Composition for resist underlayer film and method of forming pattern using the same

Abstract

To provide a resist underlayer film that avoids pattern collapse, has high sensitivity to an exposure light source, and achieves enhanced patterning performance and energy efficiency.SOLUTION: There is provided a composition for a resist underlayer film, comprising a polymer with a specific structure, at least one hydroxylamine compound with a specific structure or a compound represented by the structure below.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a composition for a resist underlayer film and a pattern forming method using the same. [Background technology]

[0002] In recent years, the semiconductor industry has evolved from patterns of hundreds of nanometers to ultrafine technologies with patterns of a few nanometers to a few tens of nanometers in size. Effective lithography technology is essential to realize such ultrafine technologies.

[0003] Lithography is a processing method in which a photoresist film is coated on a semiconductor substrate such as a silicon wafer to form a thin film, which is then irradiated with activating radiation such as ultraviolet light through a mask pattern on which a device pattern is drawn, and the thin film is developed. The resulting photoresist pattern is then used as a protective film to etch the substrate, thereby forming a fine pattern on the surface of the substrate that corresponds to the above pattern.

[0004] As semiconductor patterns become finer, thinner photoresist films are required, which in turn requires thinner resist underlayer films. Even if the resist underlayer film is thin, the photoresist pattern must not collapse, and the resist underlayer film must have high adhesion to the photoresist film and be formed with a uniform thickness. In addition, the resist underlayer film must have a high refractive index and a low absorption coefficient for the light used in photolithography, and an etching rate faster than that of the photoresist film. Summary of the Invention [Problem to be solved by the invention]

[0005] The composition for a resist underlayer film according to one embodiment provides a resist underlayer film that does not cause resist pattern collapse in a fine patterning process, has high sensitivity to an exposure light source, and has improved patterning performance and energy efficiency.

[0006] Another embodiment provides a pattern forming method using the resist underlayer film composition.

[0007] A composition for a resist underlayer film according to one embodiment includes a polymer including a structural unit represented by the following chemical formula 1, a structural unit represented by the following chemical formula 2, a structural unit represented by the following chemical formula 3, or a combination thereof, a compound represented by any one or more of the following chemical formulas 4 to 6, and a solvent.

[0008] [ka]

[0009] In chemical formula 1 to chemical formula 3, A is a heterocyclic group containing a nitrogen atom in the ring, L 1 From 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, 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 From 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)-, or -NR a - (where R a is hydrogen, deuterium, or a C1 to C10 alkyl group, or a combination thereof; Y 1 From Y 4are each independently a hydroxy group, 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, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C2 to C10 heteroalkenyl group, a substituted or unsubstituted C2 to C10 heteroalkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 heteroaryl group, or a combination thereof; R 1 and R 2 are each independently hydrogen, deuterium, a hydroxy 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; * indicates a connection point.

[0010] [ka]

[0011] 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, a substituted or unsubstituted C6 to C30 aryl group, or are linked together to form a tricycloalkyl group.

[0012] [ka]

[0013] In chemical formula 5, R 5 stands for hydrogen, deuterium, hydroxyl group, halogen atom, cyano group, =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, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, 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. e R f (where R e and R f are each independently hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl group; or -C(=O)OR g (where R g is hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group; R 6 From R 9 are each independently hydrogen, deuterium, 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 combination thereof.

[0014] [ka]

[0015] 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 are each independently -O-, -C(=O)-, -C(=O)O-, -O(C=O)O-, -C(=O)NH-, -NHC(=O)-, or a combination thereof; R 10 From R 13 are each independently hydrogen, deuterium, 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 combination thereof; n is an integer of 2 or more and less than the valence of M.

[0016] A in Chemical Formula 1 and Chemical Formula 2 may be represented by one or more of Chemical Formulas A-1 to A-4 below.

[0017] [ka]

[0018] In chemical formula A-1 to chemical formula A-4, * is a linking point.

[0019] L 1 From 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 From X 8are each independently a single bond, -O-, -S-, -C(=O)-, -(CO)O-, -O(CO)O-, or a combination thereof; Y 1 From Y 4 are each independently a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, or a combination thereof; R 1 and R 2 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a combination thereof.

[0020] The composition for a resist underlayer film may further contain a compound represented by the following Chemical Formula 7.

[0021] [ka]

[0022] In formula 7, R 13 is deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof; p and q are each independently an integer greater than or equal to 1, and p+q is 6 or less.

[0023] R in Chemical Formula 4 3 and R 4 are each independently a substituted or unsubstituted C1 to C30 alkyl group, or are linked together to form a tricycloalkyl group.

[0024] R in Chemical Formula 5 5 is hydrogen, hydroxyl group, cyano group, -NCS, -NH2, -COOH, -OR b (where R bis 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, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C6 to C10 aryl group, or a combination thereof; or -NHC(=O)R d (where R d is a substituted or unsubstituted C1 to C10 alkyl group; 6 From R 9 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a combination thereof.

[0025] M in 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 are each independently -O-, -C(=O)-, -C(=O)O-, or a combination thereof; R 10 From R 13 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a combination thereof; and n is 2 or 3.

[0026] Chemical formula 4 may be represented by any one of Chemical formulas 4-1 to 4-3 below.

[0027] [ka]

[0028] Chemical formula 5 may be represented by any one of Chemical formulas 5-1 to 5-14 below.

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] Chemical formula 6 may be represented by the following chemical formula 6-1 or the following chemical formula 6-2.

[0033] [ka]

[0034] Chemical formula 7 may be represented by any one of Chemical Formulas 7-1 to 7-5 below.

[0035] [ka]

[0036] The weight average molecular weight of the above mentioned polymers is from 1,000 g / mol to 300,000 g / mol.

