Resist base composition and method for forming pattern using the same

Abstract

The present invention discloses a resist base composition, comprising: (A) a polymer comprising a structural unit represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof; (B) a polymer comprising a structure in which at least one of the parts represented by Chemical Formula 3 or Chemical Formula 4 and a part represented by Chemical Formula 7 are bonded to each other; and (C) a solvent; and also discloses a method for forming a pattern using the resist base composition, wherein definitions of Chemical Formulas 1 to 4 and Chemical Formula 7 are as described in the specification.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2020-0006770 filed on January 17, 2020, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

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

[0004] Recently, the semiconductor industry has developed ultra-fine technology with patterns ranging from a few nanometers in size to tens of nanometers in size. This ultra-fine technology essentially requires efficient photolithography technology.

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

[0006] Exposure during formation of a photoresist pattern is one of the important factors for obtaining a photoresist image with high resolution.

[0007] Since ultra-fine pattern manufacturing technology is required, short wavelengths such as i-line (wavelength of 365 nanometers), KrF excimer laser (wavelength of 248 nanometers), and ArF excimer laser (wavelength of 193 nanometers) are used as activation radiation for exposing photoresist. Therefore, in order to solve the problem caused by diffuse reflection or standing waves of the semiconductor substrate from the activation radiation, many studies have been conducted to solve the problem by inserting a resist underlayer having optimal reflectivity between the resist and the semiconductor substrate.

[0008] On the other hand, in addition to the activating radiation, a method of using high-energy rays such as extreme ultraviolet (EUV; wavelength of 13.5 nanometers), E beam (electron beam) as a light source for forming a fine pattern is also being conducted, and the corresponding light source has almost no reflection from the substrate, but since the pattern is optimized, the resist bottom layer should have a thinner thickness, and in order to improve the collapse of the formed pattern, research on improving the adhesion between the resist and the bottom layer is also being widely studied. In addition, in order to maximize the efficiency of the light source, research on the sensitivity through the bottom layer is also being studied. Summary of the invention

[0009] Provided is a resist base layer composition, which can improve patterning performance and efficiency by improving sensitivity to exposure light sources, does not cause pattern collapse of the resist even in a fine patterning process, and is formed into a thin film, so that the etching process time can be shortened.

[0010] Another embodiment provides a method of forming a pattern using the resist underlying composition.

[0011] The embodiment provides a resist bottom layer composition, comprising:

[0012] (A) a polymer comprising a structural unit represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof;

[0013] (B) a polymer including a structure in which at least one of the moieties represented by Chemical Formula 3 or Chemical Formula 4 and the moiety represented by Chemical Formula 7 are bonded to each other; and

[0014] (C) Solvent.

[0015]

[0016] In Chemical Formula 1,

[0017] R 1 and R 2 are independently hydroxy, substituted or unsubstituted C1 to C20 alkoxy, halogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 heteroaryl, substituted or unsubstituted vinyl, or a combination thereof,

[0018] L 1 and L 2 are independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof, and

[0019] * is the bonding point;

[0020]

[0021] Wherein, in Chemical Formula 2,

[0022] R 3 to R 6are independently a hydroxyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and

[0023] L 3 is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof;

[0024]

[0025]

[0026] Among them, in Chemical Formula 3 and Chemical Formula 4,

[0027] R a and R b are independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 vinyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C1 to C10 heteroalkyl, substituted or unsubstituted C2 to C20 heteroalkenyl, substituted or unsubstituted C3 to C20 heterocycloalkyl, or substituted or unsubstituted C6 to C20 heteroaryl, or a combination thereof,

[0028] R c is the following: a terminal group which is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C2 to C20 heteroalkenyl group, a substituted or unsubstituted C3 to C20 heterocycloalkyl group, or a combination thereof; a structural unit represented by Chemical Formula 5 or Chemical Formula 6 bonded to the terminal group; a group represented by Chemical Formula 6; or a group represented by a combination thereof, and

[0029] Chemical Formula 3 or Chemical Formula 4 is bonded to the point indicated by * in Chemical Formula 7 at each * position;

[0030]

[0031]

[0032] Among them, in Chemical Formula 5 and Chemical Formula 6,

[0033] L3 and L 4 are independently substituted or unsubstituted C1 to C20 alkylene, substituted or unsubstituted C1 to C20 heteroalkylene, or a combination thereof,

[0034] R a and R b are independently the same as defined in Chemical Formula 3 and Chemical Formula 4, and

[0035] * is the bonding point;

[0036]

[0037] Among them, in chemical formula 7,

[0038] A is a single bond, a substituted or unsubstituted C1 to C10 alkylene group, -C(=O)-, -(CO)O-, -O(CO)O-, or a combination thereof,

[0039] X is a single bond, -O-, -S-, -S(=O)-, -S(=O) 2 -, -C(=O)-, -(CO)O-, -O(CO)O-, -NR- (wherein R is hydrogen, deuterium or C1 to C10 alkyl) or a combination thereof,

[0040] R d is hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, epoxy, vinyl, (meth)acrylate, oxetanyl, thiol, carboxyl, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aryloxy, or a combination thereof,

[0041] R e is one of hydrogen, deuterium and C1 to C10 alkyl,

[0042] n 1 is 1 to 10,000, and

[0043] *bonded to Chemical Formula 3 or Chemical Formula 4, or bonded to hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, epoxy, vinyl, (meth)acrylate, oxetanyl, thiol, carboxyl, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aryloxy, or a combination thereof,

[0044] The premise is that at least one of Chemical Formula 3 or Chemical Formula 4 is bonded to * in Chemical Formula 7.

[0045] R in Formula 1 1 and R 2 may independently be hydroxyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted vinyl, or a combination thereof,

[0046] L in Formula 1 1 and L 2 may independently be a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,

[0047] R in Formula 2 3 to R 6 may independently be a hydroxyl group, a thiol group, a cyano group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof, and

[0048] L in Formula 2 3 The group may be a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenyl group, or a combination thereof.

[0049] R in Formula 3 and Formula 4 a and R b may independently be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C2 to C20 heteroalkenyl group, or a substituted or unsubstituted C3 to C20 heterocycloalkyl group,

[0050] Rc may be the following: a terminal group which is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, or a substituted or unsubstituted C3 to C20 heterocycloalkyl group; a structural unit represented by Chemical Formula 5 or Chemical Formula 6 bonded to the terminal group; or a combination thereof,

[0051] In Chemical Formula 7, A may be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof.

[0052] X can be a single bond, -O-, -S-, -S(=O)-, -S(=O) 2 - or a combination thereof,

[0053] R d may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C1 to C30 thioalkyl group, or a combination thereof, and

[0054] R e It can be hydrogen, deuterium, C1 to C10 alkyl or a combination thereof.

