Amide-based compound, and composition for resist underlayer film formation and resist underlayer film which comprise same

Abstract

The present invention relates to an amide-based compound, and a composition for resist underlayer film formation and a resist underlayer film which comprise same, the amide-based compound being capable of forming a resist underlayer film enabling formation of a high-quality pattern even with low exposure energy.

Description

Amide-based compounds, composition for forming a resist underlayer containing the same, and a resist underlayer.

[0001] The present invention relates to an amide-based compound, a composition for forming a resist underlayer film comprising the same, and a resist underlayer film.

[0002]

[0003] Extreme ultraviolet lithography (EUV) is a technology capable of forming patterns of even finer sizes for the high integration of semiconductor chips. The biggest difference from conventional ArF lithography and KrF lithography is that it uses light with a wavelength of approximately 13.5 nm.

[0004] As the wavelength of light used in EUV lithography shortens and transmits most elements, the need for the underlayer anti-reflective coatings applied in conventional processes has disappeared. However, since most organic-based Chemically Amplified Resists (CARs) and inorganic-based Metal Oxide Resists (MORs) currently used for EUV do not possess excellent adhesion, there is a growing need to develop underlayer films that enhance adhesion without anti-reflective functionality. Additionally, to reduce the massive cost and maintenance expenses of EUV exposure equipment, there is a demand for performance capabilities that minimize costs by decreasing the exposure energy required for photoresist pattern formation.

[0005] Generally, photoresists have a fixed amount of light that must be irradiated to form a desired pattern, which is referred to as the optimal exposure amount. While much research is being conducted to minimize the optimal exposure amount for EUV photoresists, it is generally known that reducing the exposure amount degrades the surface roughness and size uniformity of the pattern. If the surface roughness and size uniformity of the pattern deteriorate, the performance of semiconductor products is reduced; further deterioration leads to defects, resulting in a decrease in product yield.

[0006] Accordingly, there is a need to develop technology for a resist underlayer that reduces the exposure energy required for pattern formation while maintaining excellent adhesion to the photoresist.

[0007]

[0008] The present invention provides an amide-based compound capable of forming a resist underlayer capable of realizing a high-quality pattern even at low exposure energy, a composition for forming a resist underlayer comprising the same, and a resist underlayer.

[0009] However, the problems that the present invention aims to solve are not limited to those mentioned above, and other unmentioned problems will be clearly understood by those skilled in the art from the description below.

[0010]

[0011] One embodiment of the present invention provides an amide compound comprising a repeating unit represented by the following chemical formula 1:

[0012] [Chemical Formula 1]

[0013]

[0014] In the above chemical formula 1, R1 and R2 are each independently hydrogen; or a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms; or connected to each other to form a ring,

[0015] R 11 to R14 Each is independently hydrogen; a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms; or a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms; and

[0016] The above substituted alkyl group, alkenyl group and alkynyl group are each independently a substituent which is a halogen element, a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, or a straight-chain or branched-chain alkoxy group having 1 to 5 carbon atoms.

[0017] According to one embodiment of the present invention, R1 and R2 in Chemical Formula 1 may be hydrogen.

[0018] According to one embodiment of the present invention, in Formula 1, R 11 and R 12 At least one of them is a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms; or a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms; and R 13 and R 14 At least one of them may be a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms; or a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms.

[0019] According to one embodiment of the present invention, the alkenyl group may have a carbon-carbon double bond at the terminal, and the alkenyl group may have a carbon-carbon triple bond at the terminal.

[0020] According to one embodiment of the present invention, R in Formula 1 11 to R 14 It can be the same.

[0021] According to one embodiment of the present invention, the amide compound may further include an additional repeating unit comprising at least one of the repeating units represented by the following chemical formulas 2a to 2d.

[0022] [Chemical Formula 2a] [Chemical Formula 2b]

[0023]

[0024] [Chemical Formula 2c] [Chemical Formula 2d]

[0025]

[0026] In the above chemical formula, R 21 , R 23 , R 25 and R 27 Each is independently hydrogen; or a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; and

[0027] R 22 ... is a substituted or unsubstituted straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenylene group having 2 to 5 carbon atoms; a substituted or unsubstituted cycloalkylene group having 5 to 10 carbon atoms; a substituted or unsubstituted heterocycloalkylene group having 5 to 10 carbon atoms; a substituted or unsubstituted cycloalkenylene group having 5 to 10 carbon atoms; a straight-chain or branched-chain linker having 2 to 5 carbon atoms containing a C=O bond; a cyclic linker having 5 to 10 carbon atoms containing a C=O bond; a heterocyclic linker having 5 to 10 carbon atoms containing a C=O bond; or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; and

[0028] R 24...is a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 5 carbon atoms; a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms; a substituted or unsubstituted heterocycloalkyl group having 5 to 10 carbon atoms; a substituted or unsubstituted cycloalkenyl group having 5 to 10 carbon atoms; a straight-chain or branched-chain hydrocarbon group having 2 to 5 carbon atoms containing a C=O bond; a cyclic hydrocarbon group having 5 to 10 carbon atoms containing a C=O bond; a heterocyclic hydrocarbon group having 5 to 10 carbon atoms containing a C=O bond; or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; and

[0029] R 26 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and

[0030] R 28 and R 29 Each is independently hydrogen; a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; or a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 5 carbon atoms; and

[0031] The above-mentioned substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, heterocycloalkyl group, aryl group, alkylene group, alkenylene group, cycloalkylene group, cycloalkenylene group, heterocycloalkylene group, and arylene group each independently have a substituent that is a halogen element, a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, or a straight-chain or branched-chain alkoxy group having 1 to 5 carbon atoms.

[0032] According to one embodiment of the present invention, R in Formula 2a 22 may be an unsubstituted straight-chain alkylene group having 1 to 5 carbon atoms. In the above formula 2b, R 24 may be an unsubstituted branched-chain alkyl group having 3 to 5 carbon atoms. In the above formula 2c, R 25 It can be hydrogen.

[0033] According to one embodiment of the present invention, the molar ratio of the repeating unit represented by Formula 1 and the additional repeating unit of the amide compound may be 1:1 to 1:9.

[0034] One embodiment of the present invention provides a composition for forming a resist underlayer film comprising the amide-based compound; and a solvent.

[0035] According to one embodiment of the present invention, based on 100 parts by weight of the composition for forming a resist lower layer, the content of the amide-based compound may be 0.02 parts by weight or more and 3 parts by weight or less.

[0036] According to one embodiment of the present invention, the composition for forming a resist underlayer further comprises a crosslinking agent, and based on 100 parts by weight of the composition for forming a resist underlayer, the content of the crosslinking agent may be 0.01 parts by weight or more and 5 parts by weight or less.

[0037] According to one embodiment of the present invention, the composition for forming a resist lower film further comprises a thermal acid generating agent, and based on 100 parts by weight of the composition for forming a resist lower film, the content of the thermal acid generating agent may be 0.001 parts by weight or more and 1 part by weight or less.

[0038] According to one embodiment of the present invention, the composition for forming a resist lower layer further comprises a crosslinking agent and a thermal acid generating agent, and the weight ratio of the thermal acid generating agent to the crosslinking agent may be 1:10 or less.

[0039] According to one embodiment of the present invention, the composition for forming a resist underlayer further comprises a crosslinking agent and a thermal acid generating agent, and based on 100 parts by weight of the composition for forming a resist underlayer, the total content of the crosslinking agent and the thermal acid generating agent may be 0.005 parts by weight or more and 3 parts by weight or less.

[0040] One embodiment of the present invention provides a resist underlayer comprising a cured product of a composition for forming a resist underlayer.

[0041]

[0042]

[0043] An amide-based compound according to one embodiment of the present invention can realize a resist underlayer film in which a pattern of excellent quality can be formed even at low exposure energy.

[0044] In addition, the composition for forming a resist underlayer according to one embodiment of the present invention includes the amide-based compound, thereby enabling the realization of a resist underlayer in which a pattern of excellent quality can be formed even at low exposure energy.

[0045] In addition, according to one embodiment of the present invention, a resist underlayer film can form a pattern of excellent quality even at low exposure energy.

[0046] The effects of the present invention are not limited to those described above, and unmentioned effects will be clearly understood by those skilled in the art from the present specification and the accompanying drawings.

[0047]

[0048] Throughout this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0049] Throughout this specification, when a component is described as being located "on" another component, this includes not only cases where a component is in contact with another component, but also cases where another component exists between the two components.

[0050] Throughout the entire specification, the unit "parts by weight" may refer to the ratio of weight between each component.