[0037] The polymer is contained in an amount of 0.1% by weight to 50% by weight based on the total weight of the composition for a resist underlayer film.

[0038] The above-mentioned compound is contained in an amount of 0.1% by weight to 30% by weight based on the total weight of the composition for a resist underlayer film.

[0039] The resist underlayer film composition may further include one or more polymers selected from an acrylic resin, an epoxy resin, a novolac resin, a glycoluril resin, and a melamine resin.

[0040] The resist underlayer film composition may further include an additive such as a surfactant, a thermal acid generator, a photoacid generator, a plasticizer, or a combination thereof.

[0041] According to another embodiment, there is provided a method for forming a pattern, the method including the steps of forming a film to be etched on a substrate, applying the above-described resist underlayer film composition onto the film to be etched to form a resist underlayer film, forming a photoresist pattern on the resist underlayer film, and sequentially etching the resist underlayer film and the film to be etched using the photoresist pattern as an etching mask.

[0042] The composition for a resist underlayer film according to one embodiment can provide a resist underlayer film that does not cause the collapse of a resist pattern even in a fine patterning process.

[0043] Furthermore, the composition for a resist underlayer film according to one embodiment can provide a resist underlayer film having improved sensitivity to an exposure light source, and thus improved pattern formability and energy efficiency. [Brief description of the drawings]

[0044] [Figure 1] FIG. 1 is a cross-sectional view illustrating a pattern forming method using a resist underlayer film composition according to an embodiment. [Diagram 2] FIG. 1 is a cross-sectional view illustrating a pattern forming method using a resist underlayer film composition according to an embodiment. [Diagram 3] FIG. 1 is a cross-sectional view illustrating a pattern forming method using a resist underlayer film composition according to an embodiment. [Figure 4] FIG. 1 is a cross-sectional view illustrating a pattern forming method using a resist underlayer film composition according to an embodiment. [Diagram 5]FIG. 1 is a cross-sectional view illustrating a pattern forming method using a resist underlayer film composition according to an embodiment. [Figure 6] FIG. 1 is a cross-sectional view illustrating a pattern forming method using a resist underlayer film composition according to an embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0045] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to exemplary embodiments thereof so that those skilled in the art can easily practice the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments set forth herein.

[0046] In the drawings, the thickness of the various layers and regions is exaggerated for clarity. Similar parts are designated by the same reference numerals throughout the specification. When a part, such as a layer, film, region, plate, etc., is described as being "on" another part, this includes not only when it is "directly on" the other part, but also when there is another part between them. Conversely, when a part is described as being "directly on" another part, it means that there is no other part between them.

[0047] Hereinafter, unless otherwise defined in the present specification, "substituted" means that a hydrogen atom in the compound is replaced with a substituent selected from deuterium, a halogen atom (F, Br, Cl, or I), a hydroxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono 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 phosphoric acid 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 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocyclic group, and combinations thereof.

[0048] Furthermore, two adjacent substituents among a substituted halogen atom (F, Br, Cl, or I), a hydroxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono 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 phosphoric acid 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 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, or a C2 to C30 heterocyclic group may be fused to form a ring.

[0049] Unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S, Se and P.

[0050] As used herein, the term "aryl group" refers to a group having one or more hydrocarbon aromatic moieties, and broadly includes hydrocarbon aromatic moieties linked by single bonds, as well as non-aromatic fused rings to which hydrocarbon aromatic moieties are directly or indirectly fused. Aryl groups include monocyclic, polycyclic, or fused polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional groups.

[0051] As used herein, the term "heterocyclic group" refers to a concept that includes heteroaryl groups, and additionally means that the heterocyclic group contains at least one heteroatom selected from N, O, S, P, and Si in place of carbon C in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof. When the heterocyclic group is a fused ring, the entire heterocyclic group or each ring may contain one or more heteroatoms.

[0052] More specifically, the substituted or unsubstituted aryl group and / or the substituted or unsubstituted heterocyclic group are a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted aryl ... or an unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted aryl ... Unsubstituted oxadiazolyl groups, substituted or unsubstituted thiadiazolyl groups, substituted or unsubstituted pyridinyl groups, substituted or unsubstituted pyrimidinyl groups, substituted or unsubstituted pyrazinyl groups, substituted or unsubstituted triazinyl groups, substituted or unsubstituted benzofuranyl groups, substituted or unsubstituted benzothiophenyl groups, substituted or unsubstituted benzimidazolyl groups, substituted or unsubstituted indolyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted isoquinolinyl groups, a substituted or unsubstituted aryl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazilyl group, a substituted or unsubstituted benzthiazilyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuralyl group,It may be, but is not limited to, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a pyridoindolyl group, a benzopyridoxazyl group, a benzopyridothiazyl group, a 9,9-dimethyl-9,10-dihydroacridyl group, a combination thereof, or a fused form of a combination thereof.

[0053] Unless otherwise specified herein, "combination" means blending or copolymerization.

[0054] In addition, in this specification, the term "polymer" may include both an oligomer and a polymer.

[0055] Unless otherwise specified in this specification, the "weight average molecular weight" is measured by dissolving a powder sample in tetrahydrofuran (THF) and then using an Agilent Technologies 1200 series gel permeation chromatography (GPC) (the column is a Shodex LF-804 and the standard column is a Shodex polystyrene).

[0056] Additionally, unless otherwise defined herein, "*" indicates a structural unit of a compound or a linking point of a moiety of a compound.