[0055] R in Formula 1 1 and R 2 may independently be hydroxyl groups,

[0056] L in Formula 1 1 and L 2 may independently be a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof,

[0057] R in Formula 2 3 to R 6 may independently be hydroxyl groups, and

[0058] L in Formula 2 3 The phenylene group may be substituted or unsubstituted.

[0059] R in Formula 3 and Formula 4 a and R b may independently be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,

[0060] R in Formula 3 and Formula 4 cmay be the following: a substituted or unsubstituted C1 to C10 alkyl group; a substituted or unsubstituted C1 to C10 heteroalkyl group; a structural unit represented by Chemical Formula 5 or Chemical Formula 6 bonded to a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C1 to C10 heteroalkyl group; or a combination thereof,

[0061] In Chemical Formula 7, A may be a substituted or unsubstituted C1 to C5 alkylene group,

[0062] X can be -S-,

[0063] R d may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 thioalkyl group, or a combination thereof, and

[0064] R e It can be a C1 to C10 alkyl group.

[0065] The polymer including the structural unit represented by Chemical Formula 1 may include the structural unit represented by Chemical Formula 1-1, the structural unit represented by Chemical Formula 1-2, or a combination thereof.

[0066]

[0067]

[0068] In Chemical Formula 1-1 and Chemical Formula 1-2,

[0069] * is the key point.

[0070] The compound represented by Chemical Formula 2 may be a compound represented by Chemical Formula 2-1.

[0071]

[0072] The polymer in (B) may be represented by any one of Chemical Formulae 3-1 to 3-5 or Chemical Formulae 4-1 to 4-5.

[0073]

[0074]

[0075]

[0076]

[0077] In Chemical Formulae 3-1 to 3-5 and Chemical Formulae 4-1 to 4-5, n 4 1 to 10,000,

[0078] In chemical formula 3-5, n2 is 1 to 10,000, and

[0079] In chemical formula 4-5, n 3 From 1 to 10,000.

[0080] The composition may include: a polymer including a structural unit represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof, and a polymer including a structure in which one or more of the moieties represented by Chemical Formula 3 or Chemical Formula 4 and the moiety represented by Chemical Formula 7 are bonded to each other, in a weight ratio of about 80:20 to about 20:80.

[0081] The polymer including the structural unit represented by Chemical Formula 1 may have a weight average molecular weight of about 1,000 g / mol to about 10,000 g / mol.

[0082] The polymer including a structure in which one or more of the moieties represented by Chemical Formula 3 or Chemical Formula 4 and the moiety represented by Chemical Formula 7 are bonded to each other may have a weight average molecular weight of about 2,000 g / mol to about 100,000 g / mol.

[0083] The total weight of: a polymer including the structural unit represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof; and

[0084] The polymer including a structure in which one or more of the moieties represented by Chemical Formula 3 or Chemical Formula 4 and the moiety represented by Chemical Formula 7 are bonded to each other may be about 0.01 wt % to about 5 wt % based on the total weight of the resist underlayer composition.

[0085] The composition may further include at least one polymer selected from the group consisting of acrylic resins, epoxy resins, novolac resins, glycoluril resins, and melamine resins.

[0086] The composition may further comprise an additive comprising a surfactant, a thermal acid generator, a plasticizer or a combination thereof.

[0087] Another embodiment provides a method for forming a pattern, comprising:

[0088] forming an etching target layer on the substrate,

[0089] By applying the resist underlayer composition according to the embodiment, a resist underlayer is formed on the etching target layer,

[0090] forming a photoresist pattern on the resist bottom layer, and

[0091] The resist base layer and the etching target layer are sequentially etched using the photoresist pattern as an etching mask.

[0092] The formation of the photoresist pattern may include:

[0093] forming a photoresist layer on the resist bottom layer,

[0094] exposing the photoresist layer, and

[0095] The photoresist layer is developed.

[0096] The formation of the resist underlayer may further include heat treatment at a temperature of about 100° C. to about 500° C. after coating the resist underlayer composition.

[0097] The resist bottom layer composition according to the embodiment can be formed into an ultra-thin film for a predetermined wavelength (e.g., EUV, etc.), and at the same time, a resist bottom layer is provided, which has excellent coating properties, flattening properties, and adhesion to photoresist, and also has excellent chemical resistance to the solution used during the photolithography process and a fast etching rate. Therefore, by using a high-energy light source such as EUV, the resist bottom layer composition according to the embodiment or the resist bottom layer formed therefrom can be advantageously used to form a fine pattern of a photoresist. BRIEF DESCRIPTION OF THE DRAWINGS

[0098] Figures 1 to 5 A cross-sectional view for explaining a method of forming a pattern using the resist underlayer composition according to an embodiment.

[0099] Description of Figure Numbers

[0100] 100: semiconductor substrate;

[0101] 102: Film;

[0102] 104: resist bottom layer;

[0103] 106: photoresist layer;

[0104] 106a: exposure area;

[0105] 106b: non-exposed area;

[0106] 108: photoresist pattern;

[0107] 110: exposure mask;

[0108] 112: organic layer pattern;

[0109] 114: Thin film pattern. DETAILED DESCRIPTION

[0110] Example embodiments of the present disclosure will be described in detail below and can be easily made by those skilled in the art. However, the present disclosure can be implemented in many different forms and should not be construed as limited to the example embodiments set forth herein.

[0111] In the drawings, the thickness of layers, films, panels, regions, etc. may be exaggerated for clarity, and the same reference numerals represent the same elements throughout the specification. It will be understood that when an element, such as a layer, film, region, or substrate is referred to as being "on" another element, it may be directly on the other element, or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements.

[0112] As used herein, when no definition is otherwise provided, "substituted" means that a hydrogen atom of a compound is replaced by a substituent selected from the group consisting of a halogen atom (F, Br, Cl or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazine group, a hydrazo group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a vinyl group, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 aralkyl group, a C6 to C30 allyl 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 C3 to C30 heterocycloalkyl group, and combinations thereof.

[0113] As used herein, when a definition is not otherwise provided, "hetero" refers to a heteroatom group containing 1 to 10 heteroatoms selected from N, O, S and P.

[0114] Unless otherwise specified in the specification, 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) (chromatographic column: Shodex Company LF-804, standard sample: Showa Company polystyrene).

[0115] In addition, unless otherwise defined in the specification, "*" indicates a bonding point of a structural unit of a compound or a compound moiety.

[0116] Hereinafter, a resist underlayer composition according to an embodiment is described.

[0117] The present invention provides a resist bottom layer composition, which can reduce the collapse of the resist pattern during the process of forming a fine pattern in lithography using a short-wavelength light source such as ArF excimer laser (wavelength of 193 nanometers) or high-energy rays such as EUV (extreme ultraviolet light; wavelength of 13.5 nanometers), can reduce the etching process time due to the application of an ultra-thin film, and can improve the patterning of the photoresist due to the increased sensitivity to the exposure light source; and a method for forming a photoresist pattern using the bottom layer.

