108: Photoresist pattern

[0126] 110: Mask

[0127] 112: Organic film pattern

[0128] 114: Thin film pattern DETAILED DESCRIPTION

[0129] Example embodiments of the present disclosure will be described in more detail below, and those skilled in the art can easily implement them after reviewing the present disclosure. However, the subject matter of the present disclosure can be embodied in many different forms and should not be construed as limited to the example embodiments described herein.

[0130] In the drawings, the thickness of layers, films, panels, regions, etc. may be exaggerated for clarity, and the same reference numerals represent the same components throughout the specification. It should be understood that if an element such as a layer, film, region, or substrate is referred to as being "on" another component, it may be directly on the other component, or there may also be intervening components. Conversely, if a component is referred to as being "directly on" another component, there are no intervening components.

[0131] As used herein, if a definition is not otherwise provided, "substituted" means that a hydrogen atom of a compound is replaced with a substituent selected from deuterium, a halogen atom (F, Br, Cl or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amide group, a hydrazine group, a hydrazine keto group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C6 to C30 aryl group, a C7 to C30 aralkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroaralkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocyclyl group, and combinations thereof.

[0132] In some embodiments, two adjacent substituents of a substituted halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amide group, a hydrazine group, a hydrazine keto group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C6 to C30 aryl group, a C7 to C30 aralkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroaralkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, or a C2 to C30 heterocyclyl group may be fused to each other to form a ring.

[0133] As used herein, if no definition is otherwise provided, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S, Se and P.

[0134] As used herein, "aryl" refers to a group having at least one hydrocarbon aromatic moiety, and broadly includes hydrocarbon aromatic moieties connected by a single bond (e.g., a single covalent bond) and non-aromatic fused rings containing hydrocarbon aromatic moieties fused directly or indirectly. Aryl groups can be monocyclic, polycyclic, or fused polycyclic (e.g., rings that share adjacent pairs of carbon atoms) functional groups.

[0135] As used herein, "heterocyclic group" includes heteroaryl groups, and cyclic groups containing at least one heteroatom selected from N, O, S, P and Si instead of carbon (C) of cyclic compounds such as aryl groups, cycloalkyl groups, fused rings thereof or combinations thereof. If the heterocyclic group is a fused ring, each ring or the entire ring of the heterocyclic group may contain at least one heteroatom.

[0136] In some embodiments, the substituted or unsubstituted aryl and / or substituted or unsubstituted heterocyclic group can be substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted naphthranyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted quaterphenyl, substituted or unsubstituted chrysene, substituted or unsubstituted triphenylene, substituted or unsubstituted ter ... substituted or unsubstituted peryl, substituted or unsubstituted indenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiophene, The invention also includes but is not limited to a substituted or unsubstituted acridinyl, a substituted or unsubstituted phenazinyl, a substituted or unsubstituted phenothiazinyl, a substituted or unsubstituted phenoxazinyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothiophenyl, a substituted or unsubstituted carbazolyl, a pyridoindolyl, a benzopyridooxazinyl, a benzopyridothiazinyl, a 9,9-dimethyl-9,10-dihydroacridinyl, a combination thereof, or a combination of the foregoing groups fused to a ring, but is not limited thereto.

[0137] As used herein, if no specific definition is otherwise provided, the term "combination" means mixing and / or copolymerization.

[0138] Furthermore, as used herein, "polymer" may include both oligomers and polymers.

[0139] As used herein, if no definition is otherwise provided, "weight average molecular weight" can be measured by dissolving a powder sample in tetrahydrofuran (THF) and using a 1200 series gel permeation chromatograph (GPC) from Agilent Technologies (the column can be Shodex LF-804 and the standard sample can be Shodex polystyrene).

[0140] As used herein, if no definition is otherwise provided, "*" refers to the point of attachment of a structural unit of a compound or a moiety of a compound.

[0141] In the semiconductor industry, there is an effort to reduce chip size. Therefore, the line width of the resist patterned using photolithography should be reduced to the level of tens of nanometers, and the pattern formed in this way is used to transfer the pattern to the underlying material by using an etching process on the underlying substrate. However, as the resist pattern size becomes smaller, the height of the resist that can withstand the line width (e.g., aspect ratio) is limited, and therefore, the resist may not have suitable or sufficient resistance in the etching step. Therefore, if a thin resist material is used, if the substrate to be etched is thicker, and / or if a deep pattern is formed, a resist bottom layer is used to compensate for this.

[0142] As the resist thickness thins, the resist bottom layer should become thinner, and even if the resist bottom layer is thin, the photoresist pattern should not collapse. For this reason, the resist bottom layer should have excellent adhesion to the photoresist. In certain embodiments, when forming a thin resist bottom layer, the coating uniformity of the resist bottom layer composition and the flatness of the resist bottom layer produced therefrom should be improved, and the sensitivity to the exposure light source should be improved to improve pattern forming ability and energy efficiency.

