Photoresist composition and thin film manufactured by using same

Abstract

The present invention provides a photoresist composition having excellent sensitivity while having excellent storage stability and coatability, and a thin film manufactured by using same.

Description

Composition for photoresist and thin film prepared using the same

[0001] The present invention relates to a composition for photoresist and a thin film manufactured using the same.

[0002]

[0003] Photoresist is a photoreactive material whose chemical properties change upon exposure to light, and it is a key material used in the photolithography process to form precise circuit patterns on semiconductor wafers. With the increasing integration of semiconductors, the realization of ultra-fine patterns is required, and organic-based chemically amplified resist (CAR), a representative photoresist, has been used as a standard material up to the ArF generation.

[0004] However, with the introduction of Extreme Ultraviolet (EUV) lithography and process miniaturization, problems have arisen, such as the very poor photon absorption efficiency of carbon and oxygen—the main components of chemically amplified resists—for photons in the EUV wavelength range, degradation of uniformity and roughness characteristics due to acid diffusion, and pattern collapse caused by the low mechanical strength of organic-based photoresists. Accordingly, there has been a need to develop new inorganic photoresists that possess high absorption for photons in the EUV wavelength range and excellent mechanical strength and etch resistance to satisfy RLS (Resolution, LER / LWR, Sensitivity) characteristics.

[0005] Recently, inorganic photoresists utilizing coating methods based on liquid and gas phase chemical reactions have been recognized globally as the only alternative technology for forming ultrafine patterns; however, the development of core technologies related to these materials, processes, and equipment remains insufficient. Therefore, the development of inorganic photoresist materials and processes is urgently required to secure a leading position and technological competitiveness in next-generation extreme ultraviolet (EUV) patterning technology.

[0006]

[0007] The present invention provides a composition for a photoresist having excellent storage stability and coating properties and excellent sensitivity, and a thin film manufactured using the same.

[0008] 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.

[0009]

[0010] One embodiment of the present invention provides a composition for a photoresist comprising at least one of: a first compound comprising two or more units represented by the following chemical formula 1; a second compound comprising two or more units represented by the following chemical formula 2; and a third compound comprising two or more units represented by the following chemical formula 3:

[0011] [Chemical Formula 1]

[0012]

[0013] [Chemical Formula 2]

[0014]

[0015] [Chemical Formula 3]

[0016]

[0017] In the above chemical formula,

[0018] The above R1, R2, R3, R4, R5, R6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 Each is independently a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms; a substituted or unsubstituted cycloalkyl group having 4 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; or an alkyl group-containing ester group having 1 to 5 carbon atoms, and

[0019] The above R8 is a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted straight-chain or branched alkenylene group having 2 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 4 to 10 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms; and

[0020] The above R 12 ...is a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted straight-chain or branched alkenylene group having 2 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 4 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 10 carbon atoms; or a tin-ester bond-containing linker; and

[0021] In the case of the above-mentioned substituted alkyl group, substituted alkenyl group, substituted cycloalkyl group, substituted aryl group, substituted alkylene group, substituted alkenylene group, substituted cycloalkylene group, and substituted arylene group, the substituent is a hydroxyl group; a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; or a substituent containing a tin-ester bond; and

[0022] The above X is a halogen element.

[0023] According to one embodiment of the present invention, the composition for the photoresist may include at least the second compound.

[0024] According to one embodiment of the present invention, the R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 At least one of them may be a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 10 carbon atoms.

[0025] According to one embodiment of the present invention, the R1, R2, R3, R4, R5, R 6,R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 At least one of them may be an unsubstituted branched alkyl group having 3 to 5 carbon atoms.

[0026] According to one embodiment of the present invention, the R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 may be a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 5 carbon atoms.

[0027] According to one embodiment of the present invention, the R8 and R 12 Each may be an independently substituted or unsubstituted straight-chain or branched alkylene group having 1 to 6 carbon atoms; a substituted or unsubstituted cycloalkylene group having 4 to 10 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms.

[0028] According to one embodiment of the present invention, X may be I.

[0029] According to one embodiment of the present invention, the unit represented by Formula 1 comprises at least one of the units represented by Formulas 1-1 to 1-6 below, the unit represented by Formula 2 comprises at least one of the units represented by Formulas 2-1 to 2-4 below, and the unit represented by Formula 3 may comprise at least one of the units represented by Formulas 3-1 to 3-3 below.

[0030] [Chemical Formula 1-1]

[0031]

[0032] [Chemical Formula 1-2]

[0033]

[0034] [Chemical Formula 1-3]

[0035]

[0036] [Chemical Formula 1-4]

[0037]

[0038] [Chemical Formula 1-5]

[0039]

[0040] [Chemical Formula 1-6]

[0041]

[0042] [Chemical Formula 2-1]

[0043]

[0044] [Chemical Formula 2-2]

[0045]

[0046] [Chemical Formula 2-3]

[0047]

[0048] [Chemical Formula 2-4]

[0049]

[0050] [Chemical Formula 3-1]

[0051]

[0052] [Chemical Formula 3-2]

[0053]

[0054] [Chemical Formula 3-3]

[0055] .

[0056] According to one embodiment of the present invention, based on 100 parts by weight of the composition for the photoresist, the content of any one or more of the first to third compounds may be 0.1 parts by weight or more and 30 parts by weight or less.

[0057] According to one embodiment of the present invention, the composition for the photoresist comprises a first compound, and the weight ratio of the first compound to the second compound may be 1:0.1 to 1:10.

[0058] According to one embodiment of the present invention, the first compound, the second compound, or the third compound may have two or more units coordinately bonded to each other.

[0059] According to one embodiment of the present invention, the composition may be fired at a temperature of 200°C or lower after exposure.

[0060] According to one embodiment of the present invention, the composition has a sensitivity of 40 mJ / cm² 2 It may be less than.

[0061] One embodiment of the present invention provides a thin film manufactured using the above-described composition for photoresist.

[0062] According to one embodiment of the present invention, the thin film may include a tin-ester bond.

[0063]

[0064] A composition for photoresist according to one embodiment of the present invention can easily produce a thin film with excellent sensitivity while achieving excellent storage stability and coating properties.

[0065] A thin film according to one embodiment of the present invention may have excellent sensitivity while achieving excellent storage stability and coating properties by including the photoresist composition.