[0118] Specifically, the resist underlying composition according to the embodiment includes: (A) a polymer including a structural unit represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof; (B) a polymer including a structure in which at least one of the parts represented by Chemical Formula 3 or Chemical Formula 4 and a part represented by Chemical Formula 7 are bonded to each other; and (C) a solvent.

[0119]

[0120] In Chemical Formula 1,

[0121] R 1 and R 2 are independently hydroxy, substituted or unsubstituted C1 to C20 alkoxy, halogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 heteroaryl, substituted or unsubstituted vinyl, or a combination thereof,

[0122] L 1 and L 2 are independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof, and

[0123] * is the bonding point;

[0124]

[0125]

[0126] Wherein, in Chemical Formula 2,

[0127] R 3 to R 6are independently a hydroxyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and

[0128] L 3 is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof;

[0129]

[0130] Among them, in Chemical Formula 3 and Chemical Formula 4,

[0131] R a and R b are independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 vinyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C1 to C10 heteroalkyl, substituted or unsubstituted C2 to C20 heteroalkenyl, substituted or unsubstituted C3 to C20 heterocycloalkyl, or substituted or unsubstituted C6 to C20 heteroaryl, or a combination thereof,

[0132] R c is the following: a terminal group which is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C2 to C20 heteroalkenyl group, a substituted or unsubstituted C3 to C20 heterocycloalkyl group, or a combination thereof; a structural unit represented by Chemical Formula 5 or Chemical Formula 6 bonded to the terminal group; a group represented by Chemical Formula 6; or a group represented by a combination thereof, and

[0133] Chemical Formula 3 or Chemical Formula 4 is bonded to the point indicated by * in Chemical Formula 7 at each * position;

[0134]

[0135] Among them, in Chemical Formula 5 and Chemical Formula 6,

[0136] L 3 and L 4 are independently substituted or unsubstituted C1 to C20 alkylene, substituted or unsubstituted C1 to C20 heteroalkylene, or a combination thereof,

[0137] R a and R b are independently the same as defined in Chemical Formula 3 and Chemical Formula 4, and

[0138] * is the bonding point;

[0139]

[0140] Among them, in chemical formula 7,

[0141] A is a single bond, a substituted or unsubstituted C1 to C10 alkylene group, -C(=O)-, -(CO)O-, -O(CO)O-, or a combination thereof,

[0142] X is a single bond, -O-, -S-, -S(=O)-, -S(=O) 2 -, -C(=O)-, -(CO)O-, -O(CO)O-, -NR- (wherein R is hydrogen, deuterium or C1 to C10 alkyl) or a combination thereof,

[0143] R d is hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, epoxy, vinyl, (meth)acrylate, oxetanyl, thiol, carboxyl, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aryloxy, or a combination thereof,

[0144] R e is one of hydrogen, deuterium and C1 to C10 alkyl,

[0145] n 1 is 1 to 10,000, and

[0146] * is bonded to Chemical Formula 3 or Chemical Formula 4, or is bonded to hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, epoxy, vinyl, (meth)acrylate, oxetanyl, thiol, carboxyl, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aryloxy, or a combination thereof, with the proviso that at least one of Chemical Formula 3 or Chemical Formula 4 is bonded to * in Chemical Formula 7.

[0147] The composition according to the embodiment is coated on the bottom of the photoresist and forms a film, and thus the close contact property between the film and the photoresist can be improved, and the collapse of the resist pattern can be prevented even during a fine patterning process, and in addition, the sensitivity to the exposure light source is enhanced, thereby improving the patterning performance and efficiency of the photoresist. In addition, the composition can form an ultra-thin bottom film, and thus shorten the time of the etching process.

[0148] Among the polymers included in the composition, the polymer including the structural unit represented by Chemical Formula 1 or the compound represented by Chemical Formula 2 includes a substituted polycyclic aromatic ring group capable of increasing film density. Specifically, the polymer including the structural unit represented by Chemical Formula 1 or the compound represented by Chemical Formula 2 includes a pyrene structure, which is a polycyclic aromatic ring group having a high electron density, so that a densely structured film can be implemented in the form of an ultra-thin film, and enhanced energy efficiency can be improved when a pattern is formed after exposure to high-energy rays such as EUV (extreme ultraviolet rays; a wavelength of 13.5 nanometers), E beams (electron beams), etc.

[0149] The polymer including a structure in which at least one portion represented by Chemical Formula 3 or Chemical Formula 4 and a portion represented by Chemical Formula 7 are bonded to each other includes an isocyanurate main chain or a triazine main chain and thus can exhibit an etching selectivity ratio, and includes sulfur and thus can exhibit a relatively high refractive index and a fast etching rate.

[0150] In addition, the polymer containing the moiety can be selectively substituted with various functional groups, and thus, the adhesion to the photoresist can be easily controlled, and thereby the collapse of the pattern can be suppressed during the process of forming the pattern, and also has an increased cross-linking rate, and thereby improves the film density and has excellent chemical resistance.

[0151] The moiety represented by Chemical Formula 7 may improve the solubility of a polymer including the polymer due to a flexible main chain structure. In addition, the isocyanurate or triazine unit may be densely present in the polymer, and thereby contribute to the film density and ultra-thin coating properties of the resist underlayer.

[0152] Therefore, the resist underlayer composition according to the embodiment can form a resist underlayer having improved adhesion and chemical resistance and reduced thickness, faster etching effect can be expected through the resist underlayer compared to the upper photoresist, and the absorption efficiency of the exposure light source can be increased, thereby improving patterning performance.

[0153] In the embodiment, R in Chemical Formula 1 1 and R 2 may independently be hydroxyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted vinyl, or a combination thereof,

[0154] L 1 and L 2 may independently be a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,

[0155] R in Formula 2 3 to R 6 may independently be a hydroxyl group, a thiol group, a cyano group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof, and

[0156] L 3 The group may be a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenyl group, or a combination thereof.

[0157] In the embodiment, R in Chemical Formula 3 and Chemical Formula 4 a and R b may independently be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C2 to C20 heteroalkenyl group, or a substituted or unsubstituted C3 to C20 heterocycloalkyl group,

[0158] R c may be the following: a terminal group which is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, or a substituted or unsubstituted C3 to C20 heterocycloalkyl group; a structural unit represented by Chemical Formula 5 or Chemical Formula 6 bonded to the terminal group; or a combination thereof,

[0159] In Chemical Formula 7, A may be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof, and X may be a single bond, -O-, -S-, -S(=O)-, -S(=O)-, 2 - or a combination thereof, R d may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C1 to C30 thioalkyl group, or a combination thereof, and R e It can be hydrogen, deuterium, C1 to C10 alkyl or a combination thereof.

