Resist underlayer composition and method of forming patterns using the same

Abstract

To provide 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 capable of improving patterning performance and energy efficiency.SOLUTION: A resist underlayer composition comprises: a polymer including specific structural units represented by Chemical Formula 1 and the like; a compound represented by Chemical Formula 3; and a solvent. A method of forming a pattern utilizes the resist underlayer composition.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] Recently, in the semiconductor industry, ultrafine technology with patterns of several hundreds of nanometers to several to tens of nanometers has been developed. In order to realize such ultrafine technology, effective lithography technology is essential.

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

[0004] As semiconductor patterns become increasingly finer, the thickness of the photoresist layer must be reduced, and therefore the thickness of the resist underlayer must be reduced. The resist underlayer must be small enough to prevent the photoresist pattern from collapsing, have good adhesion to the photoresist, and be formed with a uniform thickness. In addition, the resist underlayer must have a high refractive index and low absorption coefficient for the light used in photolithography, and an etching rate higher than that of the photoresist layer. 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 even in a fine patterning process, has improved sensitivity to an exposure light source, and can improve patterning performance and energy efficiency.

[0006] The composition for a resist underlayer film according to one embodiment provides a resist underlayer film having improved adhesion between the resist and the resist underlayer film.

[0007] Another embodiment provides a pattern forming method using the resist underlayer film composition.

[0008] A composition for a resist underlayer film according to one embodiment includes a polymer including a structural unit represented by Chemical Formula 1 below, a structural unit represented by Chemical Formula 2 below, or a combination thereof, a compound represented by Chemical Formula 3 below, and a solvent:

[0009] [ka]

[0010] [ka]

[0011] In Chemical Formula 1 and Chemical Formula 2, A is a heterocyclic group containing a nitrogen atom in the ring, L 1 ~L 6 each independently represents a single bond, a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 heteroalkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted C2-C20 heterocycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C1-C20 heteroarylene group, or a combination thereof; X 1 ~X 5 each independently represents a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -(CO)O-, -O(CO)O-, or -NR a - (where R a is hydrogen, deuterium, or a C1-C10 alkyl group), or a combination thereof; Y 1 ~Y3 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, and * is a linking position.

[0012] [ka]

[0013] In chemical formula 3, R 1 , R 2 , and R 4 are each independently hydrogen, deuterium, a cyano group, iodine, an azide group (-N3), a halogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 heteroalkyl group, a substituted or unsubstituted C2-C20 heteroalkenyl group, a substituted or unsubstituted C2-C20 heteroalkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, -OR b , -C(=O)R c , -C(=O)OR d , -OC(=O)OR e , -NR f R g , -NR h (C=O)R i (where R b ~R iare each hydrogen, deuterium, 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 C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, or a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R 3 -OR j , -C(=O)R k , -C(=O)OR l , -OC(=O)OR m , or -L a -OR n (Here, L a is a substituted or unsubstituted C1 to C5 alkylene group or a substituted or unsubstituted C6 to C16 arylene group, R j ~R n are each independently hydrogen, deuterium, 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 C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, or a substituted or unsubstituted C6 to C20 aryl group; x and y each independently represent an integer of 0 to 2, provided that 0≦x+y≦2.

[0014] A is represented by any one or more of the following chemical formulae A-1 to A-4. [ka]

[0015] In Chemical Formulae A-1 to A-4, * indicates a moiety that is connected to another atom or group.

[0016] L 1 ~L 6are 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 ~X 5 are each independently a single bond, -O-, -S-, -C(=O)-, -(CO)O-, -O(CO)O-, or a combination thereof; Y 1 ~Y 3 are each independently 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 C10 heteroalkenyl 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, or a combination thereof.

[0017] R 1 , R 2 , and R 4 At least one of the following is a cyano group, an iodine group, an azide group (-N3), or an -OR b , -C(=O)R c , -C(=O)OR d , -OC(=O)OR e , -NR f R g , or -NR h (C=O)R i (where R b ~R i are each independently hydrogen, deuterium, 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 C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

[0018] R 1 , R 2 , and R 4is an iodine, an azide group (-N3), 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 b , N.R. f R g , -NR h (C=O)R i (where R b , and R f ~R i are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C10 heteroalkyl group, or a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, and R 3 -OR j (where R j 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 C2 to C10 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

[0019] R 1 , R 2 , and R 4 each independently represents hydrogen, deuterium, iodine, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C6 to C30 aryl group, -OR b , -C(=O)R c , -C(=O)OR d , -OC(=O)OR e (where R b ~R eare each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, R 3 -OR j , or -C(=O)OR l (where R j and R l are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

[0020] Chemical formula 1 is represented by the following chemical formula 1-1 or chemical formula 1-2, and chemical formula 2 is represented by any one of the following chemical formulas 2-1 to 2-3.

[0021] [ka]

[0022] Chemical formula 3 is represented by at least one of the following chemical formulas 3-1 to 3-4. [ka]

[0023] The weight average molecular weight of the polymer may be from 1,000 g / mol to 300,000 g / mol.

[0024] The resist underlayer film composition may contain 10 parts by weight to 800 parts by weight of the compound based on 100 parts by weight of the polymer. The resist underlayer film composition may contain 30 parts by weight to 500 parts by weight of the compound based on 100 parts by weight of the polymer. The resist underlayer film composition may contain 0.1% by weight to 50% by weight of the polymer based on the total weight of the resist underlayer film composition. The resist underlayer film composition may contain 0.01% by weight to 30% by weight of the compound based on the total weight of the resist underlayer film composition.