[0066] 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.

[0067]

[0068] FIG. 1 is of the compound prepared in Preparation Examples 1-4 of the present invention. 1 This is the H NMR spectrum.

[0069] FIG. 2 is a schematic diagram of a monomer included in the compound prepared in Preparation Examples 1-4 of the present invention.

[0070]

[0071] 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.

[0072] 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.

[0073] Throughout the entire specification, the unit "parts by weight" may refer to the ratio of weight between each component.

[0074] 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.

[0075] Throughout this specification, “1 Å” refers to “10 -10 It can mean "m and 0.1 nm".

[0076] In this specification, the term “a and / or b” is used to mean “a or b” and “a and b”.

[0077] In this specification, the alkyl group may be of the straight chain or branched chain type. The number of carbon atoms in the alkyl group is 1 or more and 10 or less. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, i-butyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group, n-pentyl group, i-pentyl group, neopentyl group, t-pentyl group, 1-methylpentyl group, 3-methylpentyl group, 2-ethylpentyl group, 4-methyl-2-pentyl group, n-hexyl group, 1-methylhexyl group, 2-ethylhexyl group, 2-butylhexyl group, n-heptyl group, 1-methylheptyl group, 2,2-dimethylheptyl group, 2-ethylheptyl group, 2-butylheptyl group, n-octyl group, t-octyl group, 2-ethyloctyl group, 2-butyloctyl group, 2-hexyloctyl group. Examples include 3,7-dimethyloctyl groups, n-nonyl groups, n-decyl groups, adamantyl groups, etc., but are not limited to these.

[0078] In this specification, an alkenyl group refers to a hydrocarbon group comprising one or more carbon-carbon double bonds at the middle or end of an alkyl group having 2 or more carbon atoms. The alkenyl group may be straight-chain or branched-chain. The number of carbon atoms in the alkenyl group is not particularly limited, but may be, for example, 2 or more and 10 or less. Examples of alkenyl groups include, but are not limited to, vinyl groups, 1-butenyl groups, 1-pentenyl groups, 1,3-butadienyl groups, styrenyl groups, styrylvinyl groups, etc.

[0079] In this specification, a cycloalkyl group may refer to a cyclic alkyl group. The number of carbon atoms in a cycloalkyl group may be 4 or more and 10 or less. Examples of cycloalkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl groups.

[0080] In this specification, an aryl group refers to any functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. The number of ring-forming carbon atoms in the aryl group may be 6 or more and 10 or less. Examples of aryl groups include, but are not limited to, phenyl groups and naphthyl groups.

[0081] In this specification, the alkyl-containing ester group may be an alkyl ester group. The alkyl ester group refers to a carboxylic acid ester group (-COOR, where R is an alkyl group), and the alkyl group may be a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms. Examples of alkyl ester groups include, but are not limited to, methyl ester groups (-COOCH3), ethyl ester groups (-COOCH2CH3), propyl ester groups, isopropyl ester groups, butyl ester groups, t-butyl ester groups, pentyl ester groups, etc.

[0082] In this specification, an alkylene group, an alkenylene group, a cycloalkylene group, or an arylene group refers to a functional group, and the number of carbon atoms and basic structural characteristics thereof shall be in accordance with the definitions of the corresponding alkyl group, alkenyl group, cycloalkyl group, or aryl group.

[0083]

[0084] The present specification will be described in more detail below.

[0085] One embodiment of the present invention provides a composition for a photoresist comprising at least one of: a first compound comprising two or more units represented by the following chemical formula 1; a second compound comprising two or more units represented by the following chemical formula 2; and a third compound comprising two or more units represented by the following chemical formula 3:

[0086] [Chemical Formula 1]

[0087]

[0088] [Chemical Formula 2]

[0089]

[0090] [Chemical Formula 3]

[0091]

[0092] In the above chemical formula, R1, R2, R3, R4, R5, R6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 Each is independently a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms; a substituted or unsubstituted cycloalkyl group having 4 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; or an alkyl group-containing ester group having 1 to 5 carbon atoms, wherein R8 is a substituted or unsubstituted straight-chain or branched-chain alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenylene group having 2 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 4 to 10 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms; and R 12 is a substituted or unsubstituted straight-chain or branched-chain alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenylene group having 2 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 4 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 10 carbon atoms; or a tin-ester bond-containing linker; and in the case of the substituted alkyl group, substituted alkenyl group, substituted cycloalkyl group, substituted aryl group, substituted alkylene group, substituted alkenylene group, substituted cycloalkylene group and substituted arylene group, the substituent is a hydroxyl group; a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; an ester group having 1 to 5 carbon atoms; or a tin-ester bond-containing substituent; and X is a halogen element.

[0093] A composition for a photoresist according to one embodiment of the present invention can easily produce a thin film with excellent sensitivity while achieving excellent storage stability and coating properties. Specifically, the composition for a photoresist comprises at least one of a first compound comprising two or more units represented by Formula 1; a second compound comprising two or more units represented by Formula 2; and a third compound comprising two or more units represented by Formula 3, thereby enabling excellent long-term storage stability while simultaneously improving sensitivity and coating properties.

[0094] According to one embodiment of the present invention, the photoresist composition comprising a first compound containing two or more units represented by Chemical Formula 1 may have excellent storage stability and sensitivity. Additionally, the photoresist composition comprising a second compound containing two or more units represented by Chemical Formula 2 may have excellent storage stability and sensitivity. Furthermore, the photoresist composition comprising a third compound containing two or more units represented by Chemical Formula 3 may have excellent storage stability and sensitivity.

[0095] In the above chemical formula 2, X is a halogen element. Specifically, X may be F, Cl, Br, or I. A photoresist composition in which the type of X satisfies the above description may have excellent storage stability and sensitivity.

