Bismuth compound for photoresist, method for producing same, composition including same, and pattern forming method using same

Abstract

Provided is a bismuth compound for a photoresist, the bismuth compound being represented by chemical formula 1: <Chemical formula 1> In chemical formula 1, R1 to R5 are each independently selected from the group consisting of: hydrogen; deuterium; a C1-C20 alkyl group substituted or unsubstituted with at least one among deuterium, a halogen, and a cyano group; and a C6-C20 aryl group substituted or unsubstituted with at least one among deuterium, a halogen, and a cyano group, and at least one of R4 or R5 is a C1-C20 alkyl group substituted with at least one of a halogen or a cyano group.

Description

Bismuth compound for photoresist, method for producing same, composition including same, and method for forming pattern using same

[0001] The present invention relates to a bismuth compound for photoresist, a method for producing the same, a composition including the same, and a method for forming a pattern using the same.

[0002] As semiconductors become more highly integrated, patterns are becoming increasingly finer. To form ultrafine patterns, light in the extreme ultraviolet (EUV) region can be used in lithography. Compared to organic materials without metals, inorganic materials containing metals exhibit higher etching resistance and higher light absorbance, making them suitable for use as photoresist materials in lithography processes. To compensate for the limited light source output, photoresist materials require higher sensitivity. In other words, inorganic photoresist materials capable of forming fine patterns reliably even with low light source output are in demand.

[0003] The problem to be solved by the present invention is to provide a bismuth compound for photoresist that can be used to form a fine pattern without pattern collapse even with a low exposure dose, a method for producing the same, a composition including the same, and a method for forming a pattern using the same.

[0004] According to one aspect, a bismuth compound for a photoresist, represented by the following chemical formula 1, is provided:

[0005] <Chemical Formula 1>

[0006]

[0007] In the above chemical formula 1,

[0008] R1 to R5 are independently hydrogen; deuterium; C1-C substituted or unsubstituted with at least one of deuterium, halogen and cyano group. 20 Alkyl group; C6-C substituted or unsubstituted with at least one of deuterium, halogen, and cyano group 20 Aryl group; selected from the group consisting of,

[0009] At least one of R4 and R5 is C1-C substituted with at least one of halogen and cyano groups. 20 It is an alkyl group.

[0010] According to one embodiment, the bismuth compound for the photoresist may be negative tone.

[0011] According to one embodiment, R1 to R3 are each independently C1-C substituted or unsubstituted with at least one of deuterium, halogen and cyano group. 15 Alkyl group; C6-C substituted or unsubstituted with at least one of deuterium, halogen, and cyano group 10 Aryl group; can be selected from the group consisting of;

[0012] In one implementation example, R1 to R3 can be identical to each other.

[0013] According to one embodiment, any two of R1 to R3 may be connected to each other without forming a ring.

[0014] According to one embodiment, R4 and R5 are independently C1-C substituted with halogen. 15 It may be an alkyl group.

[0015] In one embodiment, R4 and R5 can be the same.

[0016] In one embodiment, the halogen may be -F, -Cl, -Br or -I.

[0017] According to one embodiment, the bismuth compound for the photoresist may be any one of the following compounds 1 to 3:

[0018]

[0019]

[0020] According to another aspect, a method for producing the above-described bismuth compound for a photoresist is provided, comprising the step of mixing a compound represented by the following chemical formula 2; and a compound represented by the following chemical formula 3:

[0021] <Chemical Formula 2>

[0022]

[0023] <Chemical Formula 3>

[0024]

[0025] Among the above chemical formulas 2 and 3,

[0026] R1 to R3 are independently hydrogen; deuterium; C1-C substituted or unsubstituted with at least one of deuterium, halogen and cyano group. 20 Alkyl group; C6-C substituted or unsubstituted with at least one of deuterium, halogen, and cyano group 20 Aryl group; selected from the group consisting of,

[0027] R 10 C1-C substituted with at least one of a halogen and a cyano group 20 It is an alkyl group.

[0028] According to another aspect, a composition for a photoresist is provided, comprising the bismuth compound for a photoresist described above; and an organic solvent.