[0051] Throughout this specification, terms including ordinal numbers, such as “first” and “second,” are used for the purpose of distinguishing one component from another and are not limited by said ordinal numbers. For example, within the scope of the invention, the first component may also be named the second component, and similarly, the second component may be named the first component.

[0052] Throughout the entire specification, “at least one of a, b and c” may include a, b, or c alone, or two or more combinations selected from the group consisting of a, b, and c.

[0053] Throughout this specification, the term “a and / or b” is used to mean “a or b” and “a and b”.

[0054] Throughout the entire specification, the “weight-average molecular weight” of a compound can be calculated using the molecular weight and molecular weight distribution of the compound. Specifically, a sample with a compound concentration of 1 wt% is prepared by placing tetrahydrofuran (THF) and the compound in a 1 ml glass vial, and after filtering the standard sample (polystyrene) and the sample through a filter (pore size 0.45 μm), the sample is injected into a GPC injector. The molecular weight and molecular weight distribution of the compound can be obtained by comparing the elution time of the sample with the calibration curve of the standard sample. At this time, an Infinity II 1260 (Agilient) can be used as the measuring instrument, and the flow rate can be set to 1.00 mL / min and the column temperature to 40.0 ℃.

[0055]

[0056] The present specification will be described in more detail below.

[0057] One embodiment of the present invention provides an amide compound comprising a repeating unit (first repeating unit) represented by the following chemical formula 1:

[0058] [Chemical Formula 1]

[0059]

[0060] In the above Chemical Formula 1, R1 and R2 are each independently hydrogen; or a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms; or connected to each other to form a ring, and R 11 to R 14 Each is independently hydrogen; a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms; or a substituted or unsubstituted straight-chain or branched-chain alkynyl group having 2 to 10 carbon atoms; and the substituted alkyl group, alkenyl group and alkynyl group are each independently a substituent which is a halogen element, a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, or a straight-chain or branched-chain alkoxy group having 1 to 5 carbon atoms.

[0061] An amide-based compound according to one embodiment of the present invention can realize a resist sublayer in which a high-quality pattern can be formed even at low exposure energy. Specifically, the amide-based compound can effectively generate radicals or secondary electrons when exposed to EUV photons. As a result, a high-quality pattern can be stably formed even at lower exposure energy. In addition, the adhesion of the resist sublayer to the photoresist can be improved by the generated radicals or secondary electrons.

[0062] That is, the above amide-based compound includes a repeating unit represented by Chemical Formula 1, thereby minimizing the deterioration of the resist pattern roughness when exposed to low exposure energy. Through this, when using a resist sublayer film containing the above amide-based compound, a high-quality pattern can be formed more effectively at low exposure energy. In addition, the resist sublayer film containing the above amide-based compound may have excellent adhesion to the photoresist. As a result, EUV process efficiency and productivity can be effectively increased.

[0063] According to one embodiment of the present invention, the repeating unit represented by Formula 1 may include at least one of the repeating units represented by Formulas 1-1 to 1-24 below. That is, the amide compound may include at least one of the repeating units represented by Formulas 1-1 to 1-24 below.

[0064]

[0065]

[0066]

[0067]

[0068]

[0069] The amide-based compound comprising at least one of the repeating units represented by Chemical Formulas 1-1 to 1-24 can effectively generate radicals or secondary electrons by EUV photons as it contains double and / or triple bonds at the ends of the repeating units. Through this, high-quality patterns can be formed more effectively at low exposure energy. In addition, when using the amide-based compound, a resist underlayer with excellent adhesion to the photoresist can be easily realized.

[0070] According to one embodiment of the present invention, the repeating unit represented by Formula 1 of the amide compound may include a structure derived from a first monomer. In this case, the repeating unit represented by Formula 1 may correspond to the first repeating unit. That is, the amide compound may include a first repeating unit. The first repeating unit may include a structure derived from a first monomer. The first monomer may include at least one of the compounds represented by Formulas 1a to 1b below.

[0071] [Chemical Formula 1a] [Chemical Formula 1b]

[0072]

[0073] In the above chemical formulas 1a and 1b, R 11 to R 14 Each is independently hydrogen; a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms; or a substituted or unsubstituted straight-chain or branched-chain alkynyl group having 2 to 10 carbon atoms; and the substituted alkyl group, alkenyl group and alkynyl group are each independently a substituent which is a halogen element, a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, or a straight-chain or branched-chain alkoxy group having 1 to 5 carbon atoms.

[0074] By using at least one of the compounds represented by Chemical Formulas 1a to 1b as the first monomer, the amide compound containing the first repeating unit can be polymerized more easily. In addition, the amide compound may have a structure capable of effectively generating radicals or secondary electrons.

[0075] According to one embodiment of the present invention, the first monomer may include at least one of the following compounds 1-1 to 1-8.

[0076]

[0077] By using at least one of compounds 1-1 to 1-8 as the first monomer, the amide compound containing the first repeating unit can be polymerized more easily. In addition, the amide compound may have a structure capable of effectively generating radicals or secondary electrons.

[0078] According to one embodiment of the present invention, the amide compound comprising a repeating unit represented by Chemical Formula 1 can be prepared through the following Reaction Scheme 1.

[0079] [Reaction Equation 1]

[0080]

[0081] In the above reaction scheme 1, R1, R2, R 11 to R 14 [It] may be the same as defined in Chemical Formula 1 above. Referring to Reaction Scheme 1 above, an intermediate can be prepared by inducing a polymerization reaction of a compound represented by Chemical Formula 3. Subsequently, an amide-based compound containing a repeating unit represented by Chemical Formula 1 can be prepared by reacting the intermediate with a first monomer. In the case of Reaction Scheme 1 above, it may correspond to using a compound represented by Chemical Formula 1a and a compound represented by Chemical Formula 1b as the first monomer. Meanwhile, one of the compound represented by Chemical Formula 1a and the compound represented by Chemical Formula 1b may also be used as the first monomer.

[0082] According to one embodiment of the present invention, in Formula 1, R1 and R2 may each independently be hydrogen; or a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms; or may be bonded to each other to form a ring. Specifically, R1 and R2 may each independently be hydrogen; or an unsubstituted straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms. In this case, the number of carbon atoms in the alkyl group may be 1 to 9, 1 to 7, 1 to 5, or 1 to 2. Additionally, R1 and R2 may be connected to each other to form an aliphatic ring having 5 to 10 carbon atoms. Additionally, R1 and R2 may be connected to each other to form a heterocyclic ring. In this case, the heterocyclic ring may include at least one of oxygen (O), nitrogen (N), and sulfur (S). The heterocyclic ring may be a pentagonal to decagonal ring.

[0083] According to one embodiment of the present invention, R1 and R2 in Formula 1 may be hydrogen. The amide compound in which R1 and R2 in Formula 1 are hydrogen may be easily polymerized and can effectively generate radicals or secondary electrons when exposed to EUV photons. Through this, a composition for forming a resist underlayer containing the amide compound can stably form a pattern of high quality even at lower exposure energy.

[0084] According to one embodiment of the present invention, R 11 to R 14 Each may independently be hydrogen; a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms; or a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms. In this case, R 11 and R 12 At least one of them is not a hydrogen or alkyl group, and R 13 and R14 At least one of them may not be hydrogen or an alkyl group. The number of carbon atoms in the alkyl group may be 1 or more and 10 or less, 1 or more and 8 or less, 1 or more and 5 or less, or 1 or more and 2 or less. The number of carbon atoms in the alkenyl group may be 2 or more and 9 or less, 2 or more and 7 or less, 2 or more and 5 or less, or 2 or more and 3 or less. Additionally, the number of carbon atoms in the alkenyl group may be 2 or more and 9 or less, 2 or more and 7 or less, 2 or more and 5 or less, or 2 or more and 3 or less.

[0085] According to one embodiment of the present invention, in Formula 1, R 11 and R 12 At least one of them is a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms; or a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms; and R 13 and R 14 At least one of them may be a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms; or a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms. In this case, the number of carbon atoms of the alkenyl group may be 2 or more and 9 or less, 2 or more and 7 or less, 2 or more and 5 or less, or 2 or more and 3 or less. Additionally, the number of carbon atoms of the alkenyl group may be 2 or more and 9 or less, 2 or more and 7 or less, 2 or more and 5 or less, or 2 or more and 3 or less.