[0096] R1 to R7, R9 to R of the above chemical formula 11 and R 13 to R 15In this, the number of carbon atoms contained in the main chain of the alkyl group may be 1 to 10, 1 to 8, or 1 to 6. Additionally, the number of carbon atoms contained in the main chain of the alkenyl group may be 2 to 10, 2 to 8, 2 to 6, or 2 to 4. In this case, the double bond present in the alkenyl group may be located at the terminal. Additionally, the number of carbon atoms contained in the main chain of the cycloalkyl group may be 4 to 10, 4 to 8, 4 to 6, or 6 to 10. Additionally, the number of carbon atoms contained in the main chain of the aryl group may be 6 to 10 or 6 to 8. Additionally, the number of carbon atoms contained in the alkyl group-containing ester group may be 1 to 4, 3 to 5, or 4 to 5. The oxygen of the alkyl group-containing ester group may be directly bonded and / or coordinately bonded to tin.

[0097] R8 and R of the above chemical formula 12 In the above, the number of carbon atoms contained in the main chain of the alkylene group may be 1 to 20, 1 to 16, 1 to 12, 1 to 10, 1 to 8, or 1 to 6. Additionally, the number of carbon atoms contained in the main chain of the alkenylene group may be 2 to 20, 2 to 16, 2 to 12, 2 to 10, 2 to 8, or 2 to 6. Additionally, the number of carbon atoms contained in the main chain of the cycloalkylene group may be 4 to 10, 4 to 8, 4 to 6, or 6 to 10. Additionally, the number of carbon atoms contained in the main chain of the arylene group may be 6 to 10 or 6 to 8. Additionally, the tin-ester bond-containing linker may be represented by the following chemical formula 11.

[0098] [Chemical Formula 11]

[0099]

[0100] In the above chemical formula 11, R 21 and R 22Each may independently be a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms; a substituted or unsubstituted cycloalkyl group having 4 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; or an alkyl group-containing ester group having 1 to 5 carbon atoms, and n may be an integer from 1 to 10. The oxygen of the alkyl group-containing ester group may be directly bonded and / or coordinately bonded to tin.

[0101] R of the above chemical formula 11 21 and R 22 In this, the number of carbon atoms contained in the main chain of the alkyl group may be 1 to 10, 1 to 8, or 1 to 6. Additionally, the number of carbon atoms contained in the alkenyl group may be 2 to 10, 2 to 8, 2 to 6, or 2 to 4. In this case, the double bond present in the alkenyl group may be located at the terminal. Additionally, the number of carbon atoms contained in the cycloalkyl group may be 4 to 10, 4 to 8, 4 to 6, or 6 to 10. Additionally, the number of carbon atoms contained in the aryl group may be 6 to 10 or 6 to 8. Additionally, the number of carbon atoms contained in the alkyl group-containing ester group having 1 to 5 carbon atoms may be 1 to 4, 3 to 5, or 4 to 5. Additionally, n may be an integer from 1 to 8, an integer from 1 to 6, an integer from 1 to 4, an integer from 1 to 2, or 1. The oxygen of the above alkyl group-containing ester group may be directly bonded and / or coordinately bonded to tin.

[0102] A first compound comprising two or more units represented by Chemical Formula 1, wherein the types of R1 to R4 satisfy the aforementioned; a second compound comprising two or more units represented by Chemical Formula 2, wherein the types of R5 to R8 satisfy the aforementioned; and R9 to R 14The photoresist composition comprising at least one of a third compound comprising two or more units represented by the chemical formula 3, which satisfies the aforementioned type, may have excellent storage stability and sensitivity.

[0103] According to one embodiment of the present invention, the composition for the photoresist may include at least the second compound. As described above, excellent sensitivity can be achieved by the composition for the photoresist including at least the second compound.

[0104] According to one embodiment of the present invention, the R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 At least one of them may be a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 10 carbon atoms. Specifically, R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 At least one of the groups may be a substituted or unsubstituted straight-chain or branched-chain alkyl group containing a main chain having 1 to 8 carbon atoms or 1 to 6 carbon atoms. The above R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 If at least one of them is of the aforementioned type, the photoresist composition can achieve improved sensitivity.

[0105] According to one embodiment of the present invention, the R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R13 , R 14 and R 15 At least one of them may be an unsubstituted branched-chain alkyl group having 3 to 5 carbon atoms. Specifically, R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 At least one of the groups may be an unsubstituted branched-chain alkyl group having 4 to 5 carbon atoms. The above R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 If at least one of them is of the aforementioned type, the photoresist composition can achieve improved sensitivity.

[0106] According to one embodiment of the present invention, the R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 may be a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 5 carbon atoms. Specifically, R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 ... may be a substituted or unsubstituted straight-chain or branched-chain alkyl group containing a main chain having 1 to 4 carbon atoms. The above R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15In the case of the aforementioned type, the photoresist composition can achieve improved sensitivity.

[0107] According to one embodiment of the present invention, the R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 At least one of them may be an alkyl group-containing ester group having 1 to 5 carbon atoms. The oxygen of the alkyl group-containing ester group may be directly bonded and / or coordinately bonded to tin. Specifically, R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 At least one of the groups may be an unsubstituted branched-chain alkyl group having 1 to 4, 3 to 5, or 4 to 5 carbon atoms. The above R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 If at least one of them is of the aforementioned type, the photoresist composition can achieve improved sensitivity.

[0108] According to one embodiment of the present invention, the R8 and R 12 Each may be an independently substituted or unsubstituted straight-chain or branched alkylene group having 1 to 6 carbon atoms; a substituted or unsubstituted cycloalkylene group having 4 to 10 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms. R8 and R 12 In the case of the aforementioned type, the photoresist composition can achieve improved sensitivity.

[0109] According to one embodiment of the present invention, X may be I. When X is of the aforementioned type, the photoresist composition can achieve improved sensitivity compared to the case where X is F.

[0110] According to one embodiment of the present invention, the unit represented by Formula 1 comprises at least one of the units represented by Formulas 1-1 to 1-6 below, the unit represented by Formula 2 comprises at least one of the units represented by Formulas 2-1 to 2-4 below, and the unit represented by Formula 3 may comprise at least one of the units represented by Formulas 3-1 to 3-3 below:

[0111] [Chemical Formula 1-1]

[0112]

[0113] [Chemical Formula 1-2]

[0114]

[0115] [Chemical Formula 1-3]

[0116]

[0117] [Chemical Formula 1-4]

[0118]

[0119] [Chemical Formula 1-5]

[0120]

[0121] [Chemical Formula 1-6]

[0122]

[0123] [Chemical Formula 2-1]

[0124]

[0125] [Chemical Formula 2-2]

[0126]

[0127] [Chemical Formula 2-3]

[0128]

[0129] [Chemical Formula 2-4]

[0130]

[0131] [Chemical Formula 3-1]

[0132]

[0133] [Chemical Formula 3-2]

[0134]

[0135] [Chemical Formula 3-3]

[0136] .