[0160] In the embodiment, R in Chemical Formula 1 1 and R2 may independently be hydroxyl,

[0161] L 1 and L 2 may independently be a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof,

[0162] R in Formula 2 3 to R 6 may independently be hydroxyl groups, and

[0163] L in Formula 2 3 The phenylene group may be substituted or unsubstituted.

[0164] In the embodiment, R in Chemical Formula 3 and Chemical Formula 4 a and R b may independently be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,

[0165] R c may be the following: a substituted or unsubstituted C1 to C10 alkyl group; a substituted or unsubstituted C1 to C10 heteroalkyl group; a structural unit represented by Chemical Formula 5 or Chemical Formula 6 bonded to a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C1 to C10 heteroalkyl group; or a combination thereof,

[0166] In Chemical Formula 7, A may be a substituted or unsubstituted C1 to C5 alkylene group,

[0167] X can be -S-, R d may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 thioalkyl group, or a combination thereof, and R e It can be a C1 to C10 alkyl group.

[0168] In an embodiment, the polymer including the structural unit represented by Chemical Formula 1 may include the structural unit represented by Chemical Formula 1-1, the structural unit represented by Chemical Formula 1-2, or a combination thereof.

[0169]

[0170] In Chemical Formula 1-1 and Chemical Formula 1-2,

[0171] * is the key point.

[0172] In addition, the compound represented by Chemical Formula 2 may be a compound represented by Chemical Formula 2-1.

[0173]

[0174] In an embodiment, the polymer (B) may be represented by any one of Chemical Formula 3-1 to Chemical Formula 3-5 or Chemical Formula 4-1 to Chemical Formula 4-5.

[0175]

[0176]

[0177]

[0178] In Chemical Formulas 3-1 to 3-5 and Chemical Formulas 4-1 to 4-5, n 4 Can be from 1 to 10,000.

[0179] In chemical formula 3-5, n 2 can be from 1 to 10,000, and

[0180] In chemical formula 4-5, n 3 Can be from 1 to 10,000.

[0181] On the other hand, the composition may include: a polymer including a structural unit represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof; and a polymer including a structure in which one or more of the moieties represented by Chemical Formula 3 or Chemical Formula 4 and a moiety represented by Chemical Formula 7 are bonded to each other, and the weight ratio thereof is about 80:20 to about 20:80, for example, about 75:25 to about 25:75, for example, about 70:30 to about 30:70, for example, about 65:35 to about 35:65, for example, about 60:40 to about 40:60, for example, about 55:45 to about 45:55, but is not limited thereto. By including: a polymer including a structural unit represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof; and a polymer including a structure in which one or more of the moieties represented by Chemical Formula 3 or Chemical Formula 4 and a moiety represented by Chemical Formula 7 are bonded to each other within the above weight ratio, the resist underlayer composition according to the embodiment can provide a resist underlayer having improved quality by improving adhesion to a photoresist and film density.

[0182] The polymer including the structural unit represented by Chemical Formula 1 may have a weight average molecular weight (Mw) of about 1,000 g / mol to about 10,000 g / mol. For example, the polymer including the structural unit represented by Chemical Formula 1 may have a weight average molecular weight of about 2,000 g / mol to about 8,000 g / mol, such as about 3,000 g / mol to about 7,000 g / mol, such as about 4,000 g / mol to about 5,000 g / mol, but is not limited thereto. When the weight average molecular weight of the polymer including the structural unit represented by Chemical Formula 1 is less than about 1,000 g / mol, the film density of the resist bottom layer generated by the polymer is reduced, and the photoresist pattern is damaged or collapsed during the patterning process, and thus the stability may be deteriorated.

[0183] The polymer including a structure in which one or more of the moieties represented by Chemical Formula 3 or Chemical Formula 4 and the moiety represented by Chemical Formula 7 are bonded to each other may have a weight average molecular weight of about 2,000 g / mol to about 100,000 g / mol, for example, about 5,000 g / mol to about 100,000 g / mol, for example, about 10,000 g / mol to about 100,000 g / mol, for example, about 20,000 g / mol to about 100,000 g / mol, for example, about 30,000 g / mol to about 100,000 g / mol, for example, about 40,000 g / mol to about 100,000 g / mol, for example, about 50,000 g / mol to about 80,000 g / mol, for example, about 50,000 g / mol to about 70,000 g / mol, but is not limited thereto. When the weight average molecular weight is within the above range, the carbon content and solubility in a solvent of a resist underlayer composition containing the polymer can be adjusted and thus optimized.

[0184] The total weight of the following two items may be about 0.01 wt % to about 5 wt % based on the total weight of the resist underlying layer composition: a polymer including a structural unit represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof; and a polymer including a structure in which one or more of the moieties represented by Chemical Formula 3 or Chemical Formula 4 and the moiety represented by Chemical Formula 7 are bonded to each other. Within the above range, the thickness, surface roughness, and planarization degree of the resist underlying layer may be adjusted.

[0185] In addition, in addition to the polymer described above, the resist underlayer composition may further include at least one other polymer selected from acrylic resin, epoxy resin, novolac resin, glycoluril resin, and melamine resin, but is not limited thereto.

[0186] The resist underlayer composition may further include an additive of a surfactant, a thermal acid generator, a plasticizer or a combination thereof.

[0187] The surfactant may be, for example, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, etc., but is not limited thereto.

[0188] The thermal acid generator may be an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarbonic acid or / and benzoin toluenesulfonate, 2-nitrobenzyl toluenesulfonate, and other organic alkyl sulfonates may be used, but are not limited thereto.

[0189] The additive may be included in an amount of about 0.001 parts by weight to about 40 parts by weight based on 100 parts by weight of the resist underlayer composition. Within the above range, solubility may be improved without changing optical properties of the resist underlayer composition.

[0190] As long as the solvent has sufficient solubility or dispersibility in the polymer, the solvent is not particularly limited, and may include, for example, at least one selected from the following: propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone, methylpyrrolidone, methyl 2-hydroxyisobutyrate, acetylacetone and ethyl 3-ethoxypropionate.

[0191] In addition, the resist underlayer composition may further include a crosslinking agent.

[0192] The crosslinking agent may be, for example, a melamine-based, substituted urea-based or polymer-based crosslinking agent. Ideally, it may be a crosslinking agent having at least two crosslinking substituents, for example, a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea or butoxymethylated thiourea.

[0193] The crosslinking agent having high heat resistance may be a compound including a crosslinking substituent including an aromatic ring (eg, a benzene ring or a naphthalene ring) in a molecule. The crosslinking agent may have, for example, two or more crosslinking sites.

[0194] According to another embodiment, a resist underlayer prepared using the resist underlayer composition is provided. The resist underlayer can be formed by coating the resist underlayer composition on, for example, a substrate and then curing it through a heat treatment process.