[0086] In the above chemical formula 1, R 11 to R 14 In the case described above, the amide-based compound can effectively generate radicals or secondary electrons upon exposure to EUV photons. That is, when using a resist sublayer containing the amide-based compound, high-quality patterns can be formed more effectively at low exposure energy. Furthermore, the resist sublayer containing the amide-based compound may exhibit excellent adhesion to the photoresist.

[0087] According to one embodiment of the present invention, the alkenyl group may have a carbon-carbon double bond at the terminal, and the alkenyl group may have a carbon-carbon triple bond at the terminal. Specifically, in Formula 1, R 11 and R 12 At least one of them may be an alkenyl group having a carbon-carbon double bond at the terminal; or an alkenyl group having a carbon-carbon triple bond at the terminal. In addition, in the above formula 1, R 13 and R 14 At least one of them may be an alkenyl group having a carbon-carbon double bond at the end; or an alkenyl group having a carbon-carbon triple bond at the end. That is, a carbon-carbon double bond and / or a carbon-carbon triple bond may be exposed at the end of the repeating unit structure represented by Chemical Formula 1. By this, the amide compound can stably and effectively generate radicals or secondary electrons upon exposure to EUV photons.

[0088] According to one embodiment of the present invention, R in Formula 1 11 to R 14 can be the same. Specifically, in the above chemical formula 1, R 11 to R 14 may be a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms; or a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms; R 11 to R 14 In the case where the above amide-based compound is the same, polymerization may be easy, and the efficiency of radical or secondary electron generation may be increased upon exposure to EUV photons.

[0089] According to one embodiment of the present invention, the substituted alkyl group, alkenyl group, and alkynyl group in Formula 1 may each independently have a substituent that is a halogen element, a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, or a straight-chain or branched-chain alkoxy group having 1 to 5 carbon atoms. Specifically, the substituent may be any one of F, Cl, Br, and I. Additionally, the substituent may be an alkyl group, and the number of carbon atoms of the alkyl group may be 1 to 3, 1 to 2, or 1. Additionally, the substituent may be an alkoxy group, and the number of carbon atoms of the alkoxy group may be 1 to 3, 1 to 2, or 1.

[0090]

[0091] According to one embodiment of the present invention, the amide compound may further include an additional repeating unit (second repeating unit) comprising at least one of the repeating units represented by the following chemical formulas 2a to 2d.

[0092] [Chemical Formula 2a] [Chemical Formula 2b]

[0093]

[0094] [Chemical Formula 2c] [Chemical Formula 2d]

[0095]

[0096]

[0097] In the above chemical formula, R 21 , R 23 , R 25 and R 27 Each is independently hydrogen; or a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; and

[0098] R 22... is a substituted or unsubstituted straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenylene group having 2 to 5 carbon atoms; a substituted or unsubstituted cycloalkylene group having 5 to 10 carbon atoms; a substituted or unsubstituted heterocycloalkylene group having 5 to 10 carbon atoms; a substituted or unsubstituted cycloalkenylene group having 5 to 10 carbon atoms; a straight-chain or branched-chain linker having 2 to 5 carbon atoms containing a C=O bond; a cyclic linker having 5 to 10 carbon atoms containing a C=O bond; a heterocyclic linker having 5 to 10 carbon atoms containing a C=O bond; or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; and

[0099] R 24 ...is a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 5 carbon atoms; a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms; a substituted or unsubstituted heterocycloalkyl group having 5 to 10 carbon atoms; a substituted or unsubstituted cycloalkenyl group having 5 to 10 carbon atoms; a straight-chain or branched-chain hydrocarbon group having 2 to 5 carbon atoms containing a C=O bond; a cyclic hydrocarbon group having 5 to 10 carbon atoms containing a C=O bond; a heterocyclic hydrocarbon group having 5 to 10 carbon atoms containing a C=O bond; or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; and

[0100] R 26 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and

[0101] R 28 and R 29 Each is independently hydrogen; a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; or a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 5 carbon atoms; and

[0102] The above-mentioned substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, heterocycloalkyl group, aryl group, alkylene group, alkenylene group, cycloalkylene group, cycloalkenylene group, heterocycloalkylene group, and arylene group each independently have a substituent that is a halogen element, a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, or a straight-chain or branched-chain alkoxy group having 1 to 5 carbon atoms.

[0103] According to one embodiment of the present invention, the amide-based compound further comprising the second repeating unit can have its reactivity with the crosslinking agent effectively improved. Through this, in the case of a resist sublayer film comprising the amide-based compound, intermixing with the photoresist can be prevented, and adhesion to the photoresist can be effectively improved.

[0104] According to one embodiment of the present invention, in the formula 2a, R 21 It may be hydrogen; or a methyl group. Also, in the above formula 2a, R 22 may be an unsubstituted straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms. More specifically, R 22 may be an unsubstituted straight-chain alkylene group, and the number of carbon atoms in the alkylene group may be 1 or more and 5 or less, 1 or more and 4 or less, 1 or more and 3 or less, or 1 or more and 2 or less. In the above formula 2a, R 21 and R 22 In the case described above, the polymerization of the amide-based compound is easy, and the amide-based compound may have excellent reactivity with the crosslinking agent.

[0105] According to one embodiment of the present invention, in the formula 2b, R 23 It may be hydrogen; or a methyl group. Also, in the above formula 2b, R 24may be an unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms. The number of carbon atoms in the straight-chain alkyl group may be 1 or more and 4 or less, 1 or more and 3 or less, 1 or more and 2 or less, 2 or more and 5 or less, 3 or more and 5 or less, or 4 or more and 5 or less. More specifically, R 24 may be an unsubstituted branched-chain alkyl group, and the number of carbon atoms of the branched-chain alkyl group may be 3 or more and 5 or less, 3 or more and 4 or less, or 4 or more and 5 or less. In the above formula 2b, R 23 and R 24 In the case described above, the polymerization of the amide-based compound is easy, and the amide-based compound may have excellent reactivity with the crosslinking agent.

[0106] According to one embodiment of the present invention, in the formula 2c, R 25 can be hydrogen. Also, in the above chemical formula 2c, R 26 may be an unsubstituted phenyl group. In the above formula 2c, R 25 and R 26 In the case described above, the polymerization of the amide-based compound is easy, and the amide-based compound may have excellent reactivity with the crosslinking agent.

[0107] According to one embodiment of the present invention, in the formula 2d, R 27 It can be hydrogen; or a methyl group. Also, in the above formula 2d, R 28 and R 29 Each may independently be hydrogen; an unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms. In this case, the number of carbon atoms in the alkyl group may be 1 or more and 4 or less, 1 or more and 3 or less, or 1 or more and 2 or less. In the above formula 2d, R 27 to R 29 In the case described above, the polymerization of the amide-based compound is easy, and the amide-based compound may have excellent reactivity with the crosslinking agent.

[0108] According to one embodiment of the present invention, the additional repeating unit may include at least one of the repeating units represented by the following chemical formulas 2-1 to 2-23. That is, the amide compound may include at least one of the repeating units represented by the following chemical formulas 2-1 to 2-23.

[0109]

[0110]

[0111] The amide-based compound comprising at least one repeating unit represented by Chemical Formulas 2-1 to 2-23 can effectively perform a crosslinking reaction with a crosslinking agent included in a composition for forming a resist sublayer. Through this, in the case of a resist sublayer containing the amide-based compound, intermixing with the photoresist can be prevented, and adhesion to the photoresist can be effectively improved.

[0112] According to one embodiment of the present invention, the amide compound may include a structure in which a repeating unit represented by Formula 1 is derived from a first monomer, and an additional repeating unit may include a structure derived from a second monomer. In this case, the repeating unit represented by Formula 1 may correspond to the first repeating unit, and the additional repeating unit may correspond to the second repeating unit. That is, the amide compound may include a first repeating unit and a second repeating unit. The first repeating unit may include a structure derived from a first monomer, and the second repeating unit may include a structure derived from a second monomer.

[0113] According to one embodiment of the present invention, the second monomer may include at least one of the compounds represented by the following formulas 2a-1 to 2d-1.

[0114] [Chemical Formula 2a-1] [Chemical Formula 2b-1]

[0115]

[0116] [Chemical Formula 2c-1] [Chemical Formula 2d-1]

[0117]

[0118]

[0119] R in the above chemical formula 2a-1 21 and R 22 is the same as defined in the above chemical formula 2a, and R in the above chemical formula 2b-1 23 and R 24 is the same as defined in the above chemical formula 2b, and R in the above chemical formula 2c-1 25 and R 26 is the same as defined in the above chemical formula 2c, and R in the above chemical formula 2d-1 27 to R 28 may be the same as defined in the above chemical formula 2d.