[0057] In the semiconductor industry, there is a constant demand for reducing the size of chips. To meet this demand, the line width of the resist patterned by lithography technology must be reduced to a size level of several tens of nanometers, and the pattern thus formed is used to transfer the pattern to the substrate by an etching process. However, as the resist pattern size becomes smaller, the aspect ratio of the resist that can withstand the line width is limited, and as a result, the resist may not have sufficient resistance in the etching step. Therefore, when a thin resist is used, when the substrate to be etched is thick, or when a deep pattern is required, a resist underlayer film has been used to compensate for the resistance of the resist.

[0058] The resist underlayer film is required to be thin as the resist thickness decreases, and the photoresist pattern must not collapse even if the resist underlayer film is thin. For this reason, the resist underlayer film must have excellent adhesion to the photoresist. In addition, when the resist underlayer film is formed thin, the coating uniformity of the resist underlayer film composition and the flatness of the resist underlayer film prepared from the resist underlayer film composition must be high, and further, the sensitivity to the exposure light source, pattern formability, and energy efficiency are required to be high.

[0059] A composition for a resist underlayer film according to one embodiment includes a polymer including a structural unit represented by the following chemical formula 1, a structural unit represented by the following chemical formula 2, a structural unit represented by the following chemical formula 3, or a combination thereof, a compound represented by any one or more of the following chemical formulas 4 to 6, and a solvent.

[0060] [ka]

[0061] In chemical formula 1 to chemical formula 3, A is a heterocyclic group containing a nitrogen atom in the ring, L 1 From L7 are each independently 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 From 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)-, or -NR a - (where R a is hydrogen, deuterium, or a C1 to C10 alkyl group, or a combination thereof; Y 1 From Y 4 are each independently a hydroxy group, 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, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C2 to C10 heteroalkenyl group, a substituted or unsubstituted C2 to C10 heteroalkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 heteroaryl group, or a combination thereof; R 1 and R 2 are each independently hydrogen, deuterium, a hydroxy 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; * indicates a connection point.

[0062] [ka]

[0063] 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, a substituted or unsubstituted C6 to C30 aryl group, or R 3 and R 4 are linked together to form a tricycloalkyl group.

[0064] [ka]

[0065] In chemical formula 5, R 5 stands for hydrogen, deuterium, hydroxyl group, halogen atom, cyano group, =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, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, 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. e R f (where Re and R f are each independently hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl group; or -C(=O)OR g (where R g is hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group; R 6 From R 9 are each independently hydrogen, deuterium, 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 combination thereof.

[0066] [ka]

[0067] In 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 are each independently -O-, -C(=O)-, -C(=O)O-, -O(C=O)O-, -C(=O)NH-, -NHC(=O)-, or a combination thereof; R 10 From R 13 are each independently hydrogen, deuterium, 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 combination thereof; n is an integer of 2 or more and less than the valence of M.

[0068] A resist underlayer film composition according to an embodiment includes a polymer including one or more structural units represented by Chemical Formulae 1 to 3, and a compound represented by Chemical Formulae 4 to 6, and thus when applied to a resist underlayer film, the resist sensitivity can be improved and the formability of a fine pattern can be improved. This is because the compounds represented by Chemical Formulae 4 to 6 can act as radical scavengers that provide electrons to highly reactive radicals to make the radicals stable.

[0069] The structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2 constituting the polymer in the resist underlayer film composition according to one embodiment contain a heterocycle containing a nitrogen atom in the ring. As a result, the polymer containing one or more of the above structural units has sp 2 -sp 2 Bonding is possible. Therefore, the polymer has high electron density, and by including a polymer having high electron density, the resist underlayer film composition according to an embodiment can realize a film having a dense structure in the form of an ultra-thin film. In addition, the high electron density of the polymer can have the effect of improving the light absorption efficiency during exposure of the resist underlayer film composition. Furthermore, by including a heterocyclic skeleton, the polymer has excellent etching selectivity, and can improve the energy efficiency during pattern formation by exposure using high-energy rays such as EUV (Extreme ultra violet; wavelength 13.5 nm) and E-Beam (electron beam).

[0070] A in Chemical Formula 1 and Chemical Formula 2 may be represented by one or more of the following Chemical Formula A-1 to Chemical Formula A-4.

[0071] [ka]

[0072] In chemical formula A-1 to chemical formula A-4, * is a linking point.

[0073] L 1 From L 7 are each independently a single 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, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof, for example, but not limited to, a single 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.

[0074] X 1 From X 8 are each independently a single bond, -O-, -S-, -S(=O)-, -C(=O)-, -(CO)O-, -O(CO)O-, -C(=O)NH-, or a combination thereof, for example, but not limited to, a single bond, -O-, -S-, -C(=O)-, -(CO)O-, -O(CO)O-, or a combination thereof.

[0075] Y 1 From Y 4are each independently a hydroxy group, 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, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 heteroaryl group, or a combination thereof, for example, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C and combinations thereof, such as, but not limited to, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, or combinations thereof, such as, but not limited to, a hydroxy group, a substituted or unsubstituted C1 to C5 alkyl group, a substituted or unsubstituted C2 to C5 alkenyl group, or combinations thereof.

[0076] R 1 and R 2 are each independently hydrogen, deuterium, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or substituted or unsubstituted C2 to C10 alkenyl group, or a combination thereof, such as, but not limited to, hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, or a combination thereof, such as, for example, hydrogen, or a substituted or unsubstituted C1 to C10 alkyl group, such as hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group, such as, but not limited to, hydrogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, or a combination thereof.

[0077] As an example, chemical formula 1 may be represented by any one of chemical formulas 1-1 to 1-3 below, chemical formula 2 may be represented by any one of chemical formulas 2-1 to 2-3 below, and chemical formula 3 may be represented by any one of chemical formulas 3-1 to 3-3 below.