[0143] The resist underlayer composition according to some embodiments includes: a polymer including a structural unit represented by Chemical Formula 1, a structural unit represented by Chemical Formula 2, a structural unit represented by Chemical Formula 3, or a combination thereof; a compound represented by one or more selected from Chemical Formulas 4 to 6; and a solvent:

[0144] Chemical formula 1

[0145]

[0146] Chemical formula 2

[0147]

[0148] Chemical formula 3

[0149]

[0150] Among them, in Chemical Formula 1 to Chemical Formula 3,

[0151] A is a heterocyclic group containing a nitrogen atom in the ring,

[0152] L 1 To L 7each is independently a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C1 to C20 heteroarylene group, or a combination thereof,

[0153] X 1 To X 8 Each is independently a single bond (e.g., a single covalent bond), -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -(C=O)O-, -O(C=O)O-, -C(=O)NH-, -NHC(=O)-, -NR a -(where R a is hydrogen, deuterium or C1 to C10 alkyl) or a combination thereof,

[0154] Y 1 To Y 4 each is independently hydroxy, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C2-C10 heteroalkenyl, substituted or unsubstituted C2-C10 heteroalkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, or a combination thereof,

[0155] R 1 and R 2 are each independently hydrogen, deuterium, a hydroxyl group, a halogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or a combination thereof, and

[0156] * is the connection point;

[0157] Chemical formula 4

[0158]

[0159] Among them, in chemical formula 4,

[0160] R 3 and R 4are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group, or R 3 and R 4 They are linked to each other to form a tricyclic alkyl group;

[0161] Chemical formula 5

[0162]

[0163] Among them, in chemical formula 5,

[0164] R 5 is hydrogen, deuterium, hydroxyl, halogen atom, cyano, =O, -NCS, -OR b (where R b is substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, or a combination thereof), -OC(=O)R c (where R c is hydrogen, deuterium, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, or a combination thereof), -NHC(=O)R d (Among them, R d is a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group), -NR e R f (where R e and R f are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl), or -C(=O)OR g (where R g is hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl), and

[0165] R 6 To R 9 each independently represents hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, or a combination thereof;

[0166] Chemical formula 6

[0167]

[0168] Among them, in chemical formula 6,

[0169] M is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C10 heterocycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group,

[0170] L 8 and L 9 are each independently a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof,

[0171] X 9 and X 10 each independently represents -O-, -C(=O)-, -C(=O)O-, -O(C=O)O-, -C(=O)NH-, -NHC(=O)-, or a combination thereof,

[0172] R 10 To R 13 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, or a combination thereof, and

[0173] n is an integer greater than or equal to 2, but less than the valence of M.

[0174] The resist underlayer composition according to some embodiments includes a compound represented by at least one selected from Chemical Formulae 4 to 6, and a polymer including at least one selected from the structural units represented by Chemical Formulae 1 to 3, respectively, thereby improving the sensitivity of the resist and improving the pattern forming ability of a fine pattern if used as a resist underlayer. This is because the compound represented by at least one selected from Chemical Formulae 4 to 6 can act as a radical scavenger, donate electrons to highly active radicals, and convert the radicals into a stable state.

[0175] The structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2 that form the polymer in the composition according to some embodiments include a heterocyclic ring containing a nitrogen atom in the ring. Therefore, the polymer including one or more of the above structural units can form sp between the polymers. 2 -sp 2Bonding. For the above reasons, the polymer has a high electron density, and according to some embodiments, the resist bottom layer composition including the polymer with high electron density can realize a film with a dense structure in the form of an ultra-thin film, and if the resist bottom layer composition is exposed to light, the high electron density of the polymer can have the effect of improving light absorption efficiency. In some embodiments, by including a heterocyclic skeleton, if a pattern is formed after exposure to high-energy rays such as EUV (extreme ultraviolet; wavelength 13.5 nanometers) and E-Beam (electron beam), the polymer can have improved etching selectivity and improved energy efficiency.

[0176] A in Chemical Formula 1 and Chemical Formula 2 may be represented by one or more selected from Chemical Formula A-1 to Chemical Formula A-4:

[0177] Chemical formula A-1

[0178]

[0179] Chemical formula A-2

[0180]

[0181] Chemical formula A-3

[0182]

[0183] Chemical formula A-4

[0184]

[0185] In Chemical Formulae A-1 to A-4, * is a connection point.

[0186] L 1 To L 7 Each is independently a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof, for example, a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof, for example, a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted C1 to C5 heteroalkylene group containing a sulfur atom, or a combination thereof, but is not limited thereto.

[0187] X 1 To X 8Each is independently a single bond (e.g., a single covalent bond), -O-, -S-, -S(=O)-, -C(=O)-, -(CO)O-, -O(CO)O-, -C(=O)NH-, or a combination thereof, for example, a single bond (e.g., a single covalent bond), -O-, -S-, -C(=O)-, -(CO)O-, -O(CO)O-, or a combination thereof, but is not limited thereto.

[0188] Y 1 To Y 4 and C2 to C10 alkyl, substituted or unsubstituted C1 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C1 to C10 heteroalkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C3 to C20 heteroaryl, or a combination thereof, for example, hydroxyl, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C1 to C10 heteroalkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C3 to C20 heteroaryl, or a combination thereof unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C1 to C10 heteroalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, or a combination thereof, for example, hydroxyl, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, or a combination thereof, for example, hydroxyl, substituted or unsubstituted C1 to C5 alkyl, substituted or unsubstituted C2 to C5 alkenyl, or a combination thereof, but are not limited thereto.

[0189] R 1 and R 2 Each is independently hydrogen, deuterium, hydroxyl, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C10 alkenyl, or a combination thereof, for example, hydrogen, substituted or unsubstituted C1 to C20 alkyl, or a combination thereof, for example, hydrogen, or substituted or unsubstituted C1 to C10 alkyl, for example, hydrogen or substituted or unsubstituted C1 to C5 alkyl, for example, hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, or a combination thereof, but is not limited thereto.