[0120] By using at least one of the compounds represented by Formulas 2a-1 to 2d-1 as the second monomer, the amide compound containing the second repeating unit can be polymerized more easily. In addition, the amide compound may have excellent reactivity with a crosslinking agent.

[0121] According to one embodiment of the present invention, the first monomer may include at least one of the following compounds 2-1 to 2-23.

[0122]

[0123]

[0124] By using at least one of compounds 2-1 to 2-23 as the second monomer, the amide compound containing the second repeating unit can be polymerized more easily. In addition, the amide compound may have excellent reactivity with a crosslinking agent.

[0125] According to one embodiment of the present invention, the amide compound comprising a repeating unit (first repeating unit) represented by Chemical Formula 1 and an additional repeating unit (second repeating unit) can be prepared through the following Reaction Scheme 2.

[0126] [Reaction Equation 2]

[0127]

[0128] In the case of the above reaction scheme 2, it may correspond to using a compound represented by chemical formula 1a and a compound represented by chemical formula 1b as the first monomer, and using a compound represented by chemical formula 2a-1 as the second monomer. In the above reaction scheme 2, R1, R2, R 11 to R 14 may be the same as defined in Chemical Formula 1 above. Also, in Reaction Scheme 2 above, R 21 and R 22 may be the same as that defined in the above chemical formula 2a.

[0129] Referring to the above reaction scheme 2, a polymerization reaction between a compound represented by chemical formula 3 and a compound represented by chemical formula 2a-1 can be induced to produce an intermediate containing a second repeating unit. Subsequently, an amide-based compound containing a first repeating unit and a second repeating unit can be produced by reacting the intermediate with a first monomer.

[0130] According to one embodiment of the present invention, the amide compound may have a molar ratio of a repeating unit (first repeating unit) represented by Formula 1 and an additional repeating unit (second repeating unit) of 1:1 to 1:9. Specifically, the molar ratio of the first repeating unit and the second repeating unit included in the amide compound may be 1:1 to 1:7, 1:1 to 1:5, 1:1 to 1:4, 1:1 to 1:3, 1:1 to 1:2, 1:3 to 1:9, 1:3 to 1:6, or 1:3 to 1:4. When the molar ratio of the first repeating unit and the second repeating unit is within the aforementioned range, the amide compound may contain a first repeating unit capable of effectively generating radicals or secondary electrons and a second repeating unit having excellent reactivity with a crosslinking agent in appropriate proportions. Accordingly, the amide-based compound can more effectively form a pattern of excellent quality at low exposure energy and provide a resist underlayer film with excellent adhesion to the photoresist.

[0131] According to one embodiment of the present invention, the molar ratio between the first repeating unit and the second repeating unit included in the amide compound can be calculated through the molecular weights of the first monomer and the second monomer used in the preparation of the amide compound and the weight ratio between them.

[0132] According to one embodiment of the present invention, the weight-average molecular weight of the amide compound may be 1,000 g / mol or more and 50,000 g / mol or less.

[0133] When the weight-average molecular weight of the above-mentioned amide-based compound is within the aforementioned range, it is possible to effectively prevent the resist sublayer film containing the above-mentioned amide-based compound from being partially dissolved by the photoresist solvent. Furthermore, by controlling the weight-average molecular weight of the above-mentioned amide-based compound to the aforementioned range, excellent solubility of the amide-based compound in the solvent can be achieved, and the etching rate for the dry etching process of the resist sublayer film can be effectively improved.

[0134]

[0135] One embodiment of the present invention provides a composition for forming a resist underlayer film comprising the amide-based compound; and a solvent.

[0136] A composition for forming a resist underlayer according to one embodiment of the present invention includes the above-mentioned amide-based compound, thereby enabling the realization of a resist underlayer in which a pattern of excellent quality can be formed even at low exposure energy.

[0137] According to one embodiment of the present invention, the solvent may be any conventional organic solvent used in compositions for forming a resist underlayer film without limitation. For example, the solvent may include at least one of cyclohexanone, cyclopentanone, butyrolactone, dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone (NMP), tetrahydrofurfural alcohol, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGME), ethyl lactate, and methyl 2-hydroxyisobutyrate (HBM). However, the type of solvent is not limited thereto.

[0138] According to one embodiment of the present invention, based on 100 parts by weight of the composition for forming a resist lower layer, the content of the amide-based compound may be 0.02 parts by weight or more and 3 parts by weight or less. Specifically, the content of the amide-based compound may be 0.05 parts by weight or more and 2.5 parts by weight or less, 0.1 parts by weight or more and 2 parts by weight or less, 0.5 parts by weight or more and 1.5 parts by weight or less, 1 part by weight or more and 1.5 parts by weight or less, 0.02 parts by weight or more and 2 parts by weight or less, 0.05 parts by weight or more and 1.8 parts by weight or less, 0.1 parts by weight or more and 1.5 parts by weight or less, 0.3 parts by weight or more and 1.2 parts by weight or less, 0.5 parts by weight or more and 1 part by weight or less, 0.5 parts by weight or more and 3 parts by weight or less, 0.5 parts by weight or more and 2.5 parts by weight or less, or 1 part by weight or more and 2 parts by weight or less, based on 100 parts by weight of the composition for forming the resist underlayer film. When the content of the above-mentioned amide-based compound is within the aforementioned range, a pattern of excellent quality can be formed more effectively at low exposure energy, and a resist underlayer with excellent adhesion to the photoresist can be easily realized. Furthermore, by controlling the content of the above-mentioned amide-based compound within the aforementioned range, the resist underlayer can be formed stably. In addition, the problem of the photoresist shape provided on the upper layer not being transferred due to the thickness of the resist underlayer becoming too thick can be prevented.

[0139] According to one embodiment of the present invention, the composition for forming a resist sublayer may further include a crosslinking agent. The crosslinking agent can form a resist sublayer by crosslinking the amide-based compound to form an ultrapolymer. The crosslinking agent may be one used in the art. For example, the crosslinking agent may include at least one of a melamine-based crosslinking agent, an epoxy-based crosslinking agent, and an acrylic-based crosslinking agent.

[0140] According to one embodiment of the present invention, the melamine-based crosslinking agent may be a condensation product of urea and formaldehyde, a condensation product of melamine and formaldehyde, or methylol urea alkyl ethers or methylol melamine alkyl ethers obtained from alcohol. Specifically, monomethylol urea, dimethylol urea, etc. may be used as the condensation product of urea and formaldehyde. Hexamethylol melamine may be used as the condensation product of melamine and formaldehyde, and other partial condensation products of melamine and formaldehyde may also be used.

[0141] In addition, the above methylol urea alkyl ethers are obtained by reacting alcohols with part or all of the methylol group in the condensation product of urea and formaldehyde, and specific examples thereof may include monomethyl urea methyl ether and dimethyl urea methyl ether. The above methylol melamine alkyl ethers are obtained by reacting alcohols with part or all of the methylol group in the condensation product of melamine and formaldehyde, and specific examples thereof may include hexamethylol melamine hexamethyl ether and hexamethylol melamine hexabutyl ether. In addition, compounds having a structure in which the hydrogen atom of the amino group of melamine is substituted with a hydroxymethyl group and a methoxymethyl group, compounds having a structure in which the hydrogen atom of the amino group of melamine is substituted with a butoxymethyl group and a methoxymethyl group, etc. may also be used, and methylol melamine alkyl ethers may be used.

[0142] According to one embodiment of the present invention, the epoxy crosslinking agent may include at least one of polyglycidyl methacrylate, diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylol ethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0143] According to one embodiment of the present invention, based on 100 parts by weight of the composition for forming a resist underlayer, the content of the crosslinking agent may be 0.01 parts by weight or more and 5 parts by weight or less. Specifically, based on 100 parts by weight of the composition for forming a resist underlayer, the content of the crosslinking agent may be 0.05 parts by weight or more and 4 parts by weight or less, 0.1 parts by weight or more and 3.5 parts by weight or less, 0.3 parts by weight or more and 3 parts by weight or less, 0.5 parts by weight or more and 2 parts by weight or less, 0.01 parts by weight or more and 2 parts by weight or less, 0.05 parts by weight or more and 1.5 parts by weight or less, 0.05 parts by weight or more and 1 part by weight or less, 0.05 parts by weight or more and 0.5 parts by weight or less, 0.05 parts by weight or more and 0.3 parts by weight or less, or 2 parts by weight or more and 5 parts by weight or less. When the content of the crosslinking agent is within the aforementioned range, the amide-based compound included in the composition for forming the resist lower layer can be stably crosslinked.