[0137] .

[0138] Compared to the unit represented by Chemical Formula 1-1 to Chemical Formula 1-6, as the types of R1 to R4 are specified, the photoresist composition comprising a compound containing two or more units represented by Chemical Formula 1-1 to Chemical Formula 1-6 may have improved sensitivity and storage stability. More specifically, a compound containing units represented by Chemical Formula 1-2 to Chemical Formula 1-6 may have improved sensitivity and storage stability compared to a compound containing a unit represented by Chemical Formula 1-1.

[0139] Compared to the unit represented by Chemical Formula 2-1 to Chemical Formula 2-4, as the types of R5 to R8 are specified, the photoresist composition comprising a compound containing two or more units represented by Chemical Formula 2-1 to Chemical Formula 2-4 can further improve sensitivity and storage stability.

[0140] The monomers represented by Chemical Formulas 3-1 to 3-3 above, with respect to the monomer represented by Chemical Formula 3 above, are R9 to R 15As the type is specified, the photoresist composition comprising a compound containing two or more units represented by Chemical Formulas 3-1 to 3-3 may have further improved sensitivity and storage stability.

[0141] According to one embodiment of the present invention, based on 100 parts by weight of the composition for the photoresist, the content of any one or more of the first to third compounds may be 0.1 parts by weight or more and 30 parts by weight or less. Specifically, based on 100 parts by weight of the composition for the photoresist, the content of any one or more of the first to third compounds may be 0.2 parts by weight or more and 20 parts by weight or less, 0.5 parts by weight or more and 10 parts by weight or less, 0.1 parts by weight or more and 10 parts by weight or less, 0.1 parts by weight or more and 5 parts by weight or less, 0.2 parts by weight or more and 15 parts by weight or less, 0.5 parts by weight or more and 30 parts by weight or less, 0.5 parts by weight or more and 20 parts by weight or less, 1 part by weight or more and 20 parts by weight or less, or 1 part by weight or more and 5 parts by weight or less. When the content of any one or more of the first to third compounds is within the aforementioned range, the sensitivity of the composition for the photoresist may be improved.

[0142] According to one embodiment of the present invention, the composition for a photoresist comprises a first compound and a second compound, and the weight ratio of the first compound to the second compound may be 1:0.1 to 1:10. Specifically, the weight ratio of the first compound to the second compound may be 1:0.2 to 1:8, 1:0.4 to 1:6, 1:0.6 to 1:5, 1:0.8 to 1:4, 1:1 to 1:2, 1:0.2 to 1:6, 1:0.4 to 1:4, 1:0.6 to 1:2, 1:0.1 to 1:2, 1:0.8 to 1:10, or 1:1 to 1:5. By adjusting the weight ratio of the first compound to the second compound to the aforementioned range, a composition for a photoresist with excellent sensitivity can be easily realized.

[0143] According to one embodiment of the present invention, the composition for a photoresist comprises a first compound and a third compound, and the weight ratio of the first compound to the third compound may be 1:0.1 to 1:10. Specifically, the weight ratio of the first compound to the third compound may be 1:0.2 to 1:8, 1:0.4 to 1:6, 1:0.6 to 1:5, 1:0.8 to 1:4, 1:1 to 1:2, 1:0.2 to 1:6, 1:0.4 to 1:4, 1:0.6 to 1:2, 1:0.1 to 1:2, 1:0.8 to 1:10, or 1:1 to 1:5. By adjusting the weight ratio of the first compound to the third compound to the aforementioned range, a composition for a photoresist with excellent sensitivity can be easily realized.

[0144] According to one embodiment of the present invention, the composition for a photoresist comprises a second compound and a third compound, and the weight ratio of the second compound to the third compound may be 1:0.1 to 1:10. Specifically, the weight ratio of the second compound to the third compound may be 1:0.2 to 1:8, 1:0.4 to 1:6, 1:0.6 to 1:5, 1:0.8 to 1:4, 1:1 to 1:2, 1:0.2 to 1:6, 1:0.4 to 1:4, 1:0.6 to 1:2, 1:0.1 to 1:2, 1:0.8 to 1:10, or 1:1 to 1:5. By adjusting the weight ratio of the second compound to the third compound to the aforementioned range, a composition for a photoresist with excellent sensitivity can be easily realized.

[0145] According to one embodiment of the present invention, the first compound, the second compound, or the third compound may each have two or more units coordinately bonded to each other. Specifically, the first compound may include two or more units represented by Formula 1 and may coordinately bond to each other. Additionally, the second compound may include two or more units represented by Formula 2 and may coordinately bond to each other. Furthermore, the third compound may include two or more units represented by Formula 3 and may coordinately bond to each other. As described above, by the first compound, the second compound, or the third compound having two or more units coordinately bonded to each other, a composition for a photoresist with excellent sensitivity, coating properties, and storage stability can be easily realized.

[0146] According to one embodiment of the present invention, the first compound, the second compound, or the third compound may each be prepared by reacting a first reactant and a second reactant. The first reactant may include at least one of Me3Sn(NMe2), Me2i-PrSn(NMe2), Me2t-BuSn(NMe2), Me2t-BuSn(NMe2), Me2t-BuSn(NMe2), and Me2PhSn(NMe2). Additionally, the second reactant may include at least one of propionic acid, acetic acid, caproic acid, fluoroacetic acid, iodoacetic acid, 3-iodopropionic acid, 4-iodobenzoic acid, 1,4-cyclohexane dicarboxylic acid, succinic acid, and suberic acid. By using the first and second reactants of the aforementioned types, a composition for a photoresist with excellent sensitivity, coating properties, and storage stability can be easily realized.

[0147] Specifically, the first reactant added to prepare the first compound may include at least one of Me3Sn (NMe2), Me2i-PrSn (NMe2), Me2t-BuSn (NMe2), Me2t-BuSn (NMe2), Me2t-BuSn (NMe2), and Me2PhSn (NMe2). Additionally, the second reactant added to prepare the first compound may include at least one of propionic acid, acetic acid, and caproic acid. By using the first and second reactants of the aforementioned types, a composition for a photoresist with excellent sensitivity, coating properties, and storage stability can be easily realized.