[0029] According to another aspect, a method for forming a pattern is provided, comprising: forming a photoresist thin film including the bismuth compound for photoresist described above on a substrate; exposing the photoresist thin film; and developing the exposed photoresist thin film in a developer.

[0030] A thin film formed of a bismuth compound for photoresist represented by the above chemical formula 1 has excellent hardness, excellent etching resistance, excellent development resistance, and excellent absorbance, and can form a fine pattern well without pattern breakdown even with a low exposure dose.

[0031] Figure 1 is a diagram showing the spectrum by Fourier transform infrared spectroscopy (FT-IR) of each of a comparative compound and a compound according to one embodiment.

[0032] The present invention will be described in more detail below. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. Generally, the nomenclature used herein is well known and commonly used in the art.

[0033] Throughout this specification, whenever a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0034] Throughout the present specification, the term "alkyl group" includes chain-like alkyl groups and cyclic alkyl groups, and the chain-like alkyl group may be a term including linear alkyl groups and branched alkyl groups. For example, the alkyl group may include a methyl group (-CH3), an ethyl group (-CH2CH3), an n-propyl group (-CH2CH2CH3), an iso-propyl group (-CH(CH3)2), an n-butyl group (-CH2CH2CH2CH3), a tert-butyl group (-C(CH3)3), a cyclopentyl group, a cyclohexyl group, and the like.

[0035] Throughout this specification, the term "aryl group" refers to a ring having a carbocyclic aromatic system. For example, an aryl group may include a phenyl group, a naphthyl group, anthracenyl group, a phenanthrenyl group, a pyrenyl group, a triphenylenyl group, a perylenyl group, and the like.

[0036] The term "substitution" means that a hydrogen atom is replaced by a different atom, so for example, a "halogen-substituted methyl group" can be -CH2F, -CH2Cl, -CH2Br, -CH2I, -CHF2, -CHCl2, -CHBr2, -CHI2, -CF3, -CCl3, -CBr3, -CI3, -CHFCl, -CHFBr, -CHFI, -CHClBr, -CClHI, -CHBrI, etc. That is, a "halogen-substituted alkyl group" is one in which at least one randomly selected hydrogen in the alkyl group is replaced by a halogen.

[0037] According to one aspect, a bismuth compound for a photoresist represented by the following chemical formula 1 is provided:

[0038] <Chemical Formula 1>

[0039]

[0040] In the above chemical formula 1,

[0041] R1 to R5 are independently hydrogen; deuterium; C1-C substituted or unsubstituted with at least one of deuterium, halogen and cyano group. 20 Alkyl group; C6-C substituted or unsubstituted with at least one of deuterium, halogen, and cyano group 20 Aryl group; selected from the group consisting of,

[0042] At least one of R4 and R5 is C1-C substituted with at least one of halogen and cyano groups. 20 It is an alkyl group.

[0043] The compound represented by the above chemical formula 1 is used in a photoresist for forming a pattern, and is clearly different from an organometallic compound that has a use unrelated to photoresist, such as being used as a catalyst in an arbitrary reaction.

[0044] The halogen may be selected from the group consisting of F, Cl, Br, and I. The bismuth compound for photoresist represented by the above chemical formula 1 may not contain a metal other than Bi. That is, the bismuth compound for photoresist may be composed of one or more elements selected from the group consisting of Bi, C, H, D (deuterium), O, F, Cl, Br, and I. For example, a compound including a metal such as Sn is clearly different from the bismuth compound for photoresist represented by the above chemical formula 1.

[0045] According to one embodiment, the bismuth compound for photoresist may be a negative tone. That is, a thin film formed using the bismuth compound for photoresist may become insoluble in a developer upon exposure to light. For example, the solubility of the bismuth compound for photoresist in an organic solvent may decrease after being irradiated with light. That is, when light is irradiated to a first region of a thin film formed using the bismuth compound for photoresist and a second region other than the first region is not irradiated with light, the first region of the thin film may be substantially insoluble in the organic solvent, and the second region of the thin film may be soluble.