[0144] According to one embodiment of the present invention, the composition for forming a resist sublayer may further include a thermal acid generator. The thermal acid generator may serve to promote the crosslinking reaction of a sangga amide-based compound. In this case, the thermal acid generator may be one used in the art. For example, the thermal acid generator may include at least one of an ammonium salt-based compound, a sulfonium salt-based compound, and an iodonium salt-based compound. Specifically, the thermal acid generator may include at least one of triphenylsulfonium nonaflate, dodecylbenzensulfonic acid, and paratoluenesulfonic acid. In this case, the composition for forming a resist sublayer may include the thermal acid generator without a crosslinking agent.

[0145] According to one embodiment of the present invention, based on 100 parts by weight of the composition for forming a resist lower layer, the content of the thermal acid generating agent may be 0.001 parts by weight or more and 1 part by weight or less. Specifically, the content of the thermal acid generating agent may be 0.005 parts by weight or more and 1 part by weight or less, 0.01 parts by weight or more and 1 part by weight or less, 0.03 parts by weight or more and 1 part by weight or less, 0.05 parts by weight or more and 1 part by weight or less, 0.1 parts by weight or more and 1 part by weight or less, 0.3 parts by weight or more and 1 part by weight or less, 0.5 parts by weight or more and 1 part by weight or less, 0.001 parts by weight or more and 0.1 parts by weight or less, 0.005 parts by weight or more and 0.1 parts by weight or less, 0.01 parts by weight or more and 0.1 parts by weight or less, 0.03 parts by weight or more and 0.1 parts by weight or less, or 0.05 parts by weight or more and 0.1 parts by weight or less, based on 100 parts by weight of the composition for forming the resist lower layer. By adjusting the content of the thermal acid generating agent to the aforementioned range, the resist lower layer can be formed stably. In addition, if the content of the above-mentioned heat-generating agent is within the aforementioned range, the generation of fumes during the heating process of the above-mentioned resist lower film can be suppressed.

[0146] Meanwhile, in the case where the composition for forming the resist lower layer does not include a crosslinking agent and includes a thermal acid generating agent, the content of the thermal acid generating agent may be 0.001 parts by weight or more and 0.5 parts by weight or less, based on 100 parts by weight of the composition for forming the resist lower layer. By controlling the content of the thermal acid generating agent to the aforementioned range, the resist lower layer can be stably formed even when the crosslinking agent is not included.

[0147] According to one embodiment of the present invention, the composition for forming a resist sublayer further comprises a crosslinking agent and a thermal acid generating agent, and the weight ratio of the thermal acid generating agent to the crosslinking agent may be 1:10 or less. Specifically, the weight ratio of the thermal acid generating agent to the crosslinking agent may be 1:8 or less, 1:6 or less, 1:5 or less, 1:3 or less, 1:1 or less, or 1:0.5 or less. In addition, the weight ratio of the thermal acid generating agent to the crosslinking agent may be 1:0.01 or more, 1:0.02 or more, 1:0.05 or more, 1:0.1 or more, 1:0.2 or more, 1:0.3 or more, 1:0.5 or more, 1:1 or more, 1:3 or more, or 1:10 or more. When the weight ratio of the above-mentioned thermal acid generating agent and the above-mentioned crosslinking agent is within the aforementioned range, the reaction between the above-mentioned amide-based compound and the crosslinking agent is carried out smoothly, so that the resist lower layer film can be stably formed.

[0148] According to one embodiment of the present invention, the composition for forming a resist underlayer further comprises a crosslinking agent and a thermal acid generating agent, and based on 100 parts by weight of the composition for forming a resist underlayer, the total content of the crosslinking agent and the thermal acid generating agent may be 0.005 parts by weight or more and 3 parts by weight or less. Specifically, the total content of the crosslinking agent and the thermal acid generating agent is, based on 100 parts by weight of the composition for forming the resist underlayer, 0.01 parts by weight or more and 2.8 parts by weight or less, 0.05 parts by weight or more and 2.5 parts by weight or less, 0.06 parts by weight or more and 2 parts by weight or less, 0.07 parts by weight or more and 1.8 parts by weight or less, 0.1 parts by weight or more and 1.5 parts by weight or less, 0.2 parts by weight or more and 1.3 parts by weight or less, 0.3 parts by weight or more and 1.1 parts by weight or less, 0.005 parts by weight or more and 1.5 parts by weight or less, 0.01 parts by weight or more and 1.2 parts by weight or less, 0.05 parts by weight or more and 1 part by weight or less, 0.065 parts by weight or more and 0.8 parts by weight or less, 0.075 parts by weight or more and 0.5 parts by weight or less, 0.1 parts by weight or more and 0.45 parts by weight or less, and 0.2 parts by weight or more. It may be 0.4 parts by weight or less, 1 part by weight or more and 3 parts by weight or less, or 2 parts by weight or more and 3 parts by weight or less. When the sum of the content of the crosslinking agent and the content of the thermal acid generating agent is within the aforementioned range, the composition for forming a resist underlayer can stably form a resist underlayer.

[0149]

[0150] One embodiment of the present invention provides a resist underlayer comprising a cured product of a composition for forming a resist underlayer.

[0151] According to one embodiment of the present invention, a resist underlayer can form a pattern of excellent quality even at low exposure energy. In addition, the resist underlayer can have excellent adhesion to the resist. That is, the resist underlayer can maintain the same roughness and size of the photoresist pattern even at a low exposure amount, and can improve the productivity and efficiency of the entire process due to its excellent adhesion to the photoresist.

[0152] According to one embodiment of the present invention, the resist sublayer may include a thermosetting product of a composition for forming a resist sublayer. The composition for forming a resist sublayer may be thermosetting at a temperature of 90°C or higher and 240°C or lower. By controlling the thermosetting temperature to the aforementioned range, the solvent contained in the composition for forming a resist sublayer can be effectively removed, and the crosslinking reaction can be stably performed. Furthermore, when the thermosetting temperature is within the aforementioned range, the resist sublayer may have excellent adhesion and stability to the resist.

[0153] According to one embodiment of the present invention, a composition for forming a resist underlayer can be applied to the upper surface of an etching target, and the composition for forming a resist underlayer can be heat-cured to form a resist underlayer. At this time, the etching target may be a silicon wafer, an aluminum substrate, etc. The method of applying the composition for forming a resist underlayer may use any application method used in the art without limitation. For example, methods such as spin coating, roller coating, and spray coating may be used.

[0154] To cure the above-mentioned composition for forming a resist underlayer, heating means used in the art may be used without limitation. For example, the above-mentioned composition for forming a resist underlayer may be heated using heating means such as a high-temperature plate or a convection oven.

[0155] According to one embodiment of the present invention, the resist lower layer may be provided below the EVU photoresist. For example, the resist lower layer may be located below the CAR (Chemically Amplified Resist) or MOR (Metal Oxide Resist).

[0156]

[0157] Hereinafter, the present invention will be described in detail with reference to examples to specifically explain the invention. However, the embodiments according to the present invention may be modified in various different forms, and the scope of the present invention is not to be interpreted as being limited to the embodiments described below. The embodiments of this specification are provided to more completely explain the present invention to those with average knowledge in the art.

[0158]

[0159] Preparation of amide compounds

[0160] compound

[0161] The following compounds were prepared as the first monomers.

[0162] Code Structure (1-1) (1-2) (1-3) (1-4)

[0163]

[0164] The following compounds were prepared as second monomers.

[0165] Code Structure (2-1) (2-2) (2-3)

[0166]

[0167] Example 1-1

[0168] Preparation of an intermediate containing a repeating unit represented by Chemical Formula 3-1

[0169] [Chemical Formula 3-1]

[0170]

[0171] 50.0 g of 2-butanone was placed in a 250 mL reactor and heated to 85 °C. Then, a solution of 25.0 g of maleic anhydride and 2.9 g of dimethyl 2,2'-azobis(2-methylpropionate) dissolved in 50 g of 2-butanone was added dropwise over 4 hours. After refluxing for 12 hours, the temperature was lowered to room temperature to terminate the polymerization reaction. The reaction solution was added dropwise to 1 kg of heptane, and the resulting precipitate was filtered and dried in a vacuum dryer at 40 °C for 24 hours. Through this process, an intermediate containing a repeating unit represented by the chemical formula 3-1 was obtained. As a result of analyzing the obtained intermediate by GPC, the weight-average molecular weight in standard polystyrene equivalent was 1,500 g / mol.