[0148] Specifically, the first reactant added to prepare the second compound may include Me2t-BuSn (NMe2). Additionally, the second reactant added to prepare the second compound may include at least one of fluoroacetic acid, iodoacetic acid, 3-iodopropionic acid, and 4-iodobenzoic acid. By using the first and second reactants of the aforementioned types, a composition for a photoresist with excellent sensitivity, coating properties, and storage stability can be easily realized.

[0149] Specifically, the first reactant added to prepare the third compound may include Me2t-BuSn (NMe2). Additionally, the second reactant added to prepare the third compound may include at least one of fluoro 1,4-cyclohexane dicarboxylic acid, succinic acid, and suberic acid. By using the first and second reactants of the types described above, a composition for a photoresist with excellent sensitivity, coating properties, and storage stability can be easily realized.

[0150] According to one embodiment of the present invention, the equivalent ratio of the first reactant and the second reactant may be 1:0.1 to 1:10. Specifically, the equivalent ratio of the first reactant and the second reactant may be 1:0.2 to 1:8, 1:0.3 to 1:6, 1:0.4 to 1:5, 1:0.5 to 1:2, 1:0.1 to 1:8, 1:0.2 to 1:6, 1:0.3 to 1:4, 1:0.4 to 1:2, 1:0.1 to 1:2, 1:0.2 to 1:10, 1:0.3 to 1:8, 1:0.4 to 1:6, or 1:0.5 to 1:4. When the equivalent ratio of the first reactant and the second reactant is within the aforementioned range, a first compound, a second compound, or a third compound can be easily prepared to easily realize a composition for photoresist with excellent sensitivity, coating properties, and storage stability.

[0151] According to one embodiment of the present invention, the composition may be sintered at a temperature of 200°C or lower after exposure. Specifically, the composition may be sintered at a temperature of 70°C or higher and 200°C or 100°C or higher and 200°C or lower after exposure. By controlling the sintering temperature of the composition to the aforementioned range, a thin film with a pattern formed thereon, which has excellent storage stability and sensitivity, can be easily realized.

[0152] According to one embodiment of the present invention, the composition has a sensitivity of 40 mJ / cm² 2 It may be less than or equal to. Specifically, the sensitivity of the above composition is 0 mJ / cm² 2 40 mJ / cm² or higher 2 Below, 1 mJ / cm² 2 Above 38 mJ / cm² 2 Below, 2 mJ / cm² 2 35 mJ / cm² or higher 2 Below, 3 mJ / cm² 2 32 mJ / cm² or higher 2 Below, 4 mJ / cm² 2 30 mJ / cm² or higher 2 Below, 1 mJ / cm² 2 35 mJ / cm² or higher 2 Below, 2 mJ / cm² 2 32 mJ / cm² or higher 2 Below, 3 mJ / cm² 2 30 mJ / cm² or higher 2 Less than or equal to 4 mJ / cm² 2 40 mJ / cm² or higher 2 It may be less than or equal to the above. When the sensitivity of the above composition is within the aforementioned range, the improved sensitivity of EUV and the resulting pattern quality may be excellent.

[0153] According to one embodiment of the present invention, the composition may have a sensitivity improvement rate of 5% or more. In this case, the sensitivity improvement rate is based on a composition for a photoresist comprising a compound 1-1 containing two or more units represented by the following chemical formula 1-1, and the content of the compound 1-1 may be 2.5 parts by weight based on 100 parts by weight of the composition for a photoresist.

[0154] [Chemical Formula 1-1]

[0155]

[0156] Specifically, the sensitivity improvement rate of the above composition may be 0% or more and 100% or less, 1% or more and 95% or less, 3% or more and 90% or less, 5% or more and 85% or less, 1% or more and 90% or less, 3% or more and 85% or less, 5% or more and 90% or less, 1% or more and 85% or less, or 3% or more and 95% or less. When the sensitivity of the above composition is within the aforementioned range, the improved sensitivity of the EUV and the resulting pattern quality may be excellent.

[0157]

[0158] One embodiment of the present invention provides a thin film manufactured using the above-described composition for photoresist.

[0159] A thin film according to one embodiment of the present invention may have excellent sensitivity while achieving excellent storage stability and coating properties by including the photoresist composition.

[0160] According to one embodiment of the present invention, the thin film may include a tin-ester bond. In this case, the oxygen of the ester in the tin-ester bond may be directly bonded and / or coordinately bonded with tin. By including the tin-ester bond, the thin film may have excellent storage stability and sensitivity.

[0161] According to one embodiment of the present invention, the thin film may comprise a composition for a photoresist comprising a tin-ester bond. Specifically, the tin-ester bond may be included in at least one of a first compound, a second compound, and a third compound included in the composition for the photoresist. More specifically, the tin-ester bond may be included in a monomer represented by Formula 1 included in the first compound, a monomer represented by Formula 2 included in the second compound, or a monomer represented by Formula 3 included in the third compound. Additionally, in the tin-ester bond, the oxygen of the ester may be directly bonded and / or coordinately bonded with tin. By including the composition for a photoresist comprising a tin-ester bond in the thin film, excellent storage stability and sensitivity may be achieved.

[0162] According to one embodiment of the present invention, the thickness of the thin film may be 200 Å or more and 500 Å or less. Specifically, it may be 220 Å or more and 480 Å or less, 250 Å or more and 450 Å or less, 280 Å or more and 420 Å or less, 200 Å or more and 480 Å or less, 220 Å or more and 450 Å or less, 250 Å or more and 420 Å or less, 280 Å or more and 500 Å or less, or 200 Å or more and 420 Å or less. By satisfying the aforementioned ranges for the thickness of the thin film, a pattern can be stably formed. According to one embodiment of the present invention, the thickness of the thin film may be 20 nm or more and 50 nm or less. Specifically, it may be 22 nm or more and 48 nm or less, 25 nm or more and 45 nm or less, 28 nm or more and 42 nm or less, 20 nm or more and 48 nm or less, 22 nm or more and 45 nm or less, 25 nm or more and 42 nm or less, 28 nm or more and 50 nm or less, or 20 nm or more and 42 nm or less. By satisfying the aforementioned ranges for the thickness of the thin film, a pattern can be stably formed.