[0190] For example, the structural unit represented by Chemical Formula 1 may be represented by any one selected from Chemical Formula 1-1 to Chemical Formula 1-3, the structural unit represented by Chemical Formula 2 may be represented by any one selected from Chemical Formula 2-1 to Chemical Formula 2-3, and the structural unit represented by Chemical Formula 3 may be represented by any one selected from Chemical Formula 3-1 to Chemical Formula 3-3:

[0191] Chemical formula 1-1

[0192]

[0193] Chemical formula 1-2

[0194]

[0195] Chemical formula 1-3

[0196]

[0197] Chemical formula 2-1

[0198]

[0199] Chemical formula 2-2

[0200]

[0201] Chemical formula 2-3

[0202]

[0203] Chemical formula 3-1

[0204]

[0205] Chemical formula 3-2

[0206]

[0207] Chemical formula 3-3

[0208]

[0209] In the compound represented by Chemical Formula 4 included in the composition according to some embodiments, R 3 and R 4 are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or a substituted or unsubstituted C6 to C30 aryl group, or R 3 and R 4 can be linked to each other to form a tricycloalkyl group, for example, R 3 and R 4 Each independently may be a substituted or unsubstituted C1 to C20 alkyl group, or R 3 and R 4 can be connected to each other to form a tricycloalkyl group, but is not limited thereto. For example, R 3 and R 4 Each independently may be a C1 to C30 alkyl group substituted with an aryl group or an unsubstituted C1 to C30 alkyl group or R 3 and R 4They may be linked to each other to form a tricycloalkyl group, and are not limited thereto.

[0210] In some embodiments, the compound represented by Chemical Formula 4 may be represented by any one selected from Chemical Formula 4-1 to Chemical Formula 4-3:

[0211] Chemical formula 4-1

[0212]

[0213] Chemical formula 4-2

[0214]

[0215] Chemical formula 4-3

[0216]

[0217] R of the compound represented by Chemical Formula 5 included in the composition according to some embodiments 5 It can be hydrogen, deuterium, hydroxyl, halogen atom, cyano, =O, -NCS, -OR b 、-OC(=O)R c 、-NHC(=O)R d 、-NR e R f OR -C(=O)OR g .

[0218] For example, R b It may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or a combination thereof, for example, a C1 to C10 alkyl group substituted with an epoxy group, an unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C2 to C5 alkynyl group, but is not limited thereto.

[0219] For example, R c It may be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, for example, a methyl-substituted C2 to C5 alkenyl group or a substituted or unsubstituted C6 to C10 aryl group, but is not limited thereto.

[0220] For example, R d The group may be a substituted or unsubstituted C1 to C5 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, for example, a C1 to C5 alkyl group substituted with a halogen atom or an unsubstituted C1 to C10 alkyl group, but is not limited thereto.

[0221] For example, R e and R fEach may independently be hydrogen, deuterium, or a substituted or unsubstituted C1 to C5 alkyl group, for example, hydrogen, but is not limited thereto.

[0222] For example, R g It may be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, for example, hydrogen, but is not limited thereto.

[0223] In some embodiments, the compound represented by Chemical Formula 5 may be represented by any one selected from Chemical Formula 5-1 to Chemical Formula 5-14:

[0224] Chemical formula 5-1

[0225]

[0226] Chemical formula 5-2

[0227]

[0228] Chemical formula 5-3

[0229]

[0230] Chemical formula 5-4

[0231]

[0232] Chemical formula 5-5

[0233]

[0234] Chemical formula 5-6

[0235]

[0236] Chemical formula 5-7

[0237]

[0238] Chemical formula 5-8

[0239]

[0240] Chemical formula 5-9

[0241]

[0242] Chemical formula 5-10

[0243]

[0244] Chemical formula 5-11

[0245]

[0246] Chemical formula 5-12

[0247]

[0248] Chemical formula 5-13

[0249]

[0250] Chemical formula 5-14

[0251]

[0252] M in the compound represented by Chemical Formula 6 included in the composition according to some embodiments may be a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C10 heterocycloalkylene group, or a substituted or unsubstituted C6 to C10 arylene group, for example, a substituted or unsubstituted C1 to C5 alkylene group or an unsubstituted C3 to C10 heterocycloalkylene group, and for example, the heterocycloalkylene group may be isocyanurate, but is not limited thereto.

[0253] L 8 and L 9 Each may independently be a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof, a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C5 alkylene group, or a combination thereof, but is not limited thereto.

[0254] X 9 and X 10 Each may independently be -O-, -C(=O)-, -C(=O)O- or a combination thereof, but is not limited thereto.

[0255] R 10 To R 13 Each may independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, for example, a substituted or unsubstituted C1 to C5 alkyl group, for example, an unsubstituted methyl group, an unsubstituted ethyl group, or a combination thereof, but is not limited thereto.

[0256] In an embodiment, n is an integer of 2 or more but less than the valence of M, for example, one of integers of 2 to 6, for example, 2 or 3, but not limited thereto. If n is an integer of 2 or more, the compound represented by Chemical Formula 6 can more efficiently donate electrons.

[0257] In some embodiments, the compound represented by Chemical Formula 6 may be represented by Chemical Formula 6-1 or Chemical Formula 6-2:

[0258] Chemical formula 6-1

[0259]

[0260] Chemical formula 6-2

[0261]

[0262] The resist underlayer composition according to some embodiments may further include a compound represented by Chemical Formula 7:

[0263] Chemical formula 7

[0264]

[0265] In chemical formula 7, R 13 is deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, or a combination thereof, p and q are each independently an integer less than or equal to 1, and p+q is less than or equal to 6.

[0266] R 13 It can be, for example, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, or a combination thereof, such as a substituted or unsubstituted C1 to C5 alkyl group, a substituted or unsubstituted C1 to C5 alkoxy group, or a combination thereof, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxy group, an ethoxy group, or a combination thereof, but is not limited thereto.

[0267] p and q are each independently one of integers from 1 to 5, such as one of integers from 1 to 3, but not limited thereto, and the sum of p and q is one of integers from 2 to 6, such as 2 to 5, or such as 2 to 4, but not limited thereto.