[0195] In the following, reference Figures 1 to 5 A method for forming a pattern using the aforementioned resist underlayer composition is described.

[0196] Figures 1 to 5 It is a cross-sectional view showing a method of forming a pattern using the resist underlayer composition according to the present invention.

[0197] refer to Figure 1 , preparing an etching target. The etching target may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the etching target is limited to the thin film 102. The entire surface of the thin film 102 is washed to remove impurities and the like remaining thereon. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, or a silicon oxide layer.

[0198] Subsequently, a resist underlayer composition including a polymer having moieties represented by Chemical Formula 1 and Chemical Formula 2 and a solvent is applied on the surface of the cleaned thin film 102 by applying a spin coating method.

[0199] Next, the coated composition is dried and baked to form a resist base layer 104 on the thin film 102. The baking may be performed at about 100° C. to about 500° C. (e.g., about 100° C. to about 300° C.) Specifically, the resist base layer composition is described in detail above and thus will be omitted.

[0200] refer to Figure 2 , a photoresist layer 106 is formed by coating a photoresist on the resist bottom layer 104 .

[0201] Examples of photoresists may include positive photoresists containing naphthoquinonediazide compounds and phenolic varnish resins, chemically amplified positive photoresists containing acid generators capable of dissociating acids upon exposure, compounds that decompose in the presence of acids and whose solubility in alkaline aqueous solutions increases, and alkali-soluble resins, chemically amplified positive photoresists containing alkali-soluble resins to which resins capable of increasing solubility in alkaline aqueous solutions can be applied, and the like.

[0202] Next, the substrate 100 having the photoresist layer 106 is primarily baked. The primary baking may be performed at about 90°C to about 120°C.

[0203] refer to Figure 3 , the photoresist layer 106 can be selectively exposed.

[0204] Exposure of the photoresist layer 106 can be performed, for example, by placing an exposure mask having a predetermined pattern on a mask stage of an exposure device and aligning the exposure mask 110 on the photoresist layer 106. Subsequently, by irradiating light into the exposure mask 110, a predetermined area of ​​the photoresist layer 106 formed on the substrate 100 selectively reacts with the light passing through the exposure mask.

[0205] For example, the light used during exposure may include short-wavelength light such as an activation radiation i-line having a wavelength of 365 nanometers, a KrF excimer laser having a wavelength of 248 nanometers, and an ArF excimer laser having a wavelength of 193 nanometers. In addition, EUV (extreme ultraviolet light) having a wavelength of 13.5 nanometers corresponding to extreme ultraviolet light may be used.

[0206] The exposed region 106a of the photoresist layer has a relatively hydrophilic property compared to the non-exposed region 106b of the non-exposed region. Therefore, the exposed region 106a and the non-exposed region 106b of the photoresist layer 106 may have different solubilities from each other.

[0207] Subsequently, the substrate 100 is secondarily baked. The second baking may be performed at about 90° C. to about 150° C. The exposed region of the photoresist layer becomes easily dissolved in a predetermined solvent due to the second baking.

[0208] refer to Figure 4 The exposed area 106a of the photoresist layer is dissolved and removed by a developing solution to form a photoresist pattern 108. Specifically, the exposed area 106a of the photoresist layer is dissolved and removed by using a developing solution (such as tetramethyl ammonium hydroxide (TMAH) etc.) to complete the photoresist pattern 108.

[0209] Subsequently, the photoresist pattern 108 is used as an etching mask to etch the resist bottom layer. Through etching, an organic layer pattern 112 is formed. The etching may be, for example, dry etching using an etching gas, and the etching gas may be, for example, CHF 3 CF 4 , Cl 2 , O 2 As described above, since the resist underlayer formed of the resist underlayer composition according to the embodiment has a fast etching rate, a smooth etching process can be performed in a short time.

[0210] refer to Figure 5 , the photoresist pattern 108 is applied as an etching mask to etch the exposed thin film 102. Thus, the thin film is formed into a thin film pattern 114. In the previously performed exposure process, the thin film pattern 114 formed by the exposure process performed using a short wavelength light source such as an active radiation i-line (wavelength of 365 nanometers), a KrF excimer laser (wavelength of 248 nanometers), and an ArF excimer laser (wavelength of 193 nanometers) may have a width of tens of nanometers to hundreds of nanometers, and the thin film pattern 114 formed by the exposure process performed using an EUV light source may have a width of less than or equal to about 20 nanometers.

[0211] Hereinafter, the present disclosure is described in more detail via examples regarding synthesis of a polymer and preparation of a resist underlayer composition including the same. However, the present disclosure is not technically limited to the following example embodiments.

[0212] Synthesis Example

[0213] Synthesis Example 1

[0214] 14.4 g of 2-hydroxynaphthalene, 21.8 g of 1-hydroxypyrene, 6 g of p-formaldehyde, 1.9 g of p-toluenesulfonic acid, and 100 g of propylene glycol monomethyl ether acetate were put into a flask, and then stirred at 85° C. for 10 hours. When the reaction was completed, methanol and water were added thereto, and a precipitate formed therein was repeatedly filtered to remove the monomer remaining therein and obtain a polymer including a structural unit represented by Chemical Formula 1aa (weight average molecular weight (Mw) = 3,500 g / mol).

[0215]

[0216] In Chemical Formula 1aa, * is a bonding point.

[0217] Synthesis Example 2

[0218] 14.4 g of 1-hydroxynaphthalene, 21.8 g of 1-hydroxypyrene, 33.2 g of 1,4-bis(methoxymethyl)benzene, 1.5 g of diethyl sulfate, and 50 g of propylene glycol monomethyl ether acetate were put into a flask, and then stirred at 100° C. for 8 hours. When the reaction was completed, hexane, methanol, and water were added thereto to remove the monomers remaining therein through precipitation and obtain a polymer including a structural unit represented by Chemical Formula 1bb (weight average molecular weight (Mw) = 6,000 g / mol).

[0219]

[0220] In the chemical formula 1bb, * is a bonding point.

[0221] Synthesis Example 3

[0222] Step 1: Friedel-Craft Acylation Reaction

[0223] 27.3 g of 1,4-benzenedicarbonyl chloride, 65.5 g of methoxypyrene and 496 g of 1,2-dichloroethane were put into a flask. Subsequently, 17.9 g of aluminum chloride was slowly added to this solution, and then stirred at room temperature for 12 hours. When the reaction was completed, methanol was added thereto, and the precipitate formed therein was filtered and dried.

[0224] Step 2: Demethylation reaction

[0225] 6.00 g of the compound, 10.13 g of 1-dodecanol, 3.37 g of potassium hydroxide, and 30.3 g of N,N-dimethylformamide were put into a flask, and then stirred for 8 hours at 120° C. The reaction mixture was cooled, and then neutralized to pH 6 to pH 7 by using a 5% hydrochloric acid solution, and the precipitate formed therein was filtered and dried.