[0078] [ka]

[0079] [ka]

[0080] In the compound represented by Chemical Formula 4 contained in the composition for resist underlayer film according to one embodiment, 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, a substituted or unsubstituted C6 to C30 aryl group, or can be linked together to form a tricycloalkyl group, for example, a substituted or unsubstituted C1 to C20 alkyl group, or can be linked together to form a tricycloalkyl group, but are not limited thereto. For example, R 3 and R 4 may each independently be a C1 to C30 alkyl group substituted with an aryl group, an unsubstituted C1 to C30 alkyl group, or may be linked together to form a tricycloalkyl group, but is not limited thereto.

[0081] In one embodiment, Chemical Formula 4 may be represented by any one of Chemical Formulas 4-1 to 4-3 below.

[0082] [ka]

[0083] R of the compound represented by Chemical Formula 5 contained in the composition for resist underlayer film according to one embodiment 5 stands for hydrogen, deuterium, hydroxyl group, halogen atom, cyano group, =O, -NCS, -OR b , -OC(=O)R c , -NHC(=O)R d , -NR e R f , or -C(=O)OR g may be also possible.

[0084] For example, 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, for example, but not limited to, an epoxy group-substituted C1 to C10 alkyl group, an unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C2 to C5 alkynyl group.

[0085] For example, R c is 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, such as, but not limited to, a C2 to C5 alkenyl group substituted with a methyl group, or a substituted or unsubstituted C6 to C10 aryl group.

[0086] For example, R d is 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.

[0087] For example, R e and R fare each independently hydrogen, deuterium, or a substituted or unsubstituted C1 to C5 alkyl group, for example, but not limited to, each hydrogen.

[0088] For example, R g is hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, for example, but not limited to, hydrogen.

[0089] In one embodiment, Formula 5 may be represented by any one of Formulas 5-1 to 5-14 below.

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] M of the compound represented by Chemical Formula 6 contained in the resist underlayer film composition according to one embodiment 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 C10 arylene group, for example, a substituted or unsubstituted C1 to C5 alkylene group or an unsubstituted C3 to C10 heterocycloalkylene group, for example, the heterocycloalkylene group may be an isocyanurate, but is not limited thereto.

[0095] L 8 and L 9 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof, including, but not limited to, a single bond, a substituted or unsubstituted C1 to C5 alkylene group, or a combination thereof.

[0096] X 9 and X 10 are each independently -O-, -C(=O)-, -C(=O)O-, or combinations thereof, but are not limited to these.

[0097] R 10 From R 13 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, for example, a substituted or unsubstituted C1 to C5 alkyl group, for example, but not limited to, an unsubstituted methyl group, an unsubstituted ethyl group, or combinations thereof.

[0098] n is an integer of 2 or more, smaller than the valence of M, and is, for example, one of integers from 2 to 6, such as, but not limited to, 2 or 3. When n is an integer of 2 or more, the compound represented by Chemical Formula 6 can more effectively donate electrons.

[0099] In one embodiment, Chemical Formula 6 may be represented by the following Chemical Formula 6-1 or the following Chemical Formula 6-2.

[0100] [ka]

[0101] The composition for a resist underlayer film according to an embodiment may further include a compound represented by the following Chemical Formula 7.

[0102] [ka]

[0103] In formula 7, R 13 is deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof; p and q are each independently an integer greater than or equal to 1, and p+q is 6 or less.

[0104] R 13 is, for example, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, or a combination thereof, for example, a substituted or unsubstituted C1 to C5 alkyl group, a substituted or unsubstituted C1 to C5 alkoxy group, or a combination thereof, for example, but not limited to, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-propyl group, a t-butyl group, a methoxy group, an ethoxy group, or a combination thereof.

[0105] p and q are each independently an integer from 1 to 5, for example, but not limited to, an integer from 1 to 3, and the sum of p and q is an integer from 2 to 6, for example, but not limited to, an integer from 2 to 5, for example, but not limited to, 2 to 4.

[0106] In one embodiment, Formula 7 may be represented by Formula 7-1 to Formula 7-5 below.

[0107] [ka]

[0108] The polymer contained in the resist underlayer film composition according to an embodiment may have a weight average molecular weight of 1,000 g / mol to 300,000 g / mol, for example, about 3,000 g / mol to 200,000 g / mol, for example, 3,000 g / mol to 100,000 g / mol, for example, 3,000 g / mol to 90,000 g / mol, for example, 3,000 g / mol to 70,000 g / mol, for example, 3,000 g / mol to 70,000 g / mol, for example, 3,000 g / mol to 50,000 g / mol, for example, 5,000 g / mol to 50,000 g / mol, for example, 5,000 g / mol to 30,000 g / mol, but is not limited thereto. By having the weight average molecular weight in the above range, the carbon content and solubility in a solvent of the composition for a resist underlayer film containing the polymer can be adjusted and optimized.

[0109] The polymer may be included in the resist underlayer film composition in an amount of 0.1% by weight to 50% by weight based on the total weight of the resist underlayer film composition. More specifically, the polymer may be included in the resist underlayer film composition in an amount of 10% by weight to 50% by weight, for example, 20% by weight to 50% by weight, for example, 20% by weight to 30% by weight, but is not limited thereto. By including the polymer in the resist underlayer film composition in the above range, the thickness, surface roughness, and flattening degree of the resist underlayer film can be adjusted.