[0025] The resist underlayer film composition may further include one or more polymers selected from an acrylic resin, an epoxy resin, a novolac resin, a glycouril resin, and a melamine resin.

[0026] 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.

[0027] According to another embodiment, there is provided a method for forming a pattern, the method including: forming a film to be etched on a substrate; applying a resist underlayer film composition according to an embodiment 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.

[0028] The resist underlayer film composition according to one embodiment can provide a resist underlayer film that does not cause resist pattern collapse even in a fine patterning process, has improved sensitivity to an exposure light source, and can improve patterning performance and energy efficiency. Also, the resist underlayer film composition according to one embodiment can provide a resist underlayer film that has excellent pattern formability and sensitivity. [Brief description of the drawings]

[0029] [Figure 1] FIG. 1 is a cross-sectional view illustrating a pattern forming method using a resist underlayer film composition according to one embodiment. [Diagram 2] FIG. 1 is a cross-sectional view illustrating a pattern forming method using a resist underlayer film composition according to one embodiment. [Diagram 3] FIG. 1 is a cross-sectional view illustrating a pattern forming method using a resist underlayer film composition according to one embodiment. [Figure 4] FIG. 1 is a cross-sectional view illustrating a pattern forming method using a resist underlayer film composition according to one embodiment. [Diagram 5] FIG. 1 is a cross-sectional view illustrating a pattern forming method using a resist underlayer film composition according to one embodiment. [Figure 6] FIG. 1 is a cross-sectional view illustrating a pattern forming method using a resist underlayer film composition according to one embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[0031] In the drawings, the thickness may be exaggerated to clearly show multiple layers and regions, and the same reference numerals may be used for similar parts throughout the specification. When a part such as a layer, film, region, or plate is on another part, this includes not only the case where it is directly on the other part, but also the case where there is another part between them. Conversely, when a part is said to be directly on another part, it means that there is no other part between them.

[0032] Hereinafter, unless otherwise defined in the present specification, "substituted" means that a hydrogen atom in a compound is substituted 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 or a salt thereof, a C1-C30 alkyl group, a C2-C30 alkenyl group, a C2-C30 alkynyl group, a C6-C30 aryl group, a C7-C30 arylalkyl group, a C1-C30 alkoxy group, a C1-C20 heteroalkyl group, a C3-C20 heteroarylalkyl group, a C3-C30 cycloalkyl group, a C3-C15 cycloalkenyl group, a C6-C15 cycloalkynyl group, a C2-C30 heterocyclic group, and combinations thereof.

[0033] Furthermore, two adjacent substituents among the substituted halogen atoms (F, Br, Cl, or I), hydroxy groups, nitro groups, cyano groups, amino groups, azido groups, amidino groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamoyl groups, thiol groups, ester groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1-C30 alkyl groups, C2-C30 alkenyl groups, C2-C30 alkynyl groups, C6-C30 aryl groups, C7-C30 arylalkyl groups, C1-C30 alkoxy groups, C1-C20 heteroalkyl groups, C3-C20 heteroarylalkyl groups, C3-C30 cycloalkyl groups, C3-C15 cycloalkenyl groups, C6-C15 cycloalkynyl groups, and C2-C30 heterocyclic groups may be fused to form a ring.

[0034] In this specification, unless otherwise defined, the term "hetero" means containing 1 to 3 heteroatoms selected from N, O, S, Se and P.

[0035] As used herein, the term "aryl group" refers to a group having one or more hydrocarbon aromatic moieties, and broadly includes both hydrocarbon aromatic moieties linked by single bonds and 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 which share adjacent pairs of carbon atoms) functionalities.

[0036] As used herein, the term "heterocyclic group" includes heteroaryl groups, and also refers to groups that contain 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 a heterocyclic group is a fused ring, the entire heterocyclic group or each ring may contain one or more heteroatoms.

[0037] 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 chrysenyl group, a substituted or unsubstituted triphenyl group, a substituted or unsubstituted ter ... Liphenylenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted pyrrolyl group, substituted or unsubstituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted thiazolyl group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazolyl group, substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzopyridothiazinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenazinyl group, substituted or unsubstituted phenothiazinyl group, substituted or unsubstituted phenoxazinyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted carbazolyl group, pyridoindolyl group, benzopyridoxazinyl group, benzopyridothiazinyl group, 9,9-dimethyl-9,10-dihydroacridinyl group, a combination thereof, or a fused form of a combination thereof.

[0038] In this specification, unless otherwise specified, "combination" means mixing or copolymerization.

[0039] In addition, in this specification, the term "polymer" can include both an oligomer and a polymer.

[0040] In this specification, unless otherwise specified, the "weight average molecular weight" is measured by dissolving a powder sample in tetrahydrofuran (THF) and then using Agilent Technologies' 1200 series gel permeation chromatography (GPC) (Shodex LF-804 column and Shodex polystyrene standard).

[0041] Additionally, in this specification, unless otherwise defined, "*" indicates the linking position of a structural unit of a compound or a moiety of a compound.

[0042] In the semiconductor industry, there is a continuing demand to reduce the size of chips. To meet this trend, the line width of the resist patterned by lithography technology must be reduced to a level of several tens of nanometers, and the pattern thus formed is then transferred to the underlying material by an etching process on the lower substrate. 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, a resist underlayer film has been used to compensate for the etching resistance of the resist when the resist is formed thin, the substrate to be etched is thick, or a pattern with a large depth is required.