[0046] According to one embodiment, in the above chemical formula 1, R1 to R3 are each independently C1-C substituted or unsubstituted with at least one of deuterium, halogen and cyano group. 15 Alkyl group; and C6-C substituted or unsubstituted with at least one of deuterium, halogen and cyano group 10Aryl group; may be selected from the group consisting of; For example, R1 to R3 are each independently a methyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; an ethyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; a propyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; a butyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; a phenyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; a naphthyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; an anthracenyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; a phenanthrenyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; A pyrenyl group unsubstituted or substituted with at least one of a deuterium, a halogen, and a cyano group; a triphenylenyl group unsubstituted or substituted with at least one of a deuterium, a halogen, and a cyano group; or a perylenyl group unsubstituted or substituted with at least one of a deuterium, a halogen, and a cyano group. R1 to R3 may be each independently an alkenyl group and an alkynyl group.

[0047] According to one embodiment, R1 to R3 in the above chemical formula 1 may be the same as each other. For example, each of R1 to R3 may be a phenyl group substituted or unsubstituted with at least one of a deuterium, a halogen, and a cyano group.

[0048] According to one embodiment, any two of R1 to R3 may not be connected to each other to form a ring. Referring to the above chemical formula 1, R1 to R3 may be connected to each other only through Bi, and any two of R1 to R3 may not be connected to each other without going through Bi. For example, when R2 and R3 are directly connected to each other through a chemical bond (e.g., a single bond, a double bond, etc.), or are connected through an arbitrary linker (e.g., -O-, -S-, etc.) without going through Bi, a ring containing Bi as a ring-forming atom is formed, such as a ring formed of R2-R3-Bi or R2-linker-R3-Bi. The bismuth compound for a photoresist represented by the above chemical formula 1 may not include a ring containing Bi as a ring-forming atom. For example, the following compound A is clearly different from the bismuth compound for photoresist represented by the chemical formula 1 described above, since the first phenyl group and the second phenyl group bonded to Bi are connected to each other through an oxygen linker (-O-), thereby forming a ring (CCOCC-Bi) containing Bi as a ring-forming atom:

[0049] .

[0050] According to one embodiment, R4 and R5 in the above chemical formula 1 are each independently C1-C substituted with halogen. 15 It may be an alkyl group. For example, R4 and R5 may be, independently of each other, a methyl group substituted or unsubstituted with a halogen; an ethyl group substituted or unsubstituted with a halogen; a propyl group substituted or unsubstituted with a halogen; or a butyl group substituted or unsubstituted with a halogen.

[0051] R4 and R5, independently of each other, may not contain an alkenyl group or an alkynyl group. R4 and R5, independently of each other, may not contain a double bond or a triple bond.

[0052] In one embodiment, R4 and R5 can be the same. For example, each of R4 and R5 can be a methyl group substituted with a halogen, and the type and number of halogens contained in R4 and the type and number of halogens contained in R5 can be the same. Specifically, when R4 is -CH2Cl, R5 can also be -CH2Cl. When R4 is -CH2Br, R5 can also be -CH2Br.

[0053] According to one embodiment, the bismuth compound for the photoresist may be represented by the following chemical formula 1-1:

[0054] <Chemical Formula 1-1>

[0055]

[0056] In the above chemical formula 1-1,

[0057] X and Y are each halogens,

[0058] Z1 to Z3 are independently selected from the group consisting of deuterium, halogen and cyano groups,

[0059] Z1 and Z2 do not directly bond to each other, Z2 and Z3 do not directly bond to each other, Z3 and Z1 do not directly bond to each other,

[0060] e is an integer selected from 0 to 5,

[0061] n is an integer selected from 0 to 10, m is an integer selected from 0 to 10,

[0062] a is an integer selected from 0 to 2, b is an integer selected from 1 to 3, and the sum of a and b is 3,

[0063] c is an integer selected from 0 to 2, d is an integer selected from 1 to 3, and the sum of c and d is 3.

[0064] According to one embodiment, the bismuth compound for the photoresist may be any one of the following compounds 1 to 3:

[0065]

[0066] .

[0067] For example, the compound 1 may correspond to a compound in which e, n, and m are each 0 in the chemical formula 1-1, a and c are each 2, b and d are each 1, and X and Y are each Cl.