[0226] Step 3: Reduction reaction

[0227] 4.00 g of the demethylated compound and 28.5 g of tetrahydrofuran were added to the flask. 5.29 g of a sodium borohydride aqueous solution was slowly added thereto, and then the mixture was stirred at room temperature for 24 hours.

[0228] When the reaction was completed, the resultant was neutralized to about pH 7 by using a 5% hydrochloric acid solution, and then extracted with ethyl acetate and dried to obtain a compound represented by Chemical Formula 2aa.

[0229]

[0230] Synthesis Example 4

[0231] 24.9 g of 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione, 8.4 g of 5-mercaptopentenol, 2.3 g of azobisisobutyronitrile (AIBN) and 15.9 g of N,N-dimethylformamide (DMF) were placed in a 500 ml 3-necked round bottle, and a condenser was connected thereto. The obtained mixture was reacted at 80° C. for 16 hours, and then cooled to room temperature. The reaction solution was dripped into a 1-liter wide-mouth bottle containing 800 g of water while stirring to produce a jelly, and the jelly was dissolved in 80 g of tetrahydrofuran (THF). The dissolved resin solution was treated with toluene to form a precipitate, and thus the monomers and small molecules were removed. Finally, 15 g of a polymer containing a structural unit represented by the chemical formula 3aa (weight average molecular weight (Mw) = 20,000 g / mol) was obtained.

[0232]

[0233] Synthesis Example 5

[0234] 25.3 g of 1,3-diallyl-5-(2-hydroxyethyl)isocyanurate, 5.3 g of propane-1-thiol (propane-1-thiol), 1.3 g of AIBN (azobisisobutyronitrile) and 15.9 g of N,N-dimethylformamide (DMF) were placed in a 500 ml 3-necked round bottle, and a condenser was connected thereto. After the mixture was reacted at 80°C for 25 hours, the reaction solution was cooled to room temperature. The reaction solution was dripped into a 1-liter wide-mouth bottle containing 800 g of water while stirring to produce a jelly, and the jelly was dissolved in 80 g of tetrahydrofuran (THF). The dissolved resin solution was treated with toluene to form a precipitate, and thus monomers and small molecules were removed. Finally, 15 g of a polymer containing a structural unit represented by chemical formula 3bb (weight average molecular weight (Mw) = 6,000 g / mol) was obtained.

[0235]

[0236] Synthesis Example 6

[0237] 25.3 g of 1,3-diallyl-5-(2-hydroxyethyl)isocyanurate, 7.3 g of butane-1-thiol (butane-1-thiol), 1.3 g of AIBN (azobisisobutyronitrile) and 15.9 g of N,N-dimethylformamide (DMF) were placed in a 500 ml 2-necked round bottle, and a condenser was connected thereto. The reaction solution was reacted at 80° C. for 25 hours, and then cooled to room temperature. Subsequently, the reaction solution was dripped into a 1-liter wide-mouth bottle containing 800 g of water while stirring to produce a jelly, and the jelly was dissolved in 80 g of tetrahydrofuran (THF). The dissolved resin solution was treated with toluene to form a precipitate, and thus monomers and small molecules were removed. Finally, 15 g of a polymer containing a structural unit represented by the chemical formula 3cc (weight average molecular weight (Mw) = 9,000 g / mole) was obtained.

[0238]

[0239] Synthesis Example 7

[0240] 25.3 grams of 1,3-diallyl-5-(2-hydroxyethyl)isocyanurate, 3.9 grams of 2-mercapto alcohol, 1.3 grams of AIBN (azobisisobutyronitrile) and 15.9 grams of N,N-dimethylformamide (DMF) were placed in a 500 ml 2-necked round bottle, and a condenser was connected thereto. The reaction solution was reacted at 80°C for 25 hours, and then cooled to room temperature. Subsequently, the reaction solution was dripped into a 1-liter wide-mouth bottle containing 800 grams of water to produce a jelly, and the jelly was dissolved in 80 grams of tetrahydrofuran (THF). The dissolved resin solution was treated with toluene to form a precipitate, and thus monomers and small molecules were removed. Finally, 15 grams of a polymer containing a structural unit represented by the chemical formula 3dd (weight average molecular weight (Mw) = 7,000 grams / mole) was obtained.

[0241]

[0242]

[0243] Synthesis Example 8

[0244] 25.3 grams of 1,3-diallyl-5-(2-hydroxyethyl)isocyanurate, 10.9 grams of 1,5-pentanedithiol, 1.3 grams of AIBN (azobisisobutyronitrile) and 15.9 grams of N,N-dimethylformamide (DMF) were placed in a 500 ml 2-necked round bottle, and a condenser was connected thereto. The obtained mixture was reacted at 80° C. for 16 hours, and 3.9 grams of 2-mercaptopropanol and 1.3 grams of AIBN (azobisisobutyronitrile) were added thereto, and then reacted for 8 hours and cooled to room temperature. The reaction solution was dripped into a 1-liter wide-mouth bottle containing 800 grams of water to produce a jelly, and the jelly was dissolved in 80 grams of tetrahydrofuran (THF). The dissolved resin solution was treated with toluene to form a precipitate, and thus monomers and small molecules were removed. Finally, 15 g of a polymer including a structural unit represented by the chemical formula 3ee (weight average molecular weight (Mw) = 3,500 g / mol) was obtained.

[0245]

[0246] Preparation of resist base composition

[0247] Examples 1 to 9 and Comparative Examples 1 to 2

[0248] 0.5 g of the polymer (or compound) according to Synthesis Examples 1 to 8, 0.125 g of PD1174 (hardener; TCI) and 0.01 g of pyridinium para-toluenesulfonate (PPTS) were completely dissolved in a mixed solvent of propylene glycol monomethyl ether and ethyl lactate (volume ratio = 7:3) at the ratios shown in Table 1 to prepare resist underlayer compositions according to Examples 1 to 9 and Comparative Examples 1 to 2.

[0249] (Table 1)

[0250] Polymer A (or compound) Polymer B Weight Ratio Example 1 Synthesis Example 1 Synthesis Example 4 20:80 Example 2 Synthesis Example 2 Synthesis Example 4 70:30 Example 3 Synthesis Example 3 Synthesis Example 4 70:30 Example 4 Synthesis Example 2 Synthesis Example 5 80:20 Example 5 Synthesis Example 2 Synthesis Example 5 50:50 Example 6 Synthesis Example 2 Synthesis Example 5 30:70 Example 7 Synthesis Example 1 Synthesis Example 6 50:50 Example 8 Synthesis Example 1 Synthesis Example 7 50:50 Example 9 Synthesis Example 2 Synthesis Example 8 40:60 Comparative Example 1 Synthesis Example 1 - Comparative Example 2 - Synthesis Example 8

[0251] Evaluation of coating uniformity

[0252] 2 ml of the composition according to Examples 1 to 9 and Comparative Example 1 were respectively taken and then cast on an 8-inch wafer and spin-coated at 1,500 rpm for 20 seconds using an automatic track (ACT-8, TEL (Tokyo Electron Limited)) and then cured at 210°C for 90 seconds to form a 250 angstrom thick film.