[0043] The resist underlayer film is required to be thinner as the resist thickness is reduced, and the photoresist pattern must not collapse even when the resist underlayer film is thin. For this reason, the resist underlayer film must have excellent adhesion to the photoresist. In addition, when forming a thin resist underlayer film, it is required to improve the coating uniformity of the resist underlayer film composition and the flatness of the resist underlayer film produced therefrom, improve the sensitivity to the exposure light source, and improve the pattern formability and energy efficiency.

[0044] 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, or a combination thereof, a compound represented by the following Chemical Formula 3, and a solvent.

[0045] [ka]

[0046] In Chemical Formula 1 and Chemical Formula 2, A is a heterocyclic group containing a nitrogen atom in the ring, L 1 ~L 6 each independently represents a single bond, a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 heteroalkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted C2-C20 heterocycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C1-C20 heteroarylene group, or a combination thereof; X 1 ~X 5 each independently represents a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -(CO)O-, -O(CO)O-, or -NR a - (where R a is hydrogen, deuterium, or a C1-C10 alkyl group), or a combination thereof; Y 1 ~Y3 each independently represents a hydroxy group, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C1-C10 heteroalkyl group, a substituted or unsubstituted C2-C10 heteroalkenyl group, a substituted or unsubstituted C2-C10 heteroalkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C20 heteroaryl group, or a combination thereof; * indicates the linkage position.

[0047] [ka]

[0048] In chemical formula 3, R 1 , R 2 , and R 4 are each independently hydrogen, deuterium, a cyano group, iodine, an azide group (-N3), a halogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 heteroalkyl group, a substituted or unsubstituted C2-C20 heteroalkenyl group, a substituted or unsubstituted C2-C20 heteroalkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, -OR b , -C(=O)R c , -C(=O)OR d , -OC(=O)OR e , -NR f R g , -NR h (C=O)R i (where R b ~R iare each hydrogen, deuterium, 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 C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, or a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R 3 -OR j , -C(=O)R k , -C(=O)OR l , -OC(=O)OR m , or -L a -OR n (Here, L a is a substituted or unsubstituted C1 to C5 alkylene group or a substituted or unsubstituted C6 to C16 arylene group, R j ~R n are each independently hydrogen, deuterium, 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 C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, or a substituted or unsubstituted C6 to C20 aryl group; x and y each independently represent an integer of 0 to 2, provided that 0≦x+y≦2.

[0049] In the composition for a resist underlayer film according to one embodiment, the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2 each contain a heterocycle containing a nitrogen atom in the ring, and therefore, the polymer containing these structural units has sp 2 -sp 2The polymer can be bonded to the substrate. This allows the polymer to have high electron density. By including a polymer with high electron density, the resist underlayer film composition according to an embodiment can realize a film with a dense structure in the form of an ultrathin 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. In addition, 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 ultraviolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0050] The resist underlayer film composition contains a compound represented by Chemical Formula 3, so that the resist underlayer film formed from the resist underlayer film composition according to an embodiment can have a structure similar to that of a photoresist film. This stabilizes the interface between the photoresist film and the resist underlayer film. The compound represented by Chemical Formula 3 contains tin (Sn), so that it can increase the EUV light source absorption rate and improve sensitivity. This increases the reactivity of the resist underlayer film and the photoresist film, so that it can improve the adhesion between them. Specifically, when the resist underlayer film composition is irradiated with an EUV light source, Sn of the compound contained in the resist underlayer film composition can be bonded to an additive or polymer in the resist underlayer film composition, and can also be bonded to oxygen or polymer of another compound in the resist underlayer film composition according to an embodiment. Therefore, it is possible to increase the adhesion between the resist underlayer film manufactured from the resist underlayer film composition according to an embodiment and the photoresist film.

[0051] In addition, since the compound contained in the composition for resist underlayer film contains tin, the resist underlayer film can be effectively and selectively removed by a developer during development of the resist underlayer film, thereby improving the pattern formability of the resist underlayer film.

[0052] A is represented by any one or more of the following chemical formulae A-1 to A-4.

[0053] [ka]

[0054] In Chemical Formulae A-1 to A-4, * indicates a moiety that is connected to another atom or group.

[0055] In one embodiment, L 1 ~L 6 are each independently a single bond, a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 heteroalkylene group, or a combination thereof, for example, but not limited to, a single bond, a substituted or unsubstituted C1-C5 alkylene group, a substituted or unsubstituted C1-C5 heteroalkylene group, or a combination thereof.

[0056] X 1 ~X 5 are each independently a single bond, -O-, -S-, -C(=O)-, -(CO)O-, -O(CO)O-, or a combination thereof, for example, but not limited to, -O-, -S-, -(CO)O-, or a combination thereof.

[0057] Y 1 ~Y 3 are each independently a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C1-C10 heteroalkyl group, a substituted or unsubstituted C2-C10 heteroalkenyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, for example, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C2-C5 alkenyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, or a combination thereof, but are not limited to these.

[0058] Chemical formula 1 is represented by the following chemical formula 1-1 or 1-2, and chemical formula 2 is represented by any one of the following chemical formulas 2-1 to 2-3.