[0268] In some embodiments, the compound represented by Chemical Formula 7 may be represented by at least one selected from Chemical Formula 7-1 to Chemical Formula 7-5:

[0269] Chemical formula 7-1

[0270]

[0271] Chemical formula 7-2

[0272]

[0273] Chemical formula 7-3

[0274]

[0275] Chemical formula 7-4

[0276]

[0277] Chemical formula 7-5

[0278]

[0279] According to some embodiments, the polymer included in the composition may have a weight average molecular weight of about 1,000 g / mol to about 300,000 g / mol, for example, about 3,000 g / mol to about 200,000 g / mol, for example, about 3,000 g / mol to about 100,000 g / mol, for example, about 3,000 g / mol to about 90,000 g / mol, for example, about 3,000 g / mol to about 70,000 g / mol, for example, about 3,000 g / mol to about 70,000 g / mol, for example, about 3,000 g / mol to about 50,000 g / mol, for example, about 5,000 g / mol to about 50,000 g / mol, or for example, about 5,000 g / mol to about 30,000 g / mol, but is not limited thereto. By having a weight average molecular weight within the above range, the carbon content and solubility in a solvent of the resist underlayer composition including the polymer can be adjusted and possibly adapted or optimized.

[0280] Based on the total weight of the resist bottom layer composition, the polymer can be included in an amount of about 0.1 wt % to about 50 wt %. In certain embodiments, based on the total weight of the resist bottom layer composition, the polymer can be included in an amount of about 10 wt % to about 50 wt % (e.g., about 20 wt % to about 50 wt % or, for example, about 20 wt % to about 30 wt %), but is not limited thereto. By including a polymer within the above range in the composition, the thickness, surface roughness, and planarization degree of the resist bottom layer can be adjusted.

[0281] According to some embodiments, based on the total weight of the resist bottom layer composition, the content of the compound included in the composition may be from about 0.01 wt % to about 30 wt %. In some embodiments, based on the total weight of the resist bottom layer composition, the content of the compound may be from about 0.1 wt % to about 30.0 wt %, for example, from about 1.0 wt % to about 30.0 wt %, for example, from about 5.0 wt % to about 30.0 wt %, for example, from about 5.0 wt % to about 25.0 wt %, for example, from about 8.0 wt % to about 25.0 wt %, for example, from about 10.0 wt % to about 25.0 wt %, or for example, about 20.0 wt %, but not limited thereto. By including the compound within the above range, the thickness, surface roughness, chemical resistance and planarization degree of the resist bottom layer can be adjusted.

[0282] According to some embodiments, the resist underlayer composition may include a solvent.

[0283] The solvent is not particularly limited as long as it has appropriate or sufficient solubility and / or dispersibility for the polymer according to some embodiments, but can be, for example, propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone, methyl 2-hydroxyisobutyrate, acetylacetone, ethyl 3-ethoxypropionate, or a combination thereof.

[0284] According to some embodiments, the resist base layer composition may include one or more additional polymers selected from acrylic resins, epoxy resins, novolac resins, glycoluril resins, and melamine resins in addition to the polymer, compound, and solvent, but is not limited thereto. According to some embodiments, the additional polymer may be added to the resist base layer composition in an amount of about 0.2 wt%.

[0285] According to some embodiments, the resist underlayer composition may further include an additive including a surfactant, a thermal acid generator, a photoacid generator, a plasticizer, or a combination thereof.

[0286] If the resist bottom layer is formed, a surfactant may be used to improve coating defects that occur as the solid content increases. For example, the surfactant may be alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, etc., but is not limited thereto.

[0287] The thermal acid generator can be, for example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine p-toluenesulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthoic acid, and / or benzoin toluenesulfonate, 2-nitrobenzyl toluenesulfonate, and / or other organic alkyl sulfonates, but is not limited thereto.

[0288] The plasticizer is not particularly limited, and various suitable types (or kinds) of plasticizers commonly used in the art can be used. Examples of plasticizers may include low molecular weight compounds such as phthalates, adipates, phosphates, trimellitates and citrates, as well as polyethers, polyesters and polyacetal compounds.

[0289] According to some embodiments, a resist underlayer manufactured using the resist underlayer composition is provided. The resist underlayer can be obtained, for example, by coating the resist underlayer composition on a substrate and then curing the substrate by a heat treatment process.

[0290] Below, we will refer to Figure 1-Figure 6 A method for forming a pattern using the above-mentioned resist underlayer composition is described. Figure 1-Figure 6 is a cross-sectional view illustrating a method of forming a pattern using a resist underlying composition according to an embodiment of the present disclosure.

[0291] Reference Figure 1 First, an object to be etched is prepared. An example of the object to be etched may be a thin film 102 on a semiconductor substrate 100. Hereinafter, only an embodiment in which the object to be etched is the thin film 102 is described, but the present disclosure is not limited thereto. The surface of the thin film 102 is cleaned to remove contaminants remaining on the thin film 102. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, and / or a silicon oxide film.

[0292] Subsequently, the above-mentioned resist underlayer composition is applied on the surface of the cleaning film 102 using, for example, a spin coating method.

[0293] Then, a drying and baking process is performed to form a resist bottom layer 104 on the thin film. The baking process may be performed at about 100° C. to about 500° C., for example, at about 100° C. to about 300° C. A more detailed description of the resist bottom layer composition will not be repeated here to avoid repetition, since it has been described in more detail above.

[0294] Reference Figure 2 , a photoresist is coated on the resist bottom layer 104 to form a photoresist layer 106. In some embodiments, the photoresist composition forming the photoresist layer 106 may include an organic metal compound containing Sn, a solvent, etc., but is not limited thereto.