[0068] According to another aspect, a method for producing a bismuth compound for a photoresist is provided, comprising the steps of mixing a compound represented by the following chemical formula 2; and a compound represented by the following chemical formula 3:

[0069] <Chemical Formula 2>

[0070]

[0071] <Chemical Formula 3>

[0072]

[0073] Among the above chemical formulas 2 and 3,

[0074] R1 to R3 are independently hydrogen; deuterium; C1-C substituted or unsubstituted with at least one of deuterium, halogen and cyano group. 20 Alkyl group; C6-C substituted or unsubstituted with at least one of deuterium, halogen, and cyano group 20 Aryl group; selected from the group consisting of,

[0075] R 10 C1-C substituted with at least one of a halogen and a cyano group 20 It is an alkyl group.

[0076] In the above chemical formula 2, R1 to R3 may correspond to R1 to R3 in the above chemical formula 1. For example, in the above chemical formula 2, R1 to R3 may independently be C1-C substituted or unsubstituted with at least one of deuterium, halogen, and cyano group. 15Alkyl group; and C6-C substituted or unsubstituted with at least one of deuterium, halogen and cyano group 10 Aryl group; may be selected from the group consisting of; For example, R1 to R3 are each independently a methyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; an ethyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; a propyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; a butyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; a phenyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; a naphthyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; an anthracenyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; a phenanthrenyl group substituted or unsubstituted with at least one of deuterium, halogen, and cyano group; A pyrenyl group unsubstituted or substituted with at least one of a deuterium, a halogen, and a cyano group; a triphenylenyl group unsubstituted or substituted with at least one of a deuterium, a halogen, and a cyano group; or a perylenyl group unsubstituted or substituted with at least one of a deuterium, a halogen, and a cyano group. In the above formula 2, R1 to R3 may be each independently an alkenyl group and an alkynyl group. In the group formula 2, R1 to R3 may be the same as each other. For example, each of R1 to R3 may be a phenyl group. Any two of R1 to R3 in the group formula 2 may not be connected to each other to form a ring.

[0077] According to one embodiment, each of R1 to R3 in the above chemical formula 2 may be a phenyl group substituted or unsubstituted with at least one of a deuterium, a halogen, and a cyano group. When each of R1 to R3 is a phenyl group, the compound represented by the above chemical formula 2 may be synthesized by the following reaction scheme A:

[0078] <Reaction Formula A>

[0079]

[0080] R in the above chemical formula 3 10 can correspond to R4 or R5 in the chemical formula 1 described above. In the chemical formula 3, R 10 C1-C substituted or unsubstituted with at least one of deuterium, halogen and cyano group 15 It can be an alkyl group. For example, R 10 C1-C substituted or unsubstituted with silver halogen 15 It can be an alkyl group. R 10 may not contain alkenyl or alkynyl groups. R 10 may not contain double bonds or triple bonds.

[0081] The method for producing a bismuth compound for a photoresist represented by the above-described chemical formula 1 may further include a step of dissolving the compound represented by the above-described chemical formula 2 in a solution containing alcohol and / or ether. The method for producing a bismuth compound for a photoresist represented by the above-described chemical formula 1 may further include a step of adding hydrogen peroxide (H2O2) to the solution.

[0082] According to another aspect, a composition for a photoresist is provided, comprising a bismuth compound for a photoresist represented by the above-described chemical formula 1; and an organic solvent.

[0083] According to one embodiment, the organic solvent may include chloroform, chloromethane, dichloromethane, chloroethane, dichloroethane, acetone, tetrahydrofuran, toluene, chlorobenzene, dichlorobenzene, and the like.

[0084] According to one embodiment, the concentration of the bismuth compound for photoresist represented by the chemical formula 1 in the composition may be 150 mg / mL or less. For example, the concentration of the bismuth compound for photoresist may be 0.5 mg / mL to 140 mg / mL. By having properties such as appropriate viscosity within the concentration range of the bismuth compound for photoresist described above, a thin film including the composition may be easily formed through spin casting or the like. If the concentration range is exceeded, the thin film may be formed unevenly. At a concentration less than 0.5 mg / mL, a low thickness may be formed that makes it difficult to perform the role of a photoresist, and at a concentration exceeding 150 mg / mL, the composition may precipitate within the solution, making it difficult to form a uniform thin film.