[0059] [ka] [ka]

[0060] R in Chemical Formula 3 1 , R 2 , and R 4 At least one of the following is a cyano group, an iodine group, an azide group (-N3), or an -OR b , -C(=O)R c , -C(=O)OR d , -OC(=O)OR e , -NR f R g , or -NR h (C=O)R i (where R b ~R i are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C10 heteroalkyl group, or a substituted or unsubstituted C6-C30 aryl group. As described above, R 3 Any one or more of the remaining substituents excluding has a functional group capable of reacting with other compounds or polymers, thereby increasing the reactivity with the photoresist film and further improving the adhesion between the resist underlayer film and the photoresist film according to one embodiment.

[0061] For example, R 1 , R 2 , and R 4is an iodine, an azide group (-N3), 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 b , N.R. f R g , -NR h (C=O)R i (where R b , and R f ~R i are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C10 heteroalkyl group, or a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, and R 3 -OR j (where R j 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 C2 to C10 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

[0062] For example, R 1 , R 2 , and R 4 each independently represents hydrogen, deuterium, iodine, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C6 to C30 aryl group, -OR b , -C(=O)R c , -C(=O)OR d , -OC(=O)OR e (where R b ~R eare each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, R 3 -OR j , -C(=O)OR l , or -L a -OR n (Here, L a is a substituted or unsubstituted C1-C5 alkylene group, R j , R l , and R n are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

[0063] In one embodiment, R 1 , R 2 , and R 4 -OR b , or -OC(=O)OR e R b and R e are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C2 to C8 alkenyl group, a substituted or unsubstituted C2 to C8 alkynyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and may be, for example, hydrogen, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propynyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof.

[0064] In another embodiment, Chemical Formula 3 is represented by any one or more of Chemical Formulas 3-1 to 3-4 below:

[0065] [ka]

[0066] The polymer may have a weight average molecular weight of 1,000g / mol to 300,000g / mol, for example, about 3,000g / mol to 200,000g / mol, 3,000g / mol to 100,000g / mol, 3,000g / mol to 90,000g / mol, 3,000g / mol to 70,000g / mol, 3,000g / mol to 70,000g / mol, 3,000g / mol to 50,000g / mol, 5,000g / mol to 50,000g / mol, or 5,000g / mol to 30,000g / mol, but is not limited thereto. By having a weight average molecular weight in the above range, the carbon content and solubility in a solvent of the composition for resist underlayer film containing the polymer can be adjusted and optimized.

[0067] The resist underlayer film composition may contain 10 parts by weight to 800 parts by weight of the above compound based on 100 parts by weight of the polymer, for example, 0 parts by weight to 800 parts by weight, 30 parts by weight to 800 parts by weight, 30 parts by weight to 700 parts by weight, 30 parts by weight to 600 parts by weight, or 30 parts by weight to 500 parts by weight, but is not limited thereto. By containing the above-mentioned compound in the above range relative to the polymer, the adhesive strength between the resist underlayer film formed from the resist underlayer film composition containing them and the resist film can be optimized, the sensitivity to the exposure light source is improved, and the patterning performance and energy efficiency are improved.

[0068] 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 resist underlayer film. More specifically, the polymer can be contained in an amount of 10% by weight to 50% by weight, for example, 20% by weight to 50% by weight, or 20% by weight to 30% by weight based on the total weight of the composition for resist underlayer film, but is not limited thereto. By containing the polymer in the composition for resist underlayer film in the above range, the thickness, surface roughness, and flattening degree of the resist underlayer film can be adjusted.

[0069] The above compound is contained in an amount of 0.01% by weight to 30% by weight based on the total weight of the composition for resist underlayer film. More specifically, the above compound can be contained in an amount of 0.1% by weight to 30.0% by weight based on the total weight of the composition for resist underlayer film, for example, 1.0% by weight to 30.0% by weight, 5.0% by weight to 30.0% by weight, 5.0% by weight to 25.0% by weight, 8.0% by weight to 25.0% by weight, or 10.0% by weight to 25.0% by weight, but is not limited thereto. By containing the above compound in the composition for resist underlayer film within this range, the thickness, surface roughness, chemical resistance, and flattening degree of the resist underlayer film can be adjusted.

[0070] 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 and compound contained in the resist underlayer film composition according to an embodiment. Examples of the solvent include, but are not limited to, propylene glycol, propylene glycol diacetate, methoxypropane diol, 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, methylpyrrolidinone, methyl 2-hydroxyisobutyrate, acetylacetone, ethyl 3-ethoxypropionate, or combinations thereof.

[0071] The composition for a resist underlayer film according to an embodiment may further include, in addition to the above-mentioned polymer, compound, and solvent, one or more other polymers selected from an acrylic-based resin, an epoxy-based resin, a novolac-based resin, a glycoluril-based resin, and a melamine-based resin, but the other polymers are not limited thereto.

[0072] The resist underlayer film composition according to another embodiment may further include additives including a surfactant, a thermal acid generator, a plasticizer, or a combination thereof.

[0073] 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 that can be used include, but are not limited to, alkylbenzenesulfonate, alkylpyridinium salt, polyethylene glycol, and quaternary ammonium salt.

[0074] Examples of the thermal acid generator that can 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 or 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters.

[0075] 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, trimellitates, and citrates, polyether-based, polyester-based, and polyacetal-based compounds.

[0076] The additive is contained in an amount of 0.001 to 40 parts by weight based on 100 parts by weight of the composition for resist underlayer film. By containing the additive in the above range, the solubility of the composition for resist underlayer film can be improved without changing the optical properties of the composition for resist underlayer film.