[0295] Subsequently, a first baking process is performed to heat the substrate 100 having the photoresist layer 106 formed thereon. The first baking process may be performed at a temperature of about 90°C to about 120°C.

[0296] Reference Figure 3 , selectively exposing the photoresist layer 106. Taking the exposure process of exposing the photoresist layer 106 as an example, an exposure mask having a set or predetermined pattern is placed on a mask stage of an exposure device, and an exposure mask 110 is placed on the photoresist layer 106. Subsequently, by irradiating light to the mask 110, a set or predetermined portion of the photoresist layer 106 formed on the substrate 100 selectively reacts with the light passing through the exposure mask.

[0297] For example, examples of light that can be used in the exposure process may include short-wavelength light, such as i-line activation radiation with a wavelength of 365 nanometers, KrF excimer laser with a wavelength of 248 nanometers, and / or ArF excimer laser with a wavelength of 193 nanometers. In some embodiments, EUV (extreme ultraviolet) with a wavelength of 13.5 nanometers may be used, which corresponds to extreme ultraviolet light.

[0298] Since a polymer is formed by a cross-linking reaction such as a condensation reaction between organic metal compounds, the exposed region 106 b of the photoresist layer 106 has a different solubility from the unexposed region 106 a of the photoresist layer 106 .

[0299] Subsequently, a second baking process is performed on the substrate 100. The second baking process may be performed at a temperature of about 90° C. to about 200° C. By performing the second baking process, the exposed region 106 b of the photoresist layer 106 becomes difficult to dissolve in a developer.

[0300] Reference Figure 4 The photoresist layer 106 a corresponding to the unexposed area is dissolved and removed using an organic solvent developer such as 2-heptanone, thereby forming a photoresist pattern 108 by leaving the photoresist layer 106 b after development.

[0301] As described above, the developer used in the method for forming a pattern according to some embodiments may be an organic solvent. Examples of the organic solvent used in the method for forming a pattern according to some embodiments may include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone, alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, and methanol, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone, aromatic compounds such as benzene, xylene, and toluene, or a combination thereof.

[0302] However, the photoresist pattern according to some embodiments is not necessarily limited to being formed as a negative image, but can also be formed as a positive image. In some embodiments, the developer that can be used to form a positive image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or a combination thereof.

[0303] As described above, the photoresist pattern 108 formed by exposure to high-energy light (e.g., not only light having a wavelength such as i-line (wavelength: 365 nm), KrF excimer laser (wavelength: 248 nm), and / or ArF excimer laser (wavelength: 193 nm), but also EUV (extreme ultraviolet; wavelength: 13.5 nm) and / or electron beam) may have a width of about 5 nm to about 100 nm. For example, the photoresist pattern 108 may be formed to have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, about 5 nm to about 20 nm, or about 5 nm to about 10 nm.

[0304] In some embodiments, the photoresist pattern 108 may have a pitch with a half pitch of less than or equal to about 50 nanometers (e.g., less than or equal to about 40 nanometers, for example, less than or equal to about 30 nanometers, for example, less than or equal to about 20 nanometers, or for example, less than or equal to about 10 nanometers) and a line width roughness of less than or equal to about 5 nanometers, less than or equal to about 3 nanometers, less than or equal to about 2 nanometers, or less than or equal to about 1 nanometer.

[0305] Subsequently, the resist bottom layer 104 is etched using the photoresist pattern 108 as an etching mask. Figure 5 An organic film pattern 112 is shown.

[0306] The formed organic film pattern 112 may also have a width corresponding to the photoresist pattern 108. Etching may be performed, for example, by dry etching using an etching gas, which may be, for example, CHF3, CF4, Cl2, O2, or a mixture thereof. As described above, since the resist underlayer formed by the resist underlayer composition according to some embodiments has a fast etching rate, a smooth etching process may be performed in a short time.

[0307] Reference Figure 6 , the exposed thin film 102 is etched by using the photoresist pattern 108 as an etching mask. As a result, the thin film is formed into a thin film pattern 114.

[0308] In the exposure process performed as described above, the thin film pattern 114 formed by the exposure process performed using a short wavelength light source such as an activation radiation i-line (wavelength: 365 nanometers), a KrF excimer laser (wavelength: 248 nanometers) and / or an ArF excimer laser (wavelength: 193 nanometers) may have a width of tens to hundreds of nanometers, while the thin film pattern 114 formed by the exposure process performed using an EUV light source may have a width less than or equal to about 20 nanometers.

[0309] Hereinafter, embodiments of the present disclosure will be described in more detail through examples related to the synthesis of the above-mentioned polymer and the preparation of a resist underlayer composition including the polymer. However, the present disclosure is not technically limited to the following examples.

[0310] Polymer synthesis

[0311] Aggregation Example 1

[0312] 24.9 g of 1,3-diallyl-5-(2-hydroxyethyl)isocyanurate, 7.4 g of mercaptoethanol, 0.7 g of azobisisobutyronitrile (AIBN) and 48 g of N,N-dimethylformamide (DMF) were added to a 500 ml three-necked round-bottom flask and connected to a condenser. After the reaction was carried out at 80 ° C for 16 hours, the resulting reaction solution was cooled to room temperature. While stirring, the reaction solution was added dropwise to a 1-liter wide-mouth bottle containing 800 g of water to produce a jelly, which was dissolved in 80 g of tetrahydrofuran (THF). The dissolved resin solution was treated with toluene to form a precipitate while removing single molecules and low molecular weight molecules. Finally, 10 grams of a polymer containing a structural unit represented by chemical formula 1-1 was obtained. (Weight average molecular weight (Mw) = 10,500 g / mol)