[0253] Additionally, the base layer composition was further diluted and then spin coated and cured as described above to form an ultra-thin film with a thickness of 50 angstroms.

[0254] The coating uniformity was evaluated by measuring the thickness at 51 points on the horizontal axis, and the results are plotted in Table 2. Next, the difference (angstroms) between the maximum and minimum values ​​in the thickness measurements at 51 points was obtained to evaluate the coating uniformity, and herein, the smaller the difference, the better the coating uniformity.

[0255] (Table 2)

[0256]

[0257] Referring to Table 2, the resist underlayer compositions according to Examples 1 to 9 exhibited excellent coating uniformity compared to the resist underlayer composition according to Comparative Example 1.

[0258] Evaluation of film density

[0259] Each of the resist underlayer compositions according to Examples 1 to 9 and Comparative Example 2 was spin-coated on a silicon substrate, and then heat-treated on a hot plate at 210° C. for 90 seconds to form a resist underlayer having a thickness of about 100 nm.

[0260] Subsequently, the density of the resist underlayer was measured, and the results are shown in Table 3. The density of the resist underlayer was measured by using an X-ray diffractometer (model: X'Pert PRO MPD, Malvern Panalytical Ltd. (Netherlands)).

[0261] (Table 3)

[0262] Film density (g / cm3) Example 1 1.39 Example 2 1.36 Example 3 1.38 Example 4 1.38 Example 5 1.35 Example 6 1.35 Example 7 1.34 Example 8 1.37 Example 9 1.33 Comparative Example 2 1.25

[0263] Referring to Table 3, the films formed from the resist underlayer compositions according to Examples 1 to 9 exhibited high density compared to the film formed from the resist underlayer composition according to Comparative Example 2. The reason for this is considered to be that the film density is improved by the polymer (or compound) containing a substituted polycyclic aromatic ring group and the polymer having a high ratio of a core containing a heterocyclic structure contained in the resist underlayer compositions according to Examples 1 to 9.

[0264] Referring to the results of Table 3, the resist underlayer compositions according to Examples 1 to 9 can form a film having a denser structure than the resist underlayer composition of the comparative example.

[0265] Evaluation of exposure characteristics

[0266] The compositions according to Examples 1 to 9 and Comparative Example 2 were respectively coated by spin coating, and then heat-treated on a hot plate at 210° C. for 90 seconds to form a resist bottom layer having a thickness of about 10 nm.

[0267] Subsequently, on the photoresist bottom layer, a photoresist solution was applied 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 to light at an accelerating voltage of 100 keV by using an e-beam exposure device (Elionix. Inc.), and then heat-treated at 110° C. for 60 seconds. Subsequently, the photoresist layer was developed with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution at 23° C., and rinsed with pure water for 15 seconds to form a line and space (L / S) photoresist pattern.

[0268] Next, the optimal energy of the photoresist pattern was evaluated, and the results are plotted in Table 4. Herein, the optimal energy (Eop, microcoulomb / cm2) indicates the exposure dose for resolving 100 nanometer lines and spaces at 1:1, and in Table 4, the Eop of the example is expressed as a relative value compared to the Eop of the comparative example 2.

[0269] (Table 4)

[0270] Eop (microcoulomb / square centimeter) Example 1 0.89 Example 2 0.88 Example 3 0.84 Example 4 0.83 Example 5 0.88 Example 6 0.89 Example 7 0.89 Example 8 0.90 Example 9 0.91 Comparative Example 2 1.0

[0271] Referring to Table 4, when the photoresist underlayer compositions according to Examples 1 to 9 were used to form a resist underlayer, Examples 1 to 9 exhibited excellent optimum energy of the photoresist pattern as compared to Comparative Example 2.

[0272] Therefore, referring to the results of Table 4, when the resist underlayer compositions according to Examples 1 to 9 are used, Examples 1 to 9 can form photoresist patterns having more excellent sensitivity than the comparative example.

[0273] In the above, certain embodiments of the present invention have been described and shown, however, it is obvious to those skilled in the art that the present invention is not limited to the embodiments as described, and various modifications and conversions may be made without departing from the spirit and scope of the present invention. Therefore, the modified or converted embodiments may not be understood solely from the technical concepts and aspects of the present invention, and the modified embodiments are within the scope of the claims of the present invention.

Claims

1. A resist bottom layer composition, comprising: (A) a polymer comprising a structural unit represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof; (B) a polymer including a structure in which at least one of the moieties represented by Chemical Formula 3 or Chemical Formula 4 and the moiety represented by Chemical Formula 7 are bonded to each other; and (C) Solvent: [Chemical formula 1] Wherein, in Chemical Formula 1, R 1 and R 2 are independently hydroxy, substituted or unsubstituted C1 to C20 alkoxy, halogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 heteroaryl, or a combination thereof, L 1 and L 2 are independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof, and * is the bonding point; [Chemical formula 2] Wherein, in Chemical Formula 2, R 3 to R 6 are independently a hydroxyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and L 3 is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof; [Chemical formula 3] [Chemical formula 4] Among them, in Chemical Formula 3 and Chemical Formula 4, R a and R b are independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C1 to C10 heteroalkyl, substituted or unsubstituted C2 to C20 heteroalkenyl, substituted or unsubstituted C3 to C20 heterocycloalkyl, or substituted or unsubstituted C6 to C20 heteroaryl, or a combination thereof, R c is the following: a terminal group which is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C2 to C20 heteroalkenyl group, a substituted or unsubstituted C3 to C20 heterocycloalkyl group, or a combination thereof; a structural unit represented by Chemical Formula 5 or Chemical Formula 6 bonded to the terminal group; or a group represented by a combination thereof, and Chemical Formula 3 or Chemical Formula 4 is bonded to the point indicated by * in Chemical Formula 7 at each * position; [Chemical formula 5] [Chemical formula 6] Among them, in Chemical Formula 5 and Chemical Formula 6, L 3 and L 4 are independently substituted or unsubstituted C1 to C20 alkylene, substituted or unsubstituted C1 to C20 heteroalkylene, or a combination thereof, R a and R b are independently the same as defined in Chemical Formula 3 and Chemical Formula 4, and * is the bonding point; [Chemical formula 7] Among them, in chemical formula 7, A is a single bond, a substituted or unsubstituted C1 to C10 alkylene group, -C(=O)-, -(CO)O-, -O(CO)O-, or a combination thereof, X is a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -(CO)O-, -O(CO)O-, -NR-, or a combination thereof, wherein R is hydrogen, deuterium, or a C1 to C10 alkyl group, R d is hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, epoxy, (meth)acrylate, oxetanyl, thiol, carboxyl, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aryloxy, or a combination thereof, R e is one of hydrogen, deuterium and C1 to C10 alkyl, n 1 is 1 to 10,000, and *bonded to Chemical Formula 3 or Chemical Formula 4, or bonded to hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, epoxy, (meth)acrylate, oxetanyl, thiol, carboxyl, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aryloxy, or a combination thereof, The premise is that at least one of Chemical Formula 3 or Chemical Formula 4 is bonded to * in Chemical Formula 7.