[0110] The compound contained in the resist underlayer film composition according to an embodiment may be contained in an amount of 0.01% by weight to 30% by weight based on the total weight of the resist underlayer film composition. More specifically, the compound may be contained in an amount of 0.1% by weight to 30.0% by weight based on the total weight of the resist underlayer film composition, for example, 1.0% by weight to 30.0% by weight, for example, 5.0% by weight to 30.0% by weight, for example, 5.0% by weight to 25.0% by weight, for example, 8.0% by weight to 25.0% by weight, for example, 10.0% by weight to 25.0% by weight, for example, 20.0% by weight, but is not limited thereto. The compound contained in the resist underlayer film composition in the above ranges can adjust the thickness, surface roughness, chemical resistance and flattening degree of the resist underlayer film.

[0111] The resist underlayer film composition according to an embodiment may contain a solvent. The solvent is not particularly limited as long as it has sufficient solubility and / or dispersibility for the polymer contained in the resist underlayer film composition according to an embodiment. The solvent may include, for example, propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, methyl 2-hydroxyisobutyrate, acetylacetone, ethyl 3-ethoxypropionate, or a combination thereof, but is not limited thereto.

[0112] The resist underlayer film composition according to an embodiment may further include, in addition to the polymer, the compound, and the solvent, one or more additional polymers selected from an acrylic resin, an epoxy resin, a novolac resin, a glycoluril resin, and a melamine resin, but is not limited thereto. The additional polymer may be added to the resist underlayer film composition according to an embodiment in an amount of about 0.2 wt %.

[0113] The resist underlayer film composition according to another embodiment may further include an additive including a surfactant, a thermal acid generator, a photoacid generator, a plasticizer, or a combination thereof.

[0114] The surfactant can be used to improve coating defects caused by an increase in solid content during the formation of the resist underlayer film. Examples of the surfactant include, but are not limited to, alkylbenzenesulfonates, alkylpyridinium salts, polyethylene glycols, and quaternary ammonium salts.

[0115] Examples of the thermal acid generator that may be used include, but are not limited to, acidic compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid, and / or benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters.

[0116] The plasticizer is not particularly limited, and various known plasticizers can be used. Examples of the plasticizer include low molecular weight compounds such as phthalates, adipic esters, phosphates, trimellitic esters, and citrates, as well as polyether, polyester, and polyacetal compounds.

[0117] According to another embodiment, there is provided a resist underlayer film prepared using the composition for a resist underlayer film. The resist underlayer film may be in a form obtained by, for example, coating the composition for a resist underlayer film on a substrate and then curing the composition through a heat treatment process.

[0118] Hereinafter, a method for forming a pattern using the above-mentioned composition for a resist underlayer film will be described with reference to Fig. 1 to Fig. 6. Fig. 1 to Fig. 6 are cross-sectional views for explaining the method for forming a pattern using the composition for a resist underlayer film according to the present invention.

[0119] Referring to FIG. 1, first, an object to be etched is prepared. An example of the object to be etched may be a thin film 102 formed on a semiconductor substrate 100. In the following, only the case where the object to be etched is the thin film 102 will be described. 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, or a silicon oxide film.

[0120] Next, the above-mentioned resist underlayer film composition is coated on the surface of the cleaned thin film 102 by spin coating.

[0121] Thereafter, a drying and baking process is performed to form a resist underlayer film 104 on the thin film 102. The baking process is performed at 100° C. to 500° C., and may be performed, for example, at 100° C. to 300° C. A more specific description of the composition for the resist underlayer film has already been given in detail, and therefore will be omitted to avoid duplication.

[0122] 2, a photoresist is coated on the resist underlayer film 104 to form a photoresist film 106. In one embodiment, the photoresist composition forming the photoresist film 106 may include, but is not limited to, an organometallic compound containing Sn, a solvent, and the like.

[0123] Next, a first baking process is performed to heat the substrate 100 on which the photoresist film 106 is formed. The first baking process may be performed at a temperature of 90°C to 120°C.

[0124] 3, the photoresist film 106 is selectively exposed to light. To explain the exposure process for exposing the photoresist film 106 as an example, an exposure mask having a predetermined pattern formed thereon is placed on a mask stage of an exposure device, and an exposure mask 110 is placed on the photoresist film 106. Next, by irradiating the mask 110 with light, a predetermined portion of the photoresist film 106 formed on the substrate 100 selectively reacts with the light transmitted through the exposure mask.

[0125] Examples of light used in the exposure process include short wavelength light such as activating radiation i-line having a wavelength of 365 nm, KrF excimer laser having a wavelength of 248 nm, and ArF excimer laser having a wavelength of 193 nm, as well as EUV (Extreme ultraviolet) having a wavelength of 13.5 nm, which corresponds to extreme ultraviolet light.

[0126] The exposed regions 106b of the photoresist film 106 form polymers through crosslinking reactions such as condensation between organometallic compounds, and as a result have a different solubility from the unexposed regions 106a of the photoresist film 106.

[0127] Next, 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 106b of the photoresist film 106 becomes less soluble in a developer.

[0128] Referring to FIG. 4, the photoresist film 106a corresponding to the unexposed area is dissolved and removed using an organic solvent developer such as 2-heptanone, and the photoresist film 106b remaining after development forms a photoresist pattern 108.

[0129] As described above, the developer used in the pattern formation method according to an embodiment may be an organic solvent. Examples of the organic solvent used in the pattern formation method according to an embodiment 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, and combinations thereof.

[0130] However, the photoresist pattern according to an embodiment is not limited to being formed as a negative tone image, and may be formed to have a positive tone image. In this case, the developer used to form the positive tone image may be a quaternary ammonium hydroxide composition such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0131] As described above, the photoresist pattern 108 formed by exposure to light having a wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam) may have a width of 5 nm to 100 nm. As an example, the photoresist pattern 108 may be formed with a width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, 5 nm to 20 nm, or 5 nm to 10 nm.