[0313] Chemical formula 1-1

[0314]

[0315] Aggregation Example 2

[0316] 24.9 g of 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione, 7.4 g of mercaptoethanol, 0.7 g of AIBN (azobisisobutyronitrile) and 48 g of N,N-dimethylformamide (DMF) were placed in a 500 ml three-necked round-bottom flask and connected to a condenser. After the reaction was carried out at 80 ° C for 16 hours, the resulting reaction solution was cooled to room temperature. While stirring, the reaction solution was added dropwise to a 1-liter wide-mouth bottle containing 800 g of water to produce a jelly, which was dissolved in 80 g of tetrahydrofuran (THF). The dissolved resin solution was treated with toluene to form a precipitate while removing single molecules and low molecular weight molecules. Finally, 10 grams of a polymer containing a structural unit represented by chemical formula 1-2 was obtained. (Weight average molecular weight (Mw) = 8,000 g / mol)

[0317] Chemical formula 1-2

[0318]

[0319] Synthesis of compounds

[0320] Synthesis Example 1

[0321] 2.5 g of succinic acid and 10 g of 4-glycidyloxy-2,2,6,6-tetramethylpiperidinium 1-oxyl radical, 3.5 g of pyridine and 50 g of N,N-dimethylformamide were added to a 250 ml flask to prepare a reaction solution, and a condenser was connected. The resulting reaction solution was heated at 100°C for 10 hours for reaction, and after checking that the reaction was complete, it was cooled to room temperature. Subsequently, the reaction solution was washed with distilled water to obtain an organic solution and remove the solvent therein, and finally a compound represented by chemical formula 6-2 was obtained.

[0322] Chemical formula 6-2

[0323]

[0324] Preparation of resist base composition

[0325] Example 1

[0326] 1.2 grams of a mixture of the polymer of polymerization example 1 and bis(octadecyl)hydroxylamine represented by chemical formula 4-3 (Sigma-Aldrich) in a ratio of 100:30, 0.4 grams of PD1174 (crosslinker) and 0.02 grams of pyridinium p-toluenesulfonate (PPTS) were completely dissolved in propylene glycol monomethyl ether to a solid content of 3%, and then diluted by additionally adding solvent to prepare the anti-etching primer composition of example 1.

[0327] Chemical formula 4-3

[0328]

[0329] Example 2

[0330] 1.2 g of a mixture including the polymer of polymerization example 1 and 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl (Sigma-Aldrich) represented by chemical formula 5-2, 0.4 g of PD1174 (crosslinker) and 0.02 g of pyridinium p-toluenesulfonate (PPTS) mixed in a ratio of 100:30 were completely dissolved in propylene glycol monomethyl ether to a solid content of 3%, and then diluted by additionally adding solvent to prepare the anti-etching primer composition of example 2.

[0331] [Chemical formula 5-2]

[0332]

[0333] Example 3

[0334] 1.2 g of a mixture including the polymer of Polymerization Example 1 and the compound of Synthesis Example 1, 0.4 g of PD1174 (crosslinker) and 0.02 g of pyridinium p-toluenesulfonate (PPTS) mixed in a ratio of 100:30 were completely dissolved in propylene glycol monomethyl ether to a solid content of 3%, and then diluted by additionally adding solvent to prepare the anti-etching primer composition of Example 3.

[0335] Example 4

[0336] 1.2 g of a mixture including the polymer of polymerization example 1 and 2,6-di-tert-butyl-4-methylphenol represented by chemical formula 7-1 (Sigma-Aldrich) in a ratio of 100:30, 0.4 g of PD1174 (cross-linker) and 0.02 g of pyridinium p-toluenesulfonate (PPTS) were completely dissolved in propylene glycol monomethyl ether to a solid content of 3%, and then diluted by additionally adding a solvent to prepare the anti-etching primer composition of example 4.

[0337] Chemical formula 7-1

[0338]

[0339] Example 5

[0340] 1.2 grams of a mixture including the polymer of polymerization example 1 and 2,6-di-tert-butyl-4-methylphenol represented by chemical formula 7-4 (Sigma-Aldrich) in a ratio of 100:30, 0.4 grams of PD1174 (cross-linker) and 0.02 grams of pyridinium p-toluenesulfonate (PPTS) were completely dissolved in propylene glycol monomethyl ether to a solid content of 3%, and then diluted by additionally adding solvent to prepare the anti-etching primer composition of Example 5.

[0341] Chemical formula 7-4

[0342]

[0343] Comparative Example 1

[0344] 1.2 g of the polymer of Polymerization Example 1, 0.4 g of PD1174 (crosslinker) and 0.02 g of pyridinium p-toluenesulfonate (PPTS) were completely dissolved in propylene glycol monomethyl ether to a solid content of 3% and then diluted by additionally adding a solvent to prepare a resist underlayer composition.

[0345] Comparative Example 2

[0346] A resist underlayer composition was prepared in the same manner as in Comparative Example 1, except that the polymer of Polymerization Example 2 was used instead of the polymer of Polymerization Example 1.

[0347] Evaluation 1: Coating uniformity evaluation

[0348] 2 ml of each composition of the example and comparative example was taken and poured on an 8-inch wafer, spin-coated at 1,500 rpm for 20 seconds using an automatic track (ACT-8, TEL (Tokyo Electron Co., Ltd.)), and then cured at 205°C for 60 seconds to form a 50 angstrom thick film.

[0349] After measuring the thickness of the film at 51 points along the horizontal axis, the difference between the maximum and minimum values ​​in the thickness was calculated and compared according to Formula 1 to evaluate the coating uniformity. Here, a higher coating uniformity value means a more excellent coating uniformity, and the results are shown in Table 1.