2. The resist base composition according to claim 1, wherein R in Formula 1 1 and R 2 are independently hydroxyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted vinyl, or a combination thereof, L in Formula 1 1 and L 2 are independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof, R in Formula 2 3 to R 6 are independently hydroxyl, thiol, cyano, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof, and L in Formula 2 3 is substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, or a combination thereof.

3. The resist base composition according to claim 1, wherein R in Formula 3 and Formula 4 a and R b are independently substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C1 to C10 heteroalkyl, substituted or unsubstituted C2 to C20 heteroalkenyl or substituted or unsubstituted C3 to C20 heterocycloalkyl, R c is the following: a terminal group which is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, or a substituted or unsubstituted C3 to C20 heterocycloalkyl group; a structural unit represented by Chemical Formula 5 or Chemical Formula 6 bonded to the terminal group; or a combination thereof, In Chemical Formula 7, A is a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof, X is a single bond, -O-, -S-, -S(=O)-, -S(=O)2- or a combination thereof, R d is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C1 to C30 thioalkyl group, or a combination thereof, and R e is hydrogen, deuterium, C1 to C10 alkyl or a combination thereof.

4. The resist base composition according to claim 1, wherein R in Formula 1 1 and R 2 are independently hydroxyl groups, L 1 and L 2 are independently substituted or unsubstituted C1 to C10 alkylene, substituted or unsubstituted C6 to C20 arylene, or a combination thereof, R in Formula 2 3 to R 6 are independently hydroxyl groups, and L in Formula 2 3 is a substituted or unsubstituted phenylene group.

5. The resist underlayer composition according to claim 1, wherein R in Formula 3 and Formula 4 a and R b are independently substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C20 alkenyl, or a combination thereof, R in Formula 3 and Formula 4 c is the following: a substituted or unsubstituted C1 to C10 alkyl group; or a substituted or unsubstituted C1 to C10 heteroalkyl group; or a structural unit represented by Chemical Formula 5 or Chemical Formula 6 bonded to a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C1 to C10 heteroalkyl group; or a combination thereof, In Chemical Formula 7, A is a substituted or unsubstituted C1 to C5 alkylene group, X is -S-, R d is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 thioalkyl group, or a combination thereof, and R e It is a C1 to C10 alkyl group.

6. The resist underlayer composition according to claim 1, wherein the polymer comprising the structural unit represented by Chemical Formula 1 comprises the structural unit represented by Chemical Formula 1-1, the structural unit represented by Chemical Formula 1-2, or a combination thereof: [Chemical formula 1-1] [Chemical formula 1-2] in, In Chemical Formula 1-1 and Chemical Formula 1-2, * is the key point.

7. The resist underlayer composition according to claim 1, wherein the compound represented by Chemical Formula 2 is a compound represented by Chemical Formula 2-1: [Chemical formula 2-1] 8. The resist underlayer composition according to claim 1, wherein the polymer in (B) is represented by any one of Chemical Formula 3-1 to Chemical Formula 3-5 or Chemical Formula 4-1 to Chemical Formula 4-5: [Chemical formula 3-1] [Chemical formula 3-2] [Chemical formula 3-3] [Chemical formula 3-4] [Chemical formula 3-5] [Chemical formula 4-1] [Chemical formula 4-2] [Chemical formula 4-3] [Chemical formula 4-4] [Chemical formula 4-5] in, In Chemical Formulae 3-1 to 3-5 and Chemical Formulae 4-1 to 4-5, n 4 1 to 10,000, In chemical formula 3-5, n 2 is 1 to 10,000, and In chemical formula 4-5, n 3 From 1 to 10,000.

9. The resist underlayer composition according to claim 1, wherein The composition comprises: The polymer comprising the structural unit represented by Chemical Formula 1, the compound represented by Chemical Formula 2, or a combination thereof; as well as The polymer comprising a structure in which one or more of the moieties represented by Chemical Formula 3 or Chemical Formula 4 and the moiety represented by Chemical Formula 7 are bonded to each other The weight ratio is 80:20 to 20:

80. 10 . The resist underlayer composition according to claim 1 , wherein the weight average molecular weight of the polymer including the structural unit represented by Chemical Formula 1 is 1,000 g / mol to 10,000 g / mol.

11. The resist underlayer composition according to claim 1, wherein the weight average molecular weight of the polymer comprising the structure in which one or more of the moieties represented by Chemical Formula 3 or Chemical Formula 4 and the moiety represented by Chemical Formula 7 are bonded to each other is 2,000 g / mol to 100,000 g / mol.

12. The resist underlayer composition according to claim 1, wherein The total weight of the following: The polymer comprising the structural unit represented by Chemical Formula 1, the compound represented by Chemical Formula 2, or a combination thereof; and the polymer comprising the structure in which one or more of the moieties represented by Chemical Formula 3 or Chemical Formula 4 and the moiety represented by Chemical Formula 7 are bonded to each other, Based on the total weight of the resist underlying composition, the amount is 0.01 wt % to 5 wt %. 13 . The resist underlayer composition according to claim 1 , further comprising at least one polymer selected from the group consisting of acrylic resin, epoxy resin, novolac resin, glycoluril resin and melamine resin. 14 . The resist underlayer composition according to claim 1 , further comprising an additive, wherein the additive comprises a surfactant, a thermal acid generator, a plasticizer or a combination thereof.

15. A method for forming a pattern, comprising: forming an etching target layer on the substrate, forming a resist underlayer on the etching target layer by applying the resist underlayer composition according to any one of claims 1 to 14, forming a photoresist pattern on the resist bottom layer, and The resist bottom layer and the etching target layer are sequentially etched using the photoresist pattern as an etching mask.

16. The method for forming a pattern according to claim 15, wherein The forming of the photoresist pattern comprises: forming a photoresist layer on the resist bottom layer, exposing the photoresist layer, and The photoresist layer is developed. 17 . The method for forming a pattern according to claim 15 , wherein the forming of the resist base layer further comprises a heat treatment performed at a temperature of 100° C. to 500° C. after coating the resist base layer composition.

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