[0077] According to another embodiment, there is provided a resist underlayer film prepared using the above-mentioned composition for a resist underlayer film. The resist underlayer film may be in a form obtained by, for example, coating the above-mentioned composition for a resist underlayer film on a substrate and then curing the composition through a heat treatment process.

[0078] A method for forming a pattern using the above-mentioned composition for a resist underlayer film will be described below 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.

[0079] Referring to Fig. 1, an object to be etched is prepared. An example of the object to be etched is a thin film 102 formed on a semiconductor substrate 100. Hereinafter, only the case where the object to be etched is the thin film 102 will be described. In order to remove contaminants remaining on the thin film 102, the surface of the thin film is cleaned. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0080] Next, the above-mentioned resist underlayer film composition is coated on the surface of the cleaned thin film 102 by spin coating.

[0081] Thereafter, drying and baking steps are performed to form a resist underlayer film 104 on the thin film 102. The baking step can be performed at 100° C. to 500° C., for example, 100° C. to 300° C. Specific descriptions regarding the composition for the resist underlayer film have already been described in detail, so they will be omitted to avoid duplication.

[0082] 2, a photoresist is coated on the resist underlayer film 104 to form a photoresist film 106. In one embodiment, the photoresist composition that forms the photoresist film 106 may include, but is not limited to, an organometallic compound containing Sn, a solvent, and the like.

[0083] Next, a first baking step is performed to heat the substrate 100 on which the photoresist film 106 is formed. The first baking step can be performed at a temperature of 90°C to 120°C.

[0084] As an example, in the photoresist film 106 of FIG. 2, a tin oxide network may be formed as represented by the following formula 1. [ka]

[0085] In addition, in the resist underlayer film 104, as shown in the following formula 2, the compound represented by Chemical Formula 3 contained in the composition for resist underlayer film according to one embodiment can be bonded to a polymer containing a structural unit represented by Chemical Formula 1 or Chemical Formula 2 to form a dense network. In the following formula 2, M1 to M10 are structural units represented by Chemical Formula 1 or Chemical Formula 2, and R is R in Chemical Formula 3. 1 ~R 4 As represented by Formula 2, in the resist underlayer film formed from the composition for a resist underlayer film according to an embodiment, the compound represented by Chemical Formula 3 can be randomly bonded to each structural unit of the polymer including the structural unit represented by Chemical Formula 1 or Chemical Formula 2. [ka]

[0086] According to an embodiment, at the interface between the resist underlayer film 104 and the photoresist film 106, a structural unit of a compound contained in the resist underlayer film 104 or a polymer bonded thereto can be bonded to tin forming the photoresist film 106 through a tin oxide bond between tin and oxygen, as represented by the following formula 3. This is roughly shown in the following formula 3, and the central dotted line in formula 3 indicates the interface between the resist underlayer film 104 and the photoresist film 106.

[0087] [ka]

[0088] Formulae 1 to 3 are shown as examples to explain the present invention, and are not meant to limit the structures constituting the resist underlayer film or the photoresist film.

[0089] 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, light is irradiated onto the exposure mask 110, so that predetermined portions of the photoresist film 106 formed on the substrate 100 selectively react with the light transmitted through the exposure mask.

[0090] Examples of light that can be used in the exposure process include short wavelength light such as an activation irradiation conductor i-line having a wavelength of 365 nm, a KrF excimer laser having a wavelength of 248 nm, and an ArF excimer laser having a wavelength of 193 nm, as well as extreme ultraviolet (EUV) having a wavelength of 13.5 nm, which corresponds to extreme light.

[0091] The exposed regions 106b of the photoresist film 106 form polymers through a crosslinking reaction such as condensation between organometallic compounds, and thus have a different solubility from the unexposed regions 106a of the photoresist film 106.

[0092] Next, a second baking step is performed on the substrate 100. The second baking step can be performed at a temperature of about 90° C. to about 200° C. By performing the second baking step, the exposed region 106b of the photoresist film 106 becomes less soluble in a developer.

[0093] Referring to FIG. 4, the photoresist film 106a corresponding to the unexposed region is dissolved and removed using an organic solvent developer such as 2-heptanone, and the remaining photoresist film 106b forms a photoresist pattern 108.

[0094] 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.

[0095] However, the photoresist pattern according to an embodiment is not necessarily limited to being formed as a negative tone image, but may be formed to have a positive tone image. In this case, examples of developers that can be used to form a positive tone image include quaternary ammonium hydroxide compositions such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof.

[0096] 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) can have a width of 5 nm to 100 nm. As an example, the photoresist pattern 108 can 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.

[0097] Meanwhile, the photoresist pattern 108 can have a pitch with a half-pitch of about 50 nm or less, e.g., 40 nm or less, 30 nm or less, 20 nm or less, 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.

[0098] Next, the resist underlayer film 104 is etched using the photoresist pattern 108 as an etching mask. By such an etching process, an organic film pattern 112 as shown in FIG.

[0099] The formed organic film pattern 112 may also have a width corresponding to the photoresist pattern 108. The etching may be, for example, dry etching using an etching gas, and the etching gas may be, for example, CHF3, CF4, Cl2, O2, or a mixture thereof. As described above, the resist underlayer film formed using the resist underlayer film composition according to an embodiment has a high etching rate, and therefore, a smooth etching process can be performed in a short time.

[0100] 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 is shaped into a thin film pattern 114.