[0350] [Calculation formula 1]

[0351] Coating uniformity (angstroms) = maximum value - minimum value of thickness measured at 51 points on the wafer

[0352] Table 1

[0353] Coating uniformity Example 1 2.8 Example 2 2.2 Example 3 2.2 Example 4 2.5 Example 5 2.4 Comparative Example 1 4.4 Comparative Example 2 4.2

[0354] Referring to Table 1, the resist underlayer formed of the composition of Example exhibits a smaller coating uniformity value than that of the resist underlayer formed of the composition of Comparative Example, and thus, exhibits more excellent coating uniformity than that of the resist underlayer formed of the composition of Comparative Example.

[0355] Evaluation 2: Chemical resistance evaluation

[0356] Take 2 ml of each resist bottom layer composition of the example and the comparative example, then pour it on a 4-inch wafer, and use a spin coater (Mikasa Co., Ltd.) to spin coat at a speed of 1,500 rpm for 20 seconds. Subsequently, the coated composition was cured at 210°C for 90 seconds, and the thickness of the film was measured using a film thickness meter manufactured by K-MAC (Korea Materials and Analysis Corp.). Subsequently, the film was immersed in a mixed solvent (70% by weight of propylene glycol monomethyl ether + 30% by weight of propylene glycol monomethyl ether acetate) for 1 minute, and then the thickness of the film was measured again. The thickness reduction rate before and after immersion was calculated according to Formula 2 to evaluate the chemical resistance of the bottom layer. The smaller the thickness reduction rate, the more excellent the chemical resistance, and the results are shown in Table 2.

[0357] Calculation formula 2

[0358] Base thickness reduction rate (%) = {(film thickness before immersion - film thickness after immersion) / film thickness before immersion} × 100

[0359] Table 2

[0360] Thickness reduction rate Example 1 0.9 Example 2 0.5 Example 3 0.6 Example 4 0.7 Example 5 0.7 Comparative Example 1 1.7 Comparative Example 2 1.9

[0361] In Table 2, the thickness reduction rate results before and after immersion in the mixed solution of PGME and PGMEA in the example are smaller than that of the comparative example, which confirms that the resist underlayer of the example has excellent chemical resistance compared with the thin film of the comparative example.

[0362] Evaluation 3: Delayed evaluation

[0363] Take 2 ml of each resist bottom layer composition of the example and the comparative example, then pour it on a 4-inch wafer and use a spin coater (Mikasa Co., Ltd.) to spin coat at a speed of 1,500 rpm for 20 seconds. Subsequently, the coated composition is cured at 210°C for 90 seconds to form a thin film. On these bottom layers, a photoresist for EUV lithography is applied using a spin coater and cured at 110°C for 60 seconds on a hot plate to form a photoresist film, and then an electron beam drawing device (E-beam) is used to draw a 50-nanometer line width and a 50-nanometer spacing (L / S) pattern thereon. Subsequently, tetramethylammonium hydroxide aqueous solution is immediately used as a developing solution for development to form a resist pattern on a silicon wafer, which is referred to as a 0-minute result without delay. On the other hand, except that the line width and spacing (L / S) pattern drawn using an electron beam drawing device (E-beam) is placed for 30 minutes and then developed using a developing solution to form a resist pattern on a silicon wafer, the other steps are the same as above, which is referred to as a 30-minute delay result. As shown in calculation formula 3, the size difference (nanometer) between the 0-minute pattern without delay and the 30-minute delay pattern was calculated to evaluate the delay.

[0364] Calculation formula 3

[0365] Pattern size change (nm) = (30-minute delay pattern size - 0-minute pattern size)

[0366] Table 3

[0367] Pattern size changes Example 1 5.2 Example 2 2.6 Example 3 2.2 Example 4 3.8 Example 5 2.8 Comparative Example 1 17 Comparative Example 2 9

[0368] Referring to Table 3, the resist underlayer of Example exhibited less pattern change at the time of delay after exposure. Therefore, the resist underlayer of Example exhibited excellent resist pattern change compared with the thin film of Comparative Example.

[0369] Heretofore, exemplary embodiments of the present disclosure have been described and illustrated, however, it should be understood by those skilled in the art that the subject matter of the present disclosure is not limited to the described embodiments, and various modifications and conversions may be made without departing from the spirit and scope of the present disclosure. Therefore, these modified or converted embodiments should not be understood separately from the technical ideas and aspects of the present disclosure, and the modified embodiments are within the scope of the attached claims and their equivalents.

Claims

1. A resist bottom layer composition, comprising: A polymer including a structural unit represented by Chemical Formula 1, a structural unit represented by Chemical Formula 2, a structural unit represented by Chemical Formula 3, or a combination thereof; a compound represented by one or more selected from Chemical Formulas 4 to 6; and a solvent: Chemical formula 1 Chemical formula 2 Chemical formula 3 Among them, in Chemical Formula 1 to Chemical Formula 3, A is a heterocyclic group containing a nitrogen atom in the ring, L 1 To L 7 each independently represents a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C1 to C20 heteroarylene group, or a combination thereof, X 1 To X 8 each independently represents a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -(C=O)O-, -O(C=O)O-, -C(=O)NH-, -NHC(=O)-, -NR a - or a combination thereof, wherein R a is hydrogen, deuterium or C1 to C10 alkyl, Y 1 To Y 4 each is independently hydroxy, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C2-C10 heteroalkenyl, substituted or unsubstituted C2-C10 heteroalkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, or a combination thereof, R 1 and R 2 are each independently hydrogen, deuterium, a hydroxyl group, a halogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or a combination thereof, and * is the connection point; Chemical formula 4 Among them, in chemical formula 4, R 3 and R 4 are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group, or R 3 and R 4 They are linked to each other to form a tricyclic alkyl group; Chemical formula 5 Among them, in chemical formula 5, R 5 is hydrogen; deuterium; hydroxyl; halogen atom; cyano; =O; -NCS; -OR b , where R b is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or a combination thereof; -OC(=O)R c , where R c is hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof; -NHC(=O)R d , where R d is a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group; -NR e R f , where R e and R f are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl; or -C(=O)OR g , where R g is hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl or substituted or unsubstituted C6 to C20 aryl, and R 6 To R 9 each independently represents hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, or a combination thereof; Chemical formula 6 Among them, in chemical formula 6, M is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C10 heterocycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group, L 8 and L 9 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof, X 9 and X 10 each independently represents -O-, -C(=O)-, -C(=O)O-, -O(C=O)O-, -C(=O)NH-, -NHC(=O)-, or a combination thereof, R 10 To R 13 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, or a combination thereof, and n is an integer of 2 or more but smaller than the valence of M.