[0163] According to one embodiment of the present invention, the sensitivity of the thin film is 40 mJ / cm² 2 It may be less than or equal to. Specifically, the sensitivity of the thin film is 0 mJ / cm² 2 40 mJ / cm² or higher 2 Below, 1 mJ / cm² 2 Above 38 mJ / cm² 2 Below, 2 mJ / cm² 2 35 mJ / cm² or higher 2 Below, 3 mJ / cm² 2 32 mJ / cm² or higher 2 Below, 4 mJ / cm² 2 30 mJ / cm² or higher 2 Below, 1 mJ / cm² 2 35 mJ / cm² or higher 2 Below, 2 mJ / cm² 2 32 mJ / cm² or higher 2 Below, 3 mJ / cm² 2 30 mJ / cm² or higher 2 Less than or equal to 4 mJ / cm² 2 40 mJ / cm² or higher 2 It may be less than that. When the sensitivity of the thin film is within the aforementioned range, the improved sensitivity of EUV and the resulting pattern quality may be excellent.

[0164]

[0165] 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.

[0166]

[0167] Preparation of compounds

[0168] Preparation Example 1-1

[0169] 100 ml of Me3Sn(NMe2) (Sigma Aldrich) and anhydrous toluene (Sigma Aldrich) were added to a branched round-bottom flask as the first reactant, and propionic acid (Sigma Aldrich) was dissolved in anhydrous toluene (Sigma Aldrich) and added as the second reactant. At this time, the equivalent ratio of the first reactant to the second reactant was 1:1. After the addition was completed, the reaction was terminated by stirring at 25°C for 18 hours.

[0170] Afterwards, the solvent was removed by reducing the pressure of the reaction product solution, and the remaining solid product was washed three times with pentane to obtain a white solid (yield 82%).

[0171]

[0172] Preparation Examples 1-2 to 3-3

[0173] As shown in Table 1 below, a compound was prepared in the same manner as in Preparation Example 1-1, except that the type of the first reactant, the type of the second reactant, and the equivalent ratio of the first and second reactants were adjusted.

[0174]

[0175] Preparation Examples A and B

[0176] As shown in Table 1 below, a compound was prepared in the same manner as in Preparation Example 1-1, except that the type of the first reactant, the type of the second reactant, and the equivalent ratio of the first and second reactants were adjusted.

[0177]

[0178] Reactor 1 Reactor 2 Equivalent ratio of Reactor 1 and Reactor 2 Yield (%) Preparation Example 1 - 1 Me3Sn(NMe2)propionic acid 1:182 Preparation Example 1 - 2 Me2i-PrSn(NMe2)propionic acid 1:182 Preparation Example 1 - 3 Me2t-BuSn(NMe2)acetic acid 1:179 Preparation Example 1 - 4 Me2t-BuSn(NMe2)propionic acid 1:181 Preparation Example 1 - 5 Me2t-BuSn(NMe2)caproic acid 1:181 Preparation Example 1 - 6 Me2PhSn(NMe2)propionic acid 1:182 Preparation Example 2 - 1 Me2t-BuSn(NMe2)fluoroacetic acid 1:185 Preparation Example 2 - 2 Me2t-BuSn(NMe2)iodine Acetic acid 1:184 Preparation Example 2 -3Me2t-BuSn(NMe2)3-iodopropionic acid 1:180 Preparation Example 2 -4Me2t-BuSn(NMe2)4-iodobenzoic acid 1:185 Preparation Example 3 -1Me2t-BuSn(NMe2)1,4-cyclohexane dicarboxylic acid 2:181 Preparation Example 3 -2Me2t-BuSn(NMe2)succinic acid 2:180 Preparation Example 3 -3Me2t-BuSn(NMe2)suberic acid 2:175 Preparation Example AMe2t-BuSnCl lithium dimethylamide 1:172 Preparation Example BMe2t-BuSnCl sodium methoxide 1:174

[0179]

[0180] The structures of the compounds of Preparation Examples 1-1 to 3-3, Preparation Example A, and Preparation Example B above are 1 It was confirmed by H NMR and is shown in Table 2 below.

[0181]

[0182] NMR Spectroscopic Analysis 1H-NMR (CDCl3) Preparation Example 1-1 δ 0.428 (s, 9H), δ 1.108 (t, 3H), δ 2.332 (q, 2H) Preparation Example 1-2 δ 0.439 (s, 6H), δ 1.110 (t, 3H), δ 1.222 (s, 9H), δ 2.330 (q, 2H) Preparation Example 1-3 δ 0.428 (s, 6H), δ 0.828 (d, 6H), δ 1.108 (t, 3H), δ 1.728 (m, 1H), δ 2.332 (q, 2H) Preparation Example 1-4 δ 0.419 (s, 6H), δ 0.904 (t, 3H), δ 1.226 (s, 9H), δ 1.294 (m, 4H), δ 1.521 (m, 2H), δ 2.318 (t, 2H) Preparation Example 1-5 δ 0.424 (s, 6H), δ 1.221 (s, 9H), δ 2.281 (s, 3H) Preparation Example 1-6 δ 0.429 (s, 6H), δ 1.114 (t, 3H), δ 2.331 (q, 2H), δ 7.442 (m, 5H) Preparation Example 2-1 δ 0.492 (s, 6H), δ 1.249 (s, 9H), δ 3.711 (s, 2H) Preparation Example 2-2 δ 0.471 (s, 6H), Preparation Example 2-3: δ 1.218 (s, 9H), δ 5.018 (d, 2H) Preparation Example 2-4: δ 0.549 (s, 6H), δ 1.279 (s, 9H), δ 7.761 (s, 4H) Preparation Example 3-1: δ 0.427 (s, 12H), δ 1.212 (s, 18H), δ 1.665~2.5 (m, 10H) Preparation Example 3-2: δ 0.428 (s, 12H), δ 1.213 (s, 18H), δ 2.595(s, 4H) Preparation Example 3-3δ 0.432(s, 12H), δ 1.219(s, 18H), δ 1.341(m, 4H), δ 1.619(m, 4H), δ 2.305(m, 4H) Preparation Example Aδ 0.081(s, 6H), δ 1.109(s, 9H), δ 2.791(s, 6H) Preparation Example Bδ 0.083(s, 6H), δ 1.114(s, 9H), δ 3.391(s, 3H).