[0101] In the preceding exposure process, the thin film pattern 114 formed by the exposure process performed using a short wavelength light source such as an activation irradiation conductor i-line (wavelength 365 nm), a KrF excimer laser (wavelength 248 nm), or an 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 performed using an EUV light source can have a width of 20 nm or less. EXAMPLES

[0102] The present invention will be described in more detail below through examples of the synthesis of the above-mentioned polymer and the preparation of a composition for a resist underlayer film containing the same. However, the present invention is not technically limited by the following examples.

[0103] Polymer synthesis Synthesis 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 placed in a 500ml three-necked flask, and a condenser was connected. After the reaction was allowed to proceed at 80°C for 16 hours, the reaction solution was cooled to room temperature. The reaction solution was poured into a 1L wide-mouthed bottle containing 800g of water while stirring to precipitate a gum-like polymer, which was then dissolved in 80g of tetrahydrofuran (THF). The resulting polymer solution was added to toluene to form a precipitate, and monomolecular and low molecular weight molecules were removed to obtain 10g of polymer A represented by the following chemical formula 1-1. (Weight average molecular weight (Mw) = 10,500g / mol)

[0104] [ka]

[0105] Synthesis 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 flask, and a condenser was connected. After the reaction was allowed to proceed at 80°C for 16 hours, the reaction solution was cooled to room temperature. The reaction solution was poured into a 1L wide-mouthed bottle containing 800g of water while stirring to precipitate a gum-like polymer, and the polymer was then dissolved in 80g of tetrahydrofuran (THF). The resulting polymer solution was added to toluene to form a precipitate, and monomolecules and low molecules were removed to obtain 10g of polymer B composed of structural units represented by the following chemical formula 1-2. (Weight average molecular weight (Mw)=8,000g / mol)

[0106] [ka]

[0107] Synthesis Example 3 A reaction solution was prepared by adding 20g of 1,3-diallyl-5,5-dimethyl-1,3-diazinane-2,4,6(1H,3H,5H)-trione, 8.4g of 2,3-dimercapto-1-propanol, 0.5g of AIBN (azobisisobutyronitrile), and 50g of N,N-dimethylformamide (DMF) to a 250mL four-neck flask, and a condenser was connected. The reaction solution was heated at 60°C for 5 hours to proceed with the reaction, and then cooled to room temperature. The reaction solution was then poured into a beaker containing 300g of distilled water while stirring to produce a gum-like polymer, and the polymer was then dissolved in 30g of tetrahydrofuran (THF). The dissolved polymer solution was added to toluene to precipitate the precipitate, and the single molecules and low molecules were removed to obtain polymer C composed of structural units represented by the following chemical formula 2-1. (Weight average molecular weight (Mw) = 3,700 g / mol)

[0108] [ka]

[0109] Synthesis Example 4 In a 1L two-necked round flask, 148.6g (0.5mol) of 1,3,5-triglycidylisocyanurate, 60.0g (0.4mol) of 2,2'-thiodiacetic acid, 9.1g of benzyltriethylammonium chloride, and 350g of N,N-dimethylformamide were placed and connected to a condenser. The temperature was raised to 100°C, and the reaction was allowed to proceed for 8 hours, after which the reaction solution was cooled to room temperature (23°C). The reaction solution was then transferred to a 1L wide-mouthed bottle, and washed three times with hexane, followed by purified water. The resulting gum-like polymer was completely dissolved using 80g of THF, and then slowly dropped into 700g of toluene under stirring to obtain a precipitate. The solvent was then removed from the precipitate to obtain polymer D composed of structural units represented by the following chemical formula 2-2. (Weight average molecular weight (Mw) = 9,100g / mol)

[0110] [ka]

[0111] Synthesis Example 5 A reaction solution was prepared by adding 20g of 1,3-diallyl-5-(1-hydroxyethyl)-isocyanurate, 6.0g of 1,2-dithiol, 1g of AIBN (azobisisobutyronitrile), and 50g of N,N-dimethylformamide (DMF) to a 250mL four-neck flask, and a condenser was connected. The reaction solution was heated at 50°C for 5 hours to proceed with the reaction, and then 10g of 3,4-difluorobenzylmercatan and 1g of AIBN (azobisisobutyronitrile) were added, and the reaction was continued for an additional 2 hours, after which the solution was cooled to room temperature. The reaction solution was then dropped into a beaker containing 300g of distilled water while stirring to produce a gum-like polymer, which was then dissolved in 30g of tetrahydrofuran (THF). The dissolved polymer solution was added to toluene to form a precipitate, and the monomolecules and low molecular weights were removed to obtain polymer E, represented by the following chemical formula 2-3. (Weight average molecular weight (Mw) = 5,500g / mol)

[0112] [ka]

[0113] Synthesis of compounds Synthesis Example 6 In a 100ml two-necked round flask, 11.56g of triphenyltin chloride, 10.21g of sodium ethoxide, and 21.77g of methanol were placed and connected to a condenser. The reaction was allowed to proceed at 40°C for 12 hours. After this, the reaction solution was cooled to room temperature, and the powder obtained by drying was dissolved in dichloromethane and washed with distilled water. The organic solvent was removed and the residue was dried to obtain the compound represented by chemical formula 3-1. [ka]

[0114] Synthesis Example 7 Diphenyltindichloride 10.3g, sodium hydroxide 6.0g, and methanol 16.3g were placed in a 100ml two-necked round flask and a condenser was connected. The reaction was allowed to proceed at 70°C for 12 hours, and the reaction solution was then cooled to room temperature. The dried powder was dissolved in dichloromethane and washed with distilled water, after which the organic solvent was removed and the residue was dried to obtain a compound represented by the following chemical formula 3-2.