2. The resist underlayer composition according to claim 1, wherein A is represented by one or more selected from Chemical Formula A-1 to Chemical Formula A-4: Chemical formula A-1 Chemical formula A-2 Chemical formula A-3 Chemical formula A-4 in, In Chemical Formulae A-1 to A-4, * is a connection point.

3. The resist base composition according to claim 1, wherein L 1 To L 7 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof, X 1 To X 8 are each independently a single bond, -O-, -S-, -C(=O)-, -(CO)O-, -O(CO)O-, or a combination thereof, Y 1 To Y 4 are each independently hydroxy, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, or a combination thereof, and R 1 and R 2 Each is independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof.

4. The resist underlying layer composition according to claim 1, wherein the resist underlying layer composition further comprises a compound represented by Chemical Formula 7: Chemical formula 7 in, In Chemical Formula 7, R 13 is deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C1 to C20 alkoxy, or a combination thereof, and p and q are each independently an integer of 1 or greater, and p+q is 6 or less.

5. The resist underlayer composition according to claim 1, wherein R 3 and R 4 are each independently a substituted or unsubstituted C1 to C30 alkyl group, or R 3 and R 4 They are connected to each other to form a tricycloalkyl group.

6. The resist underlayer composition according to claim 1, wherein R 5 Hydrogen; hydroxyl; cyano; -NCS; -NH2; -COOH; -OR b , where R b is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, or a combination thereof; -OC(=O)R c , where R c is hydrogen, deuterium, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C10 aryl, or a combination thereof; or -NHC(=O)R d , where R d is a substituted or unsubstituted C1 to C10 alkyl group, and R 6 To R 9 Each is independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof.

7. The resist underlayer composition according to claim 1, wherein M in Chemical Formula 6 is a substituted or unsubstituted C3 to C10 heterocycloalkylene group, L 8 and L 9 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof, X 9 and X 10 Each is independently -O-, -C(=O)-, -C(=O)O- or a combination thereof, R 10 To R 13 are each independently hydrogen, deuterium, substituted or unsubstituted C1-C10 alkyl, or a combination thereof, and n is 2 or 3.

8. The resist underlayer composition according to claim 1, wherein the compound represented by Chemical Formula 4 is represented by any one selected from Chemical Formula 4-1 to Chemical Formula 4-3: Chemical formula 4-1 Chemical formula 4-2 Chemical formula 4-3 9. The resist underlayer composition according to claim 1, wherein the compound represented by Chemical Formula 5 is represented by any one selected from Chemical Formula 5-1 to Chemical Formula 5-14: Chemical formula 5-1 Chemical formula 5-2 Chemical formula 5-3 Chemical formula 5-4 Chemical formula 5-5 Chemical formula 5-6 Chemical formula 5-7 Chemical formula 5-8 Chemical formula 5-9 Chemical formula 5-10 Chemical formula 5-11 Chemical formula 5-12 Chemical formula 5-13 Chemical formula 5-14 10. The resist underlayer composition according to claim 1, wherein the compound represented by Chemical Formula 6 is represented by Chemical Formula 6-1 or Chemical Formula 6-2: Chemical formula 6-1 Chemical formula 6-2 11. The resist underlayer composition according to claim 1, wherein the compound represented by Chemical Formula 7 is represented by any one selected from Chemical Formula 7-1 to Chemical Formula 7-5: Chemical formula 7-1 Chemical formula 7-2 Chemical formula 7-3 Chemical formula 7-4 Chemical formula 7-5 12 . The resist underlayer composition according to claim 1 , wherein the weight average molecular weight of the polymer is 1,000 to 300,000 g / mol. 13 . The resist underlayer composition according to claim 1 , wherein the polymer is included in an amount of 0.1 wt % to 50 wt % based on the total weight of the resist underlayer composition. 14 . The resist underlayer composition according to claim 1 , wherein the compound is included in an amount of 0.1 wt % to 30 wt % based on the total weight of the resist underlayer composition.

15. The resist underlayer composition according to claim 1, wherein the resist underlayer composition further comprises one or more additional polymers selected from acrylic resins, epoxy resins, novolac-based resins, glycoluril-based resins, and melamine-based resins. 16 . The resist underlayer composition according to claim 1 , wherein the resist underlayer composition further comprises an additive consisting of a surfactant, a thermal acid generator, a photoacid generator, a plasticizer or a combination thereof.

17. A method for forming a pattern, comprising: forming a film to be etched on a substrate, coating the resist base layer composition as claimed in claim 1 on the film to be etched to form a resist base layer, forming a photoresist pattern on the resist bottom layer, and The resist base layer and the film to be etched are sequentially etched using the photoresist pattern as an etching mask.

Images