[0183]

[0184] FIG. 1 is of the compound prepared in Preparation Examples 1-4 of the present invention. 1 This is the H NMR spectrum.

[0185] FIG. 2 is a schematic diagram of the monomers included in the compounds prepared in Preparation Examples 1-4 of the present invention. Specifically, FIG. 2 schematically shows the molecular structure of the monomers included in the compounds prepared in Preparation Examples 1-4 with reference to Table 2 and FIG. 1. With reference to FIG. 2, it can be confirmed that in the monomers included in the compounds prepared in Preparation Examples 1-4, R1 and R3 in Chemical Formula 1 are methyl groups, R2 is a tert-butyl group, and R4 is an ethyl group.

[0186]

[0187] Referring to Table 2 and Figures 1 to 7 above, the monomers included in the compounds prepared in each preparation example are shown in Tables 3 to 6 below.

[0188] Structural Chemical Formula 1-1 (Preparation Example 1-1) Chemical formula 1-2 (Preparation example 1-2) Chemical formula 1-3 (Preparation example 1-3) Chemical formula 1-4 (Preparation example 1-4) Chemical formula 1-5 (Preparation example 1-5) Chemical formula 1-6 (Preparation example 1-6)

[0189]

[0190] Structural Chemical Formula 2-1 (Preparation Example 2-1) Chemical formula 2-2 (Preparation example 2-2) Chemical formula 2-3 (Preparation example 2-3) Chemical formula 2-4 (Preparation Example 2-4)

[0191]

[0192] Structural Chemical Formula 3-1 (Preparation Example 3-1) Chemical formula 3-2 (Preparation Example 3-2) Chemical formula 3-3 (Preparation Example 3-3)

[0193]

[0194] Structural chemical formula A (Preparation example A) Chemical formula B (Preparation example B)

[0195]

[0196] Reference Example 1

[0197] A composition for a photoresist was prepared by dissolving the compound prepared in Preparation Example 1-1 in 4-methyl-2-pentanol (Manufacturer: Sigma Aldrich), mixing the mixture, and then filtering it. At this time, the content of the compound in 1-1 was 2.5 parts by weight based on 100 parts by weight of the composition.

[0198]

[0199] Examples 1 to 14

[0200] As shown in Table 7 below, a photoresist composition was prepared in the same manner as Reference Example 1, except that the type and content of the compound included in the photoresist composition were adjusted.

[0201]

[0202] Compound Content (Parts by Weight) Reference Example 1 Preparation Example 1-12.5 Example 1 Preparation Example 1-22.5 Example 2 Preparation Example 1-32.5 Example 3 Preparation Example 1-42.5 Example 4 Preparation Example 1-52.5 Example 5 Preparation Example 1-62.5 Example 6 Preparation Example 2-12.5 Example 7 Preparation Example 2-21 Example 8 Preparation Example 2-22.5 Example 9 Preparation Example 2-25 Example 10 Preparation Example 2-32.5 Example 11 Preparation Example 2-42.5 Example 12 Preparation Example 3-12.5 Example 13 Preparation Example 3-22.5 Example 14 Preparation Example 3-32.5

[0203]

[0204] In Table 7 above, the content (parts by weight) of each compound prepared in Preparation Examples 1-1 to 3-3 is based on 100 parts by weight of the composition for photoresist.

[0205]

[0206] Examples 15 and 16

[0207] As shown in Table 8 below, Example 15 prepared a photoresist composition by mixing 2.5 parts by weight of the compound prepared in Preparation Example 1-4 and 2.5 parts by weight of the compound prepared in Preparation Example 2-2, and Example 16 prepared a photoresist composition by mixing 2.5 parts by weight of the compound prepared in Preparation Example 1-4 and 2.0 parts by weight of the compound prepared in Preparation Example 2-2.

[0208]

[0209] Compound Content (parts by weight) Example 15 Preparation Example 1-4 Preparation Example 2-22.52.5 Example 16 Preparation Example 1-4 Preparation Example 2-22.52.0

[0210] In Table 8 above, the content (parts by weight) of the compounds prepared in Preparation Examples 1-4 and Preparation Example 2-2 is based on 100 parts by weight of the composition for photoresist.

[0211]

[0212] Comparative Example 1 and Comparative Example 2

[0213] Comparative examples of compositions containing the above compounds are shown in Table 9 below.

[0214]

[0215] Compound Content (Parts by Weight) Comparative Example 1 Preparation Example A 2.5 Comparative Example 2 Preparation Example B 2.5

[0216] In Table 9 above, the content (parts by weight) of the compound prepared in Preparation Example A and the compound prepared in Preparation Example B is based on 100 parts by weight of the composition for photoresist.

[0217]

[0218] Experimental Example

[0219] 1. Evaluation of coating properties and sensitivity

[0220] A photoresist composition prepared in Reference Example 1, Examples 1 to 16, Comparative Example 1, and Comparative Example 2 was spin-coated onto the pre-treated substrate at 1,750 rpm for 30 seconds, and baked at 100 ℃ for 120 seconds to form a thin film.

[0221] After exposing the formed thin film to ASML NXE:3400 EUV radiation, it was calcined at 150°C for 120 seconds.

[0222] A negative tone image was formed by immersing the sintered thin film in a 2-heptanone developer for 1 minute and then washing it.

[0223] Afterwards, the residual resist thickness was measured using an ellipsometer, and the sensitivity for each type of resist was shown in Table 10 below.

[0224]

[0225] The degree to which the above coating film was formed was visually observed and evaluated in two stages, and the results are shown in Table 10 below.

[0226] O: Formation of a coating film

[0227] X: Coating film not formed

[0228]

[0229] 2. Storage Stability

[0230] The photoresist compositions of Reference Example 1, Examples 1 to 16, Comparative Example 1, and Comparative Example 2 were left for a specific period under conditions of 25°C (room temperature), and the degree of precipitation and / or gelation progressed was evaluated in 4 stages after visual observation, and the results are shown in Table 10 below.