[0172]

[0173] Preparation of amide compounds

[0174] An amide compound containing a repeating unit represented by the following chemical formula 1-1 was prepared.

[0175] [Chemical Formula 1-1]

[0176]

[0177] 10.0 g of an intermediate containing a repeating unit represented by the chemical formula 3-1 and 69.4 g of 2-butanone were added to a 250 mL reactor. Subsequently, 59.4 g of diallylamine, corresponding to code (1-1) as the first monomer, was added to the reactor. Afterward, the temperature of the reactor was raised to 90 ℃ and refluxed for 20 hours, then lowered to room temperature to terminate the reaction. The reaction solution was neutralized with acetic acid, ethyl acetate and deionized water were added, stirred, and then separated into layers using a separatory funnel. After removing the aqueous layer, deionized water was added again, stirred, and allowed to stand to separate into layers. After removing the lower aqueous layer, the organic solvent was removed using a rotary evaporator and dissolved in 90 g of tetrahydrofuran. The solution prepared in this way was added dropwise to 1 kg of heptane, and the resulting precipitate was filtered to obtain an amide compound. The weight-average molecular weight of the obtained amide compound was 1,700 g / mol.

[0178]

[0179] Examples 1-2

[0180] Preparation of an intermediate containing a repeating unit represented by Chemical Formula 3-2

[0181] [Chemical Formula 3-2]

[0182]

[0183] 58.3 g of 2-butanone was placed in a 250 mL reactor and heated to 85 °C. A solution containing 21.5 g of maleic anhydride, 28.5 g of 2-hydroxyethyl methacrylate (corresponding to code (2-1) as the second monomer), and 3.0 g of dimethyl 2,2'-azobis(2-methylpropionate) dissolved in 58.3 g of 2-butanone was added dropwise to the reactor over 4 hours. After refluxing for 12 hours, the temperature was lowered to room temperature to terminate the polymerization reaction. The reaction solution was added dropwise to 1.2 kg of isopropyl ether to form a precipitate, which was then filtered and dried in a vacuum dryer at 40°C for 24 hours. Through this process, an intermediate containing repeating units represented by the chemical formula 3-2 was obtained. As a result of analyzing the obtained intermediate by GPC, the weight-average molecular weight in terms of standard polystyrene was 3,500 g / mol.

[0184]

[0185] Preparation of amide compounds

[0186] An amide compound comprising a first repeating unit represented by the following chemical formula 1-1 and a second repeating unit represented by the following chemical formula 2-2 was prepared.

[0187]

[0188] 10.0 g of an intermediate containing a repeating unit represented by the chemical formula 3-2 and 61.1 g of 2-butanone were added to a 250 mL reactor. Subsequently, 51.1 g of diallylamine, corresponding to code (1-1) as the first monomer, was added to the reactor. Afterward, the temperature of the reactor was raised to 90 °C and refluxed for 20 hours, then lowered to room temperature to terminate the reaction. The reaction solution was neutralized with acetic acid, ethyl acetate and deionized water were added, stirred, and then separated into layers using a separatory funnel. After removing the aqueous layer, deionized water was added again, stirred, and allowed to stand to separate into layers. After removing the lower aqueous layer, the organic solvent was removed using a rotary evaporator and dissolved in 90 g of tetrahydrofuran. The solution thus prepared was added dropwise to 1 kg of heptane, and the resulting precipitate was filtered to obtain an amide compound. The weight-average molecular weight of the obtained amide compound was 4,000 g / mol.

[0189]

[0190] Examples 1-3 to 1-7

[0191] The intermediate and amide compounds were prepared in the same manner as in Examples 1-2 above, except that the type and content of the first monomer and the second monomer used in the preparation of the intermediate and amide compounds were adjusted so that the molar ratio between the first repeating unit and the second repeating unit was as shown in Table 4 below.

[0192]

[0193] Examples 1-8

[0194] Preparation of an intermediate containing a repeating unit represented by Chemical Formula 3-1

[0195] [Chemical Formula 3-1]

[0196]

[0197] An intermediate containing a repeating unit represented by Chemical Formula 3-1 prepared in Example 1-1 above was prepared.

[0198]

[0199] Preparation of amide compounds

[0200] An amide compound containing repeating units represented by the following chemical formula 1-7 was prepared.

[0201] [Chemical Formula 1-7]

[0202]

[0203] 10 g of an intermediate containing repeating units represented by the chemical formula 3-1 and 67.0 g of 2-butanone were added to a 250 mL reactor. Then, 57.0 g of dipropagylamine corresponding to code (1-4) as the first monomer was added to the reactor.

[0204] Subsequently, the reactor temperature was raised to 90 ℃ and refluxed for 20 hours, after which the temperature was lowered to room temperature to terminate the reaction. The reaction solution was neutralized with acetic acid, followed by the addition of ethyl acetate and deionized water. After stirring, the mixture was separated into layers using a separatory funnel. After removing the aqueous layer, deionized water was added again, stirred, and allowed to stand to separate into layers. After removing the lower aqueous layer, the organic solvent was removed using a rotary evaporator and dissolved in 90 g of tetrahydrofuran. The solution prepared in this way was added dropwise to 1 kg of heptane, and the resulting precipitate was filtered to obtain an amide compound. The weight-average molecular weight of the obtained amide compound was 1,900 g / mol.

[0205]

[0206] Examples 1-9

[0207] The intermediate and amide compounds were prepared in the same manner as in Examples 1-8, except that the type and content of the first monomer and the second monomer used in the preparation of the intermediate and amide compounds were adjusted so that the molar ratio between the first repeating unit and the second repeating unit was as shown in Table 4 below.

[0208]

[0209] Examples 1-10

[0210] Preparation of an intermediate containing a repeating unit represented by Chemical Formula 3-2

[0211] [Chemical Formula 3-2]

[0212]

[0213] An intermediate containing a repeating unit represented by Chemical Formula 3-2 prepared in Example 1-2 above was prepared.

[0214]

[0215] Preparation of amide compounds

[0216] An amide compound comprising a first repeating unit represented by the following chemical formula 1-7 and a second repeating unit represented by the following chemical formula 2-2 was prepared.

[0217] [Chemical Formula 1-7]

[0218]

[0219] 10.0 g of an intermediate containing a repeating unit represented by the chemical formula 3-2 and 49.0 g of 2-butanone were added to a 250 mL reactor. Subsequently, 49 g of dipropagylamine, corresponding to code (1-4) as the first monomer, was added to the reactor. Afterward, the temperature of the reactor was raised to 90 °C and refluxed for 20 hours, then lowered to room temperature to terminate the reaction. The reaction solution was neutralized with acetic acid, ethyl acetate and deionized water were added, stirred, and then separated into layers using a separatory funnel. After removing the aqueous layer, deionized water was added again, stirred, and allowed to stand to separate into layers. After removing the lower aqueous layer, the organic solvent was removed using a rotary evaporator and dissolved in 90 g of tetrahydrofuran. The solution thus prepared was added dropwise to 1 kg of heptane, and the resulting precipitate was filtered to obtain an amide compound. The weight-average molecular weight of the obtained amide compound was 4,100 g / mol.

[0220]

[0221] Examples 1-11 to 1-15

[0222] The intermediate and amide compounds were prepared in the same manner as in Examples 1-8, except that the type and content of the first monomer and the second monomer used in the preparation of the intermediate and amide compounds were adjusted so that the molar ratio between the first repeating unit and the second repeating unit was as shown in Table 4 below.

[0223]

[0224] Comparative Example 1-1

[0225] A compound containing a repeating unit represented by the following chemical formula 2-2 and a repeating unit represented by chemical formula 2-14 was prepared.

[0226]

[0227] 58 g of 2-butanone was placed in a 250 mL reactor and heated to 85 °C. Then, a solution prepared by dissolving 23.9 g of 2-hydroxyethyl methacrylate, 26.1 g of tert-butyl methacrylate, and 2.5 g of dimethyl 2,2'-azobis(2-methylpropionate) in 58.3 g of 2-butanone was added dropwise over 4 hours. After refluxing for 12 hours, the temperature was lowered to room temperature to terminate the polymerization reaction. The reaction solution was added dropwise to 1.2 kg of heptane, and the resulting precipitate was filtered and dried in a vacuum dryer at 40 °C for 24 hours. Through this, a compound containing a repeating unit represented by Chemical Formula 2-2 and a repeating unit represented by Chemical Formula 2-14 was obtained. As a result of analyzing the obtained compound by GPC, the weight-average molecular weight in terms of standard polystyrene was 6,000 g / mol.