[0115] [ka]

[0116] Synthesis Example 8 Butyltin trichloride 8.47g, sodium hydroxide 6.0g, and water 14.47g were put into a 100ml two-necked flask and a condenser was connected. The reaction was carried out at 55°C for 6 hours, and then the temperature was raised to 95°C and the reaction was carried out for 12 hours. The reaction solution was cooled to room temperature, and the powder obtained by drying was dissolved in dichloromethane and washed with distilled water, and the organic solvent was removed by distillation. The residue was dried to obtain a compound represented by the following chemical formula 3-3.

[0117] [ka]

[0118] Preparation of Resist Underlayer Film Composition Example 1 A total of 1.2 g of the polymer A obtained in Synthesis Example 1 and the compound of Chemical Formula 3-1 obtained in Synthesis Example 6 in a ratio of 100:50, 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 of Example 1.

[0119] Example 2 A composition for a resist underlayer film was prepared in the same manner as in Example 1, except that the compound of Chemical Formula 3-2 obtained in Synthesis Example 7 was used instead of the compound of Chemical Formula 3-1.

[0120] Example 3 A composition for a resist underlayer film was prepared in the same manner as in Example 1, except that the compound of Chemical Formula 3-3 obtained in Synthesis Example 8 was used instead of the compound of Chemical Formula 3-1.

[0121] Example 4 A composition for a resist underlayer film was prepared in the same manner as in Example 1, except that a compound of the following formula 3-4 (PR-79356, Atomaxchem) was used instead of the compound of the formula 3-1.

[0122] [ka]

[0123] Example 5 A composition for a resist underlayer film was prepared in the same manner as in Example 1, except that Polymer B was used instead of Polymer A.

[0124] Comparative Example 1 1.2 g of the polymer A obtained in Synthesis 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 resist underlayer film composition of Comparative Example 1.

[0125] Comparative Example 2 A composition for a resist underlayer film was prepared in the same manner as in Comparative Example 1, except that Polymer B was used instead of Polymer A.

[0126] Evaluation 1: Exposure characteristics evaluation The resist underlayer film compositions prepared in Examples 1 to 5, Comparative Example 1, and Comparative Example 2 were each applied by spin coating, and then heat-treated on a hot plate at 205°C for 60 seconds to form a resist underlayer film with a thickness of 5 nm. Then, a photoresist solution was applied on the resist underlayer film by spin coating, and then heat-treated on a hot plate at 110°C for 1 minute to form a photoresist layer. The photoresist layer was exposed at 200 μC / cm using an e-beam exposure tool (manufactured by Elionix). 2 ~2000μC / cm 2 After exposure in the range of 1:1, the photoresist layer was heat-treated at 150°C for 60 seconds. The photoresist layer was then developed with a 2.38% by mass aqueous solution of TMAH and rinsed with pure water for 15 seconds to form a 50 nm line and space (L / S) photoresist pattern. The optimal exposure dose for the photoresist pattern was evaluated, and the results are shown in Table 4. Here, the optimal exposure dose (Optimumenergy) (Eop, μC / cm) was defined as the exposure dose for developing a 50 nm line and space pattern size at 1:1. 2 The smaller this value, the better the sensitivity. The minimum CD is the smallest size at which a pattern can be formed without the lines of the pattern connecting or collapsing, and the smaller this value, the better the resolution.

[0127] [Table 1]

[0128] Referring to Table 1, it can be seen that the resist underlayer films of Examples 1 to 5 are superior to those of Comparative Example 1 and Comparative Example 2 in terms of fine pattern (50 nmL / S) formability and sensitivity.

[0129] Evaluation 2: Line width roughness (LWR) evaluation The resist underlayer film compositions prepared in Examples 1 to 5, Comparative Example 1, and Comparative Example 2 were each applied by spin coating, and then heat-treated on a hot plate at 205°C for 60 seconds to form a resist underlayer film with a thickness of 5 nm. Then, a photoresist solution was applied on the underlayer film by spin coating, and then heat-treated on a hot plate at 110°C for 1 minute to form a photoresist layer. The resist layer was exposed using an e-beam exposure device (manufactured by Elionix, accelerating voltage 100 keV) under conditions of a line width of 30 nm and a space width between lines of 30 nm. Then, after heat treatment at 95°C for 60 seconds, the resist was developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and rinsed with pure water for 15 seconds to form a resist pattern.

[0130] Line width roughness (LWR) was measured by observing a pattern formed with a width of 30 nm with a scanning electron microscope (SEM) S-9260 (manufactured by Hitachi) and measuring the distance from the reference line where the edge should be within a 2 μm range in the longitudinal direction of the pattern. The results are shown in Table 1, and the smaller the value of line width roughness (LWR), the better.

[0131] Referring to Table 1, it can be seen that the resist underlayer films of Examples 1 to 5 have smaller LWR values ​​than those of Comparative Example 1 and Comparative Example 2, and therefore the patterns are more uniform.