[0231] ◎: No precipitation / gelation occurs up to 6 months

[0232] ○: No precipitation / gelation occurs up to 3 months

[0233] △: No precipitation / gelation occurs up to 1 month

[0234] X: No precipitation / gelation occurs up to 1 week

[0235]

[0236] Thickness (Å) Coating Sensitivity (mJ / cm²) 2 ) Storage Stability Reference Example 1281O30◎Example 1294O29◎Example 2294O27◎Example 3285O27◎Example 4271O27◎Example 5274O28◎Example 6288O26◎Example 7292O7◎Example 8322O<5◎Example 9389O<5◎Example 10273O9◎Example 11281O9◎Example 12291O26◎Example 13289O28◎Example 14288O27◎Example 15324O<5◎Example 16394O<5◎Comparative Example 1 Cannot form XXXComparative Example 2 Cannot form XXX

[0237]

[0238] Based on the sensitivity value of Reference Example 1 in Table 10 above as 100%, the sensitivity values ​​of Examples 1 to 16, Comparative Example 1, and Comparative Example 2 were calculated as sensitivity improvement rates (%) and are shown in Table 11 below.

[0239]

[0240] Sensitivity Improvement Rate (%) Reference Example 10 Example 13.3 Example 210.0 Example 310.0 Example 410.0 Example 56.7 Example 613.3 Example 776.7 Example 8≥83.3 Example 9≥83.3 Example 1070.0 Example 1170.0 Example 1213.3 Example 136.7 Example 1410.0 Example 15≥83.3 Example 16≥83.3 Comparison Example 1X Comparison Example 2X

[0241] Referring to Tables 10 and 11 above, it was confirmed that the photoresist compositions prepared in Examples 1 to 16 of the present invention exhibited excellent physical properties through evaluation values ​​of thickness, coating properties, sensitivity, and storage stability. In particular, when compared to the photoresist composition prepared in Reference Example 1, it was confirmed that the photoresist compositions prepared in Examples 1 to 16 had excellent sensitivity, with a sensitivity improvement rate of 3% or more. Specifically, it was confirmed that the photoresist compositions prepared in Examples 2 to 16 had a sensitivity improvement rate of 5% or more when compared to the photoresist composition prepared in Reference Example 1.

[0242] In addition, when compared to Examples 1 to 16, it was confirmed that Comparative Examples 1 and 2 decompose in air and are unstable, so they failed to form a coating layer.

[0243] Referring to the experimental data described above, it can be seen that a thin film manufactured using a photoresist composition according to one embodiment of the present invention achieves excellent storage stability and sensitivity, while simultaneously achieving improved coating properties.

Claims

1. A composition for a photoresist comprising at least one of: a first compound comprising two or more units represented by the following chemical formula 1; a second compound comprising two or more units represented by the following chemical formula 2; and a third compound comprising two or more units represented by the following chemical formula 3: A composition for a photoresist comprising one is provided: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the above chemical formula, The above R1, R2, R3, R4, R5, R6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 Each is independently a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms; a substituted or unsubstituted straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms; a substituted or unsubstituted cycloalkyl group having 4 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; or an alkyl group-containing ester group having 1 to 5 carbon atoms, and The above R8 is a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted straight-chain or branched alkenylene group having 2 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 4 to 10 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms; and The above R 12 is a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted straight-chain or branched alkenylene group having 2 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 4 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 10 carbon atoms; or a tin-ester bond-containing linker; and In the case of the above-mentioned substituted alkyl group, substituted alkenyl group, substituted cycloalkyl group, substituted aryl group, substituted alkylene group, substituted alkenylene group, substituted cycloalkylene group, and substituted arylene group, the substituent is a hydroxyl group; a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; or a substituent containing a tin-ester bond; and The above X is a halogen element.

2. In Paragraph 1, The above-mentioned composition for photoresist is, A composition for photoresist comprising at least the above-mentioned second compound.

3. In Paragraph 1, The above R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 A composition for a photoresist in which at least one of the groups is a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms.

4. In Paragraph 1, The above R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 A composition for a photoresist in which at least one of the groups is an unsubstituted branched alkyl group having 3 to 5 carbon atoms.

5. In Paragraph 1, The above R1, R2, R3, R4, R5, R 6, R7, R9, R 10 , R 11 , R 13 , R 14 and R 15 A composition for a photoresist that is a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms.

6. In Paragraph 1, The above R8 and R 12 A composition for a photoresist comprising: a straight-chain or branched-chain alkylene group having 1 to 6 carbon atoms, each independently substituted or unsubstituted; a cycloalkylene group having 4 to 10 carbon atoms, substituted or unsubstituted; or an arylene group having 6 to 10 carbon atoms, substituted or unsubstituted.

7. In Paragraph 1, The above X is a composition for photoresist in which I.

8. In Paragraph 1, The monomer represented by the above chemical formula 1 comprises at least one of the monomers represented by the following chemical formulas 1-1 to 1-6, and The monomer represented by the above chemical formula 2 comprises at least one of the monomers represented by the following chemical formulas 2-1 to 2-4, and A composition for a photoresist comprising at least one of the monomers represented by the following chemical formulas 3-1 to 3-3, wherein the monomer represented by the above chemical formula 3 comprises: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] [Chemical Formula 1-6] [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] [Chemical Formula 2-4] [Chemical Formula 3-1] [Chemical Formula 3-2] [Chemical Formula 3-3] .

9. In Paragraph 1, A photoresist composition having a content of at least one of the first to third compounds of 0.1 parts by weight or more and 30 parts by weight or less, based on 100 parts by weight of the photoresist composition.

10. In Paragraph 2, The above-mentioned composition for photoresist comprises a first compound, and A composition for a photoresist in which the weight ratio of the first compound to the second compound is 1:0.1 to 1:

10.

11. In Paragraph 1, A composition for a photoresist in which the first compound, the second compound, or the third compound is a combination of two or more monomers coordinately bonded to each other.

12. In Paragraph 1, The above composition is a photoresist composition that is fired at a temperature of 200°C or lower after exposure.

13. In Paragraph 1, The above composition has a sensitivity of 40 mJ / cm² 2 A composition for photoresist that is as follows.

14. A thin film manufactured using the photoresist composition of claim 1.

15. In Paragraph 14, The above thin film is a thin film containing tin-ester bonds.

Images