[0228]

[0229] Table 3 below shows the types of monomer compounds used in the preparation of the compounds of Examples 1-1 to 1-15 and Comparative Example 1-1, and Table 4 below shows the types and molar ratios of repeating units and weight-average molecular weight (Mw) among the compounds of Examples 1-1 to 1-15 and Comparative Example 1-1.

[0230] First Monomer Second Monomer Type (Compound) Type (Compound) Type (Compound) Type (Compound) Example 1-1 (1-1) --- Example 1-2 (1-1) - (2-1) - Example 1-3 (1-1) - (2-1) - Example 1-4 (1-1) - (2-1) - Example 1-5 (1-1) - (2-1) - Example 1-6 (1-2) - (2-1) - Example 1-7 (1-3) - (2-1) - Example 1-8 (1-4) ---Example 1-9(1-1)(1-4)(2-1)-Example 1-10(1-4)-(2-1)-Example 1-11(1-4)-(2-2)-Example 1-12(1-4)-(2-1)-Example 1-13(1-4)-(2-3)-Example 1-14(1-4)-(2-1)(2-2)Example 1-15(1-4)-(2-1)(2-2)Comparative Example 1-1--(2-1)(2-2)

[0231] First repeating unit Second repeating unit Molar ratio of first repeating unit to second repeating unit Mw (g / mol) Example 1-1 Chemical Formula 1-1 --1,700 Example 1-2 Chemical Formula 1-1 Chemical Formula 2-21:14,000 Example 1-3 Chemical Formula 1-1 Chemical Formula 2-21:34,500 Example 1-4 Chemical Formula 1-1 Chemical Formula 2-21:44,800 Example 1-5 Chemical Formula 1-1 Chemical Formula 2-21:96,000 Example 1-6 Chemical Formula 1-3 Chemical Formula 2-21:14,000 Example 1-7 Chemical Formula 1-5 Chemical Formula 2-21:14,200 Example 1-8 Chemical Formula 1-7 --1,900 Example 1-9 Chemical Formula 1-1, Chemical Formula 1-7 Chemical Formula 2-21:13,800 Example 1-10 Chemical Formula 1-7 Chemical Formula 2-21:14,100 Example 1-11 Chemical Formula 1-7 Chemical Formula 2-141:14,000 Example 1-12 Chemical Formula 1-7 Chemical Formula 2-21:34,700 Example 1-13 Chemical Formula 1-7 Chemical Formula 2-191:13,800 Example 1-14 Chemical Formula 1-7 Chemical Formula 2-2, Chemical Formula 2-141:13,800 Example 1-15 Chemical Formula 1-7 Chemical Formula 2-2, Chemical Formula 2-141:34,400 Comparative Example 1-1---6,000

[0232]

[0233] Preparation of a composition for forming a resist underlayer

[0234] compound

[0235] Methyl 2-hydroxyisobutyrate was prepared as a solvent. As crosslinking agents, NICKALC MX-270 (Sanwa Chemical), a melamine-based crosslinking agent, and diglycidyl ether, an epoxy-based crosslinking agent, were prepared. Triethylammonium triflate (TAG-2678) was prepared as a thermal acid generator.

[0236]

[0237] Example 2-1

[0238] A composition for forming a resist underlayer was prepared by mixing the amide-based compound prepared in Example 1-1 above with a solvent. At this time, the content of the amide-based compound was 0.5 parts by weight based on 100 parts by weight of the composition for forming a resist underlayer.

[0239]

[0240] Examples 2-2 to 2-15

[0241] A composition for forming a resist underlayer was prepared in the same manner as in Example 2-1, except that the type and content of the amide compound were controlled as shown in Table 5 below.

[0242]

[0243] Type and Content of Amide Compounds Example 2-1 Example 1-10.5 Example 2-2 Example 1-20.5 Example 2-3 Example 1-30.5 Example 2-4 Example 1-40.5 Example 2-5 Example 1-50.5 Example 2-6 Example 1-60.5 Example 2-7 Example 1-70.5 Example 2-8 Example 1-80.5 Example 2-9 Example 1-90.5 Example 2-10 Example 1-100.5 Example 2-11 Example 1-110.5 Example 2-12 Example 1-120.5 Example 2-13 Example 1-130.5 2-14 Example 1-140.5 Example 2-15 Example 1-150.5

[0244]

[0245] In Table 5 above, the content of the amide compound is the content (parts by weight) based on 100 parts by weight of the composition for forming the resist underlayer film.

[0246]

[0247] Example 2-16

[0248] An amide-based compound prepared in Examples 1-11 above was prepared. Subsequently, an amide-based compound, a melamine-based crosslinking agent, a thermal acid generating agent, and a solvent were mixed to prepare a composition for forming a resist underlayer. At this time, based on 100 parts by weight of the composition for forming a resist underlayer, the content of the amide-based compound was 0.5 parts by weight, the content of the melamine-based crosslinking agent was 0.05 parts by weight, and the content of the thermal acid generating agent was 0.005 parts by weight.

[0249]

[0250] Examples 2-17 to 2-25

[0251] A composition for forming a resist underlayer was prepared in the same manner as in Examples 2-16 above, except that the type and content of the crosslinking agent and the content of the thermal acid generating agent were adjusted as shown in Table 6 below.

[0252]

[0253] Amide-based compound crosslinking agent thermal acid generating agent Type Content Type Content Content Example 2-16 Example 1-110.5 Melamine 0.05 0.005 Example 2-17 Example 1-110.5 Melamine 0.05 0.015 Example 2-18 Example 1-110.5 Melamine 0.05 0.025 Example 2-19 Example 1-110.5 Epoxy 0.05 0.025 Example 2-20 Example 1-110.5 Melamine 0.15 0.025 Example 2-21 Example 1-110.5 Melamine 0.25 0.025 Example 2-22 Example 1-110.5 Melamine 0.05 0.25 Example 2-23 Example 1-110.5 Melamine 10.025 Example 2-24 Example 1-110.5 Melamine 0.05 0.3 Example 2-25 Example 1-110.5 Melamine 0.025

[0254]

[0255] In Table 6 above, the content of the amide compound, crosslinking agent, and thermal acid generating agent is the content (parts by weight) based on 100 parts by weight of the composition for forming the resist underlayer film.

[0256]

[0257] Comparative Example 2-1

[0258] A composition for forming a resist underlayer was prepared by mixing the compound prepared in Comparative Example 1-1 above with a solvent. At this time, the content of the compound was 0.5 parts by weight based on 100 parts by weight of the composition for forming a resist underlayer.

[0259]

[0260] Comparative Example 2-2

[0261] Preparation of isocyanurate compounds

[0262] 297.6 g of triglycidyl isocyanurate, 8.7 g of lithium bromide, and 762.8 g of acetonitrile were added to a round-bottom flask reactor and stirred for 30 minutes. After lowering the temperature of the stirred solution to 10 ℃, 456.8 g of carbon disulfide was added dropwise, and then the temperature was slowly raised to room temperature and stirred under a nitrogen stream for 24 hours to prepare a compound represented by the following chemical formula A-1.

[0263] [Chemical Formula A-1]

[0264]

[0265] Preparation of a polymer having repeating units represented by chemical formula A-2

[0266] 20 g of the compound prepared above (Chemical Formula A-1), 4.2 g of 1,2-bis(2-aminoethoxy)ethane, 3.4 g of propylamine, and 156.4 g of dimethylformamide were added to a reactor and reacted at room temperature (25 ℃) for 8 hours while stirring to prepare a polymer having repeating units represented by the following Chemical Formula A-2. (Weight-average molecular weight (Mw): approx. 5,500, Polydispersity Index (PDI): 1.5)

[0267] [Chemical Formula A-2]

[0268]

[0269] Preparation of a polymer having repeating units represented by chemical formula A-3

[0270] 10 g of the compound prepared above (Chemical Formula A-2) and 81.6 g of tetrahydrofuran (THF) were placed in a reactor and dissolved at room temperature. Then, 6.1 g of triethylamine was added dropwise while stirring continuously. After stirring at room temperature for 1 hour, the temperature was lowered to 0 ℃, 4.3 g of acetyl chloride was added dropwise, and the reaction was carried out for 30 minutes. Subsequently, the temperature was slowly raised to room temperature (25 ℃) and the reaction was continued for 12 hours. After removing the solid formed after the reaction, the reaction solution was added dropwise to diethyl ether, and the precipitate was dried to prepare a polymer having repeating units represented by the following Chemical Formula A-3. (Weight-average molecular weight (Mw): approx. 5,700, Polydispersity Index (PDI): 1.5)

[0271] [Chemical Formula A-3]

[0272]

[0273] Preparation of a composition for forming a resist underlayer

[0274] A composition for forming a resist underlayer was prepared by mixing the compound (Chemical Formula A-3) prepared above, a melamine crosslinking agent (NICKALC MX-270), a thermal acid generating agent (TAG-2678), and a solvent. At this time, based on 100 parts by weight of the composition for forming a resist underlayer, the content of the compound (Chemical Formula A-3) was 0.5 parts by weight, the content of the melamine-based crosslinking agent was 0.15 parts by weight, and the content of the thermal acid generating agent was 0.015 parts by weight.