[0132] Meanwhile, the photoresist pattern 108 can have a half-pitch of about 50 nm or less, e.g., 40 nm or less, e.g., 30 nm or less, e.g., 20 nm or less, e.g., 10 nm or less, and a linewidth roughness of about 5 nm or less, about 3 nm or less, about 2 nm or less, about 1 nm or less.

[0133] Next, the resist underlayer film 104 is etched using the photoresist pattern 108 as an etching mask. By this etching process, an organic film pattern 112 as shown in FIG.

[0134] The formed organic film pattern 112 may also have a width corresponding to the photoresist pattern 108. The etching may be performed by dry etching using an etching gas. The etching gas may be, for example, CHF3, CF4, Cl2, O2, or a mixture thereof. As described above, the resist underlayer film formed by the resist underlayer film composition according to an embodiment has a high etching rate, and therefore, a smooth etching process can be performed within a short time.

[0135] 6, the photoresist pattern 108 is applied as an etching mask to etch the exposed thin film 102. As a result, the thin film 102 provides a thin film pattern 114.

[0136] The thin film pattern 114 formed by the exposure process using a short wavelength light source such as activating radiation i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), or ArF excimer laser (wavelength 193 nm) can have a width of several tens of nm to several hundreds of nm, and the thin film pattern 114 formed by the exposure process using an EUV light source can have a width of 20 nm or less. EXAMPLES

[0137] The present invention will be described in more detail below with reference to examples of synthesis of the above-mentioned polymer and preparation of a composition for a resist underlayer film containing the same. However, the present invention is not technically limited to the following examples.

[0138] Polymer Synthesis Polymerization Example 1 24.9g of 1,3-diallyl-5-(2-hydroxyethyl)isocyanurate, 7.4g of mercaptoethanol, 0.7g of AIBN (azobisisobutyronitrile), and 48g of N,N-dimethylformamide (DMF) were added to a 500mL three-neck round-bottom flask, and a condenser was connected. After reacting at 80°C for 16 hours, the reaction solution was cooled to room temperature. The reaction solution was dropped into a 1L wide-mouth bottle containing 800g of water while stirring the water to generate gum, and the gum was then dissolved in 80g of tetrahydrofuran (THF). A precipitate was formed from the dissolved resin solution using toluene to remove monomolecules and low molecules, and 10g of a polymer consisting of a structural unit represented by the following chemical formula 1-1 was obtained. (Weight average molecular weight (Mw)=10,500g / mol)

[0139] [ka]

[0140] Polymerization Example 2 24.9g of 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione, 7.4g of mercaptoethanol, 0.7g of AIBN (azobisisobutyronitrile), and 48g of N,N-dimethylformamide (DMF) were added to a 500mL three-necked round-bottom flask, and a condenser was connected. After reacting at 80°C for 16 hours, the reaction solution was cooled to room temperature. The reaction solution was dropped into a 1L wide-mouth bottle containing 800g of water while stirring the water to generate gum, and the gum was then dissolved in 80g of tetrahydrofuran (THF). A precipitate was formed from the dissolved resin solution using toluene to remove monomolecules and low molecules, and 10g of a polymer consisting of a structural unit represented by the following chemical formula 1-2 was obtained. (Weight average molecular weight (Mw)=8,000g / mol)

[0141] [ka]

[0142] Compound synthesis Synthesis Example 1 A reaction solution was prepared by adding 2.5g of succinic acid, 10g of 4-glycidyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 3.5g of pyridine, and 50g of N,N-dimethylformamide to a 250mL flask, and a condenser was connected to the flask. The reaction solution was heated at 100°C for 10 hours, and the end of the reaction was confirmed and cooled to room temperature. The reaction solution was then washed with distilled water, and the solvent was removed from the organic layer to obtain a compound represented by the following chemical formula 6-2.

[0143] [ka]

[0144] Preparation of Resist Underlayer Film Composition Example 1 The polymer obtained in Polymerization Example 1 and 1.2 g of Bis(octadecyl)hydroxylamine (Sigma-Aldrich) represented by the following chemical formula 4-3 in a ratio of 100:30, 0.4 g of PD1174 (crosslinking agent), and 0.02 g of pyridinium para-toluenesulfonate (PPTS) were mixed and completely dissolved in propylene glycol monomethyl ether to a solid content of 3%, and then diluted with an additional solvent to prepare a resist underlayer film composition according to each Example. preparation did.

[0145] [ka]

[0146] Example 2 The polymer obtained in Polymerization Example 1 and 1.2 g of 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (Sigma-Aldrich) represented by the following chemical formula 5-2 were mixed in a ratio of 100:30, 0.4 g of PD1174 (crosslinking agent), and 0.02 g of pyridinium para-toluenesulfonate (PPTS) were mixed and completely dissolved in propylene glycol monomethyl ether to a solid content of 3%, and then diluted with an additional solvent to prepare a resist underlayer film composition according to each Example.

[0147] [ka]

[0148] Example 3 The polymer obtained in Polymerization Example 1 and the compound obtained in Synthesis Example 1 (1.2 g) were mixed in a ratio of 100:30 with 0.4 g of PD1174 (crosslinking agent) and 0.02 g of pyridinium para-toluenesulfonate (PPTS) in propylene glycol monomethyl ether to a solid content of 3% and completely dissolved therein, followed by dilution with an additional solvent to prepare a resist underlayer film composition according to each Example.

[0149] Example 4 The polymer obtained in Polymerization Example 1 and 1.2 g of 2,6-Di-tert-butyl-4-methylphenol (Sigma-Aldrich) represented by the following chemical formula 7-1 in a ratio of 100:30, 0.4 g of PD1174 (crosslinking agent), and 0.02 g of pyridinium para-toluenesulfonate (PPTS) were mixed and completely dissolved in propylene glycol monomethyl ether to a solid content of 3%, and then diluted with an additional solvent to prepare a resist underlayer film composition according to each Example.