[0132] Although specific embodiments of the present invention have been described and illustrated above, 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 or perspective of the present invention, and the modified or altered embodiments should be considered to belong to the scope of the claims of the present invention. [Explanation of symbols]

[0133] 100 Substrates 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. The present invention includes a polymer including a structural unit represented by the following chemical formula 1, a structural unit represented by the following chemical formula 2, or a combination thereof, a compound represented by the following chemical formula 3, and a solvent, 【Chemistry 1】 In the above Chemical Formula 1 and Chemical Formula 2, A is a heterocyclic group containing a nitrogen atom in the ring, L 1 ~L 6 are each independently a single bond, a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 heteroalkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted C2-C20 heterocycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C1-C20 heteroarylene group, or a combination thereof; X 1 ~X 5 are each independently a single bond, -O-, -S-, -S(=O)-, -S(=O) 2 -, -C(=O)-, -(CO)O-, -O(CO)O-, -NR a - (where R a is hydrogen, deuterium, or a C1-C10 alkyl group), or a combination thereof; Y 1 ~Y 3 are each independently a hydroxy group, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C1-C10 heteroalkyl group, a substituted or unsubstituted C2-C10 heteroalkenyl group, a substituted or unsubstituted C2-C10 heteroalkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C20 heteroaryl group, or a combination thereof; * indicates the linking position, 【Chemistry 2】 In the above Chemical Formula 3, R 1 , R 2 , and R 4 are each independently hydrogen, deuterium, a cyano group, an iodine group, an azide group (-N 3 ), a halogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 heteroalkyl group, a substituted or unsubstituted C2-C20 heteroalkenyl group, a substituted or unsubstituted C2-C20 heteroalkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, -OR b , -C(=O)R c , -C(=O)OR d , -OC(=O)OR e , -NR f R g , -NR h (C=O)R i (Here, R b ~R i are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C10 heteroalkyl group, or a substituted or unsubstituted C6-C30 aryl group, or a combination thereof; R 3 is -OR j , -C(=O)R k , -C(=O)OR l , -OC(=O)OR m , or -L a -O-R n (Here, L a is a substituted or unsubstituted C1 to C5 alkylene group or a substituted or unsubstituted C6 to C16 arylene group, R j ~R n are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C10 heteroalkyl group, or a substituted or unsubstituted C6-C20 aryl group; A composition for a resist underlayer film, wherein x and y each independently represent an integer of 0 to 2, and 0≦x+y≦2.

2. A is represented by one or more of the following chemical formulas A-1 to A-4: 【Chemistry 3】 2. The composition for a resist underlayer film according to claim 1, wherein in said chemical formulas A-1 to A-4, * represents a moiety connecting to another atom or group.

3. L 1 ~L 6 are each independently a single bond, a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 heteroalkylene group, or a combination thereof; X 1 ~X 5 each independently represents a single bond, —O—, —S—, —C(═O)—, —(CO)O—, —O(CO)O—, or a combination thereof, Y 1 ~Y 3 are each independently 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 C10 heteroalkenyl 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, or a combination thereof.

4. R 1 , R 2 , and R 4 At least one of the following is a cyano group, an iodine group, an azide group (-N 3 ), -OR b , -C(=O)R c , -C(=O)OR d , -OC(=O)OR e , -NR f R g or -NR h (C=O)R i (Here, R b ~R i are each independently hydrogen, deuterium, 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 C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

5. R 1 , R 2 , and R 4 is an iodine, azide group (-N 3 ), 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 b , N.R. f R g , -NR h (C=O)R i (Here, R b , and R f From R i are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C10 heteroalkyl group, or a substituted or unsubstituted C6-C30 aryl group, or a combination thereof; R 3 is -OR j (Here, R j 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 C2 to C10 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

6. R 1 , R 2 , and R 4 are each independently hydrogen, deuterium, iodine, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C6 to C30 aryl group, -OR b , -C(=O)R c , -C(=O)OR d , -OC(=O)OR e (Here, R b ~R e are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, or a substituted or unsubstituted C6-C30 aryl group, or a combination thereof; R 3 is -OR j , -C(=O)OR l , or -L a -O-R n (Here, L a is a substituted or unsubstituted C1-C5 alkylene group, R j , R l , and R n are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

7. The composition for a resist underlayer film according to claim 1, wherein the chemical formula 1 is represented by the following chemical formula 1-1 or 1-2, and the chemical formula 2 is represented by any one of the following chemical formulas 2-1 to 2-3. 【Chemistry 4】 【Chemistry 5】

8. The composition for a resist underlayer film according to claim 1, wherein the chemical formula 3 is represented by any one or more of the following chemical formulas 3-1 to 3-4. 【Chemistry 6】

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

10. 2. The resist underlayer film composition according to claim 1, comprising 10 to 800 parts by weight of the compound based on 100 parts by weight of the polymer.

11. 2. The resist underlayer film composition according to claim 1, comprising 30 to 500 parts by weight of the compound based on 100 parts by weight of the polymer.

12. 2. 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.

13. 2. The composition for a resist underlayer film according to claim 1, wherein the compound is contained in an amount of 0.01% by weight to 30% by weight based on the total weight of the composition for a resist underlayer film.

14. 2. The resist underlayer film composition according to claim 1, further comprising one or more polymers selected from the group consisting of acrylic resins, epoxy resins, novolac resins, glycouril resins, and melamine resins.

15. 2. 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.

16. forming a film to be etched on a substrate; A step of forming a resist underlayer film by applying the composition for a resist underlayer film according to claim 1 onto the film to be etched; forming a photoresist pattern on the resist underlayer film; and The method of forming a pattern includes sequentially etching the resist underlayer film and the film to be etched using the photoresist pattern as an etching mask.

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