[0275]

[0276] Experimental Example

[0277] Evaluation of optimal photoresist exposure amount and minimum diameter size

[0278] For the manufactured composition for forming a resist underlayer, the optimal photoresist exposure amount and minimum diameter size were evaluated using the following method.

[0279] A composition for forming a resist sublayer was spin-coated onto a silicon wafer, and then baked at 205°C for 60 seconds to form a resist sublayer with a thickness of approximately 50 Å. On the formed resist sublayer, one type of the company's evaluation inorganic-based photoresist (MOR, Metal Oxide Resist) was applied to a thickness of 280 Å, and then soft-baked at 100°C for 120 seconds.

[0280] Subsequently, the image was exposed using an EUV exposure machine (ASML, NXE3400) with an exposure mask having a hexagonal array hole pattern, and post-baked at 180 °C for 120 seconds. Afterward, the image was developed with n-butyl acetate to form a hexagonal array hole pattern with a diameter of 26 nm.

[0281] The pattern of the photoresist obtained through the above process was observed using a scanning electron microscope to determine the optimal exposure amount capable of forming a diameter of 26 nm. Additionally, the minimum critical dimension (nm) at which pattern collapse begins was observed in a pattern exposed to an exposure amount less than the optimal exposure amount.

[0282]

[0283] Optimal exposure dose (mJ / cm²) 2 Minimum Diameter Size (nm) Example 2-174.616.8 Example 2-282.117.5 Example 2-388.419.2 Example 2-489.019.3 Example 2-592.119.1 Example 2-683.517.5 Example 2-785.717.7 Example 2-867.515.5 Example 2-984.417.8 Example 2-1078.216.7 Example 2-1177.217.2 Example 2-1282.517.7 Example 2-1374.216.4 Example 2-1476.417.3 Example 2-1583.518.7 Example 2-1678.517.4 Example 2-1778.817.4 Example 2-1878.517.4 Example 2-1978.517.4 Example 2-2079.216.8 Example 2-2181.217.8 Example 2-2282.417.9 Example 2-2390.119.1 Example 2-2488.218.4 Example 2-2578.517.8

[0284]

[0285] Optimal exposure dose (mJ / cm²) 2 )Minimum diameter size (nm) Comparative Example 2-193.5 19.4 Example 2-295.2 19.9

[0286]

[0287] Referring to Tables 7 and 8 above, it was confirmed that the compositions for forming a resist underlayer prepared in Examples 2-1 to 2-25 of the present invention have a smaller appropriate exposure amount and minimum diameter size compared to the compositions prepared in Comparative Examples 2-1 to 2-2. A smaller minimum diameter size indicates superior adhesion to the photoresist, and suggests that mass production and yield can be improved.

[0288] Referring to the experimental data described above, it can be seen that a composition for forming a resist underlayer film comprising an amide-based compound according to one embodiment of the present invention can form a pattern of excellent quality even at a lower exposure energy.

Claims

1. An amide compound containing a repeating unit represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1 and R2 are each independently hydrogen; or a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms; or connected to each other to form a ring, R 11 to R 14 Each is independently hydrogen; a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms; or a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms; and The above substituted alkyl group, alkenyl group and alkynyl group are each independently a substituent which is a halogen element, a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, or a straight-chain or branched-chain alkoxy group having 1 to 5 carbon atoms.

2. In Paragraph 1, R1 and R2 are hydrogen in an amide compound.

3. In Paragraph 1, R 11 and R 12 At least one of them is a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms; or a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms; and R 13 and R 14 An amide compound wherein at least one of which is a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms; or a substituted or unsubstituted straight-chain or branched alkenyl group having 2 to 10 carbon atoms.

4. In Paragraph 1, An amide compound in which the alkenyl group has a carbon-carbon double bond at the terminal and the alkenyl group has a carbon-carbon triple bond at the terminal.

5. In Paragraph 1, R 11 to R 14 is an amide compound that is identical.

6. In Paragraph 1, An amide compound comprising an additional repeating unit comprising at least one of the repeating units represented by the following chemical formulas 2a to 2d: [Chemical Formula 2a] [Chemical Formula 2b] [Chemical Formula 2c] [Chemical Formula 2d] In the above chemical formula, R 21 , R 23 , R 25 and R 27 Each is independently hydrogen; or a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; and R 22 ... is a substituted or unsubstituted straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenylene group having 2 to 5 carbon atoms; a substituted or unsubstituted cycloalkylene group having 5 to 10 carbon atoms; a substituted or unsubstituted heterocycloalkylene group having 5 to 10 carbon atoms; a substituted or unsubstituted cycloalkenylene group having 5 to 10 carbon atoms; a straight-chain or branched-chain linker having 2 to 5 carbon atoms containing a C=O bond; a cyclic linker having 5 to 10 carbon atoms containing a C=O bond; a heterocyclic linker having 5 to 10 carbon atoms containing a C=O bond; or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; and R 24 ...is a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 5 carbon atoms; a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms; a substituted or unsubstituted heterocycloalkyl group having 5 to 10 carbon atoms; a substituted or unsubstituted cycloalkenyl group having 5 to 10 carbon atoms; a straight-chain or branched-chain hydrocarbon group having 2 to 5 carbon atoms containing a C=O bond; a cyclic hydrocarbon group having 5 to 10 carbon atoms containing a C=O bond; a heterocyclic hydrocarbon group having 5 to 10 carbon atoms containing a C=O bond; or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; and R 26 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and R 28 and R 29 Each is independently hydrogen; a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; or a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 5 carbon atoms; and The above-mentioned substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, heterocycloalkyl group, aryl group, alkylene group, alkenylene group, cycloalkylene group, cycloalkenylene group, heterocycloalkylene group, and arylene group each independently have a substituent that is a halogen element, a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, or a straight-chain or branched-chain alkoxy group having 1 to 5 carbon atoms.

7. In Paragraph 6, R in the above chemical formula 2a 22 is an unsubstituted straight-chain alkylene group having 1 to 5 carbon atoms, and In the above chemical formula 2b, R 24 is an unsubstituted branched-chain alkyl group having 3 to 5 carbon atoms, and In the above chemical formula 2c, R 25 is a hydrogen-based amide compound.

8. In Paragraph 6, The above-mentioned amide compound is, An amide compound having a molar ratio of the repeating unit represented by the above chemical formula 1 and the above additional repeating unit of 1:1 to 1:

9.

9. An amide compound according to paragraph 1; and A composition for forming a resist underlayer film comprising a solvent.

10. In Paragraph 9, A composition for forming a resist lower film, wherein, based on 100 parts by weight of the composition for forming a resist lower film, the content of the amide-based compound is 0.02 parts by weight or more and 3 parts by weight or less.

11. In Paragraph 9, It further contains a crosslinking agent, A composition for forming a resist lower layer, wherein, based on 100 parts by weight of the composition for forming a resist lower layer, the content of the crosslinking agent is 0.01 parts by weight or more and 5 parts by weight or less.

12. In Paragraph 9, It further includes a heat-generating agent, A composition for forming a resist lower film, wherein, based on 100 parts by weight of the composition for forming a resist lower film, the content of the thermal acid generating agent is 0.001 parts by weight or more and 1 part by weight or less.

13. In Paragraph 9, It further includes a crosslinking agent and a thermal acid generating agent, A composition for forming a resist lower film, wherein the weight ratio of the above-mentioned thermal acid generating agent to the above-mentioned crosslinking agent is 1:10 or less.

14. In Paragraph 9, It further includes a crosslinking agent and a thermal acid generating agent, A composition for forming a resist lower layer, wherein, based on 100 parts by weight of the composition for forming a resist lower layer, the total content of the crosslinking agent and the thermal acid generating agent is 0.005 parts by weight or more and 3 parts by weight or less.

15. A resist underlayer comprising a cured product of a composition for forming a resist underlayer according to claim 9.

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