[0150] [ka]

[0151] Example 5 The polymer obtained in Polymerization Example 1 and 1.2 g of 2,6-Di-tert-butyl-4-methoxyphenol (Sigma-Aldrich) represented by the following chemical formula 7-4 in a ratio of 100:30, 0.4 g of PD1174 (crosslinking agent), and 0.02 g of pyridinium para-toluenesulfonate (PPTS) were mixed and completely dissolved in propylene glycol monomethyl ether to a solid content of 3%, and then diluted with an additional solvent to prepare a resist underlayer film composition according to each Example.

[0152] [ka]

[0153] Comparative Example 1 1.2 g of the polymer obtained in Polymerization Example 1, 0.4 g of PD1174 (crosslinking agent), and 0.02 g of pyridinium para-toluenesulfonate (PPTS) were mixed and completely dissolved in propylene glycol monomethyl ether to a solid content of 3%, and then diluted with an additional solvent to prepare a composition for a resist underlayer film.

[0154] Comparative Example 2 A composition for a resist underlayer film was prepared in the same manner as in Comparative Example 1, except that the polymer obtained in Polymerization Example 2 was used instead of the polymer obtained in Polymerization Example 1.

[0155] Evaluation 1: Coating uniformity evaluation 2 mL of each of the resist underlayer film compositions obtained in the Examples and Comparative Examples was dispensed onto an 8-inch wafer, and spin-coated at a main spin speed of 1,500 rpm for 20 seconds using an auto track (TEL Corporation's ACT-8), and then cured at 205° C. for 60 seconds to form a thin film with a thickness of 5 nm.

[0156] The thickness was measured at 51 points along the horizontal axis, and the difference between the maximum and minimum thickness values ​​was compared to evaluate the coating uniformity according to the following calculation formula 1. The smaller the coating uniformity value, the better the coating uniformity. The results are shown in Table 1 below. [Formula 1] Coating uniformity (nm) = Maximum - minimum thickness measured at 51 points on the wafer

[0157] [Table 1]

[0158] Referring to Table 1, the resist underlayer film formed from the resist underlayer film composition according to the Example exhibits a smaller coating uniformity than the film formed from the resist underlayer film composition according to the Comparative Example, and it can be seen that the resist underlayer film composition according to the Example is superior in coating uniformity of the formed resist underlayer film to the resist underlayer film composition according to the Comparative Example.

[0159] Evaluation 2: Chemical resistance evaluation 2 mL of each of the resist underlayer film compositions prepared in the examples and comparative examples was dropped onto a 4-inch wafer, and spin-coated at 1,500 rpm for 20 seconds using a spin coater (Mikasa). Then, curing was performed at 210°C for 90 seconds, and the thickness of the thin film formed was measured using a K-MAC thin film thickness measuring device. Next, the thin 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, removed, and the thickness of the thin film was measured. The chemical resistance of the underlayer film was evaluated from the reduction rate of the thickness measured before and after immersion according to the following calculation formula 2. The smaller the thickness reduction rate, the better the chemical resistance. The results are shown in Table 2 below. [Formula 2] Lower layer thickness reduction rate (%) = {(thin film thickness before immersion - thin film thickness after immersion) / thin film thickness before immersion} × 100

[0160] [Table 2]

[0161] From Table 2, it can be seen that the thickness reduction rate before and after immersion in the mixed solution of PGME and PGMEA in the Examples is smaller than that in the Comparative Examples, and therefore it can be seen that the chemical resistance of the resist underlayer films in the Examples is superior to that of the resist underlayer films in the Comparative Examples.

[0162] Rating 3: Delay rating 2 mL of each of the resist underlayer film compositions according to the examples and comparative examples was dropped onto a 4-inch wafer, and then spin-coated at 1,500 rpm for 20 seconds using a spin coater (Mikasa). Then, curing was performed at 210°C for 90 seconds to form a thin film. A photoresist for EUV lithography was applied onto these underlayer films using a spinner, and curing was performed on a hot plate at 110°C for 60 seconds to form a photoresist film, and a 50 nm line & 50 nm space (L / S) pattern was drawn using an electron beam lithography device (E-beam). The resist pattern on the silicon wafer formed by immediately developing the resist pattern using an aqueous solution of tetramethylammonium hydroxide as a developer is called the pattern result with no delay of 0 minutes. On the other hand, the resist pattern on the silicon wafer formed by drawing a line & space (L / S) pattern using an electron beam lithography device (E-beam), leaving it for 30 minutes, and then developing it with a developer is called the pattern result with delay of 30 minutes. The delay was evaluated based on the difference in size (nm) between a 0 minute pattern with no delay and a 30 minute pattern with a delay, according to the following formula 3. The results are shown in Table 3 below. [Formula 3] Pattern size change (nm) = (pattern size at 30 minutes delay - pattern size at 0 minutes delay)

[0163] [Table 3]

[0164] Referring to Table 3, it can be seen that the resist underlayer film according to the embodiment has a smaller change in pattern when the exposure is delayed, and therefore the resist pattern change due to the resist underlayer film according to the embodiment is superior to that of the resist underlayer film according to the comparative example.

[0165] As described above, although specific embodiments of the present invention have been described and illustrated, the present invention is not limited to the described embodiments, and it is obvious to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or variations should not be understood separately from the technical spirit and perspective of the present invention, and the modified embodiments should belong to the scope of the claims of the present invention. [Explanation of symbols]

[0166] 100: Substrate 102: Thin film 104: Resist underlayer film 106: Photoresist film 106a: Unexposed area 106b: Exposed area 108: Photoresist pattern 110: Mask 112: Organic film pattern 114: Thin film pattern

Claims

1. A polymer including a structural unit represented by the following chemical formula 1, a structural unit represented by the following chemical formula 2, a structural unit represented by the following chemical formula 3, or a combination thereof, a compound represented by any one or more of the following chemical formulas 4 to 6, and a solvent, 【Chemistry 1】 In the formula 1 to the formula 3, A is a heterocyclic group containing a nitrogen atom in the ring, L １ From 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, 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 From X ８ are each independently 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 - (where R ａ is hydrogen, deuterium, or a C1 to C10 alkyl group, or a combination thereof; Y １ From Y ４ are each independently a hydroxy group, 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, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C2 to C10 heteroalkenyl group, a substituted or unsubstituted C2 to C10 heteroalkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 heteroaryl group, or a combination thereof; R １ and R ２ are each independently hydrogen, deuterium, a hydroxy 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; * indicates a connection point. 【Chemistry 2】 In the above 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, a substituted or unsubstituted C6 to C30 aryl group, or are linked together to form a tricycloalkyl group; 【Chemistry 3】 In the above Chemical Formula 5, R ５ represents hydrogen, deuterium, a hydroxyl group, a halogen atom, a cyano group, ═O, —NCS, —OR ｂ (Here, 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. ｃ (Here, R ｃ is 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 C30 aryl group, or a combination thereof. ), -NHC(=O)R ｄ (Here, R ｄ is a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group. ｅ R ｆ (Here, R ｅ and R ｆ are each independently hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl group; ｇ (Here, R ｇ is hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group; R ６ From R ９ are each independently hydrogen, deuterium, 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 combination thereof; 【Chemistry 4】 In the above 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 From R １３ are each independently hydrogen, deuterium, 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 combination thereof; The composition for a resist underlayer film, wherein n is an integer of 2 or more and is smaller than the valence of M.

2. A in the formula 1 and the formula 2 is represented by one or more of the following formulas A-1 to A-4: 【Chemistry 5】 The composition for a resist underlayer film according to claim 1, wherein in the chemical formulae A-1 to A-4, * represents a linking point.

3. Said L １ From 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; The X １ From X ８ each independently represents a single bond, —O—, —S—, —C(═O)—, —(CO)O—, —O(CO)O—, or a combination thereof, The Y １ From Y ４ are each independently a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, or a combination thereof; R １ and R ２ 2. The resist underlayer film composition according to claim 1, wherein each independently is hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a combination thereof.

4. The compound further includes a compound represented by the following formula 7: 【Chemistry 6】 In the above Chemical Formula 7, R １３ is deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof; 2. The resist underlayer film composition according to claim 1, wherein p and q are each independently an integer of 1 or more, and p+q is 6 or less.

5. R of Formula 4 ３ and R ４ The resist underlayer film composition according to claim 1 , wherein each of the groups is independently a substituted or unsubstituted C1 to C30 alkyl group, or is linked together to form a tricycloalkyl group.

6. R of Formula 5 ５ is hydrogen, a hydroxyl group, a cyano group, -NCS, -NH ２ , -COOH, -OR ｂ (Here, 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. ｃ (Here, R ｃ is 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 C10 aryl group, or a combination thereof; or -NHC(=O)R ｄ (Here, R ｄ is a substituted or unsubstituted C1 to C10 alkyl group; R ６ From R ９ 2. The resist underlayer film composition according to claim 1, wherein each independently is hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a combination thereof.

7. M in the above 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 independently represents -O-, -C(=O)-, -C(=O)O-, or a combination thereof; R １０ From R １３ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a combination thereof; The resist underlayer film composition according to claim 1 , wherein n is 2 or 3.

8. The composition for a resist underlayer film according to claim 1, wherein the chemical formula 4 is represented by any one of the following chemical formulas 4-1 to 4-3. 【Chemistry 7】

9. The composition for a resist underlayer film according to claim 1, wherein the chemical formula 5 is represented by any one of the following chemical formulas 5-1 to 5-14. 【Chemistry 8】 【Chemistry 9】 【Chemistry 10】

10. The composition for a resist underlayer film according to claim 1, wherein the chemical formula 6 is represented by the following chemical formula 6-1 or 6-2: 【Chemistry 11】

11. The composition for a resist underlayer film according to claim 4, wherein the chemical formula 7 is represented by any one of the following chemical formulas 7-1 to 7-5. 【Chemistry 12】

12. 2. The composition for a resist underlayer film according to claim 1, wherein the weight average molecular weight of the polymer is from 1,000 g / mol to 300,000 g / mol.

13. The composition for a resist underlayer film according to claim 1 , wherein the polymer is contained in an amount of 0.1% by weight to 50% by weight based on the total weight of the composition for a resist underlayer film.

14. The composition for a resist underlayer film according to claim 1 , wherein the compound is contained in an amount of 0.1% by weight to 30% by weight based on the total weight of the composition for a resist underlayer film.

15. 2. The resist underlayer film composition according to claim 1, further comprising one or more polymers selected from an acrylic resin, an epoxy resin, a novolac resin, a glycoluril resin, and a melamine resin.

16. The resist underlayer film composition according to claim 1 , further comprising an additive selected from the group consisting of a surfactant, a thermal acid generator, a photoacid generator, a plasticizer, and combinations thereof.

17. forming a film to be etched on a substrate; A step of applying the resist underlayer film composition according to any one of claims 1 to 16 onto the etching target film to form a resist underlayer film; forming a photoresist pattern on the resist underlayer film; and sequentially etching the resist underlayer film and the etching target film using the photoresist pattern as an etching mask; A pattern forming method comprising the steps of:

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