[0085] According to another aspect, a method for forming a pattern using a bismuth compound for photoresist represented by the above-described chemical formula 1 is provided. The method for forming a pattern may include: forming a pattern layer on a substrate; forming a photoresist thin film including the bismuth compound for photoresist represented by the above-described chemical formula 1 on the pattern layer; exposing the photoresist thin film; developing the exposed photoresist thin film in a developer; and etching the pattern layer that does not overlap the photoresist thin film.

[0086] The substrate may be a silicon wafer. The pattern layer is a thin film on which a fine circuit pattern is formed, and may be formed substantially flat through a chemical vapor deposition method or a physical vapor deposition method. For example, the pattern layer may include silicon nitride, silicon oxide, silicon oxynitride, or the like.

[0087] The above photoresist thin film can be formed by coating a composition including a bismuth compound for photoresist represented by the above chemical formula 1 through a solution process such as spin casting. The spin casting speed can be 500 rpm to 3,000 rpm. After the solution process such as spin casting, the photoresist thin film can be formed by heat treatment at 50° C. to 180° C. for 1 minute to 10 minutes. The formed photoresist thin film can have a thickness of 10 nm to 1,000 nm.

[0088] Examples of light used in the step of exposing the above photoresist thin film include an excimer laser, extreme ultraviolet (EUV), and an electron beam (E-beam). According to one embodiment, the photoresist thin film can be patterned using an E-beam. In the development process following the exposure process, a certain level of exposure dose may be required in the exposure process in order to clearly distinguish between exposed and unexposed areas.

[0089] Examples of the developer used in the step of developing the exposed photoresist thin film in the developer include chloroform, chloromethane, dichloromethane, chloroethane, dichloroethane, acetone, tetrahydrofuran, toluene, chlorobenzene, dichlorobenzene, etc. The developing time may be 10 seconds to 30 minutes. An unexposed area of ​​the photoresist thin film may be removed by dissolving in the developer. An exposed area of ​​the photoresist thin film may not be dissolved in the developer. That is, the photoresist thin film may be a negative tone thin film. By removing a portion of the photoresist thin film, a certain pattern may be formed, and the line width of the formed pattern may be 10 nm or less. Since the above photoresist thin film includes the bismuth compound for photoresist represented by the above-described chemical formula 1 having excellent hardness, excellent etching resistance, excellent development resistance, etc., a pattern having a line width of 10 nm or less can be formed without pattern breakdown even with a relatively small exposure dose.

[0090] By removing a portion of the photoresist thin film, some areas of the pattern layer may overlap with the remaining photoresist thin film, and other areas of the pattern layer may not overlap with the remaining photoresist thin film. By etching the pattern layer that does not overlap with the photoresist thin film, a pattern identical to that of the photoresist thin film may be formed in the pattern layer. Thereafter, by removing the photoresist thin film, a patterned layer having a pattern formed thereon may be obtained.

[0091] Hereinafter, a bismuth compound for photoresist according to an implementation example will be described in more detail with examples of synthesis and evaluation.

[0092] Comparative Synthesis Example 1 (Synthesis of Comparative Compound CE1)

[0093]

[0094] Triphenylbismuth (440 mg, 1 mmol, 1 eq) was dissolved in a solution of 2-propanol and diethyl ether in a volume ratio of 7:1 in a round-bottomed flask. After stirring at room temperature, acetic acid (120.1 mg, 3 mmol, 3 eq) was added and cooled to 0°C. Hydrogen peroxide (H2O2) (1.1 mL, 10.5 mmol) was slowly added and stirred for 3 hours. After the reaction, the precipitate was filtered through a filter and washed several times with 2-propanol to obtain compound CE1 (triphenylbismuth diacetate) (275 mg, yield: 49%). About compound CE1 1 H NMR was performed and specific data is described below.

[0095] 1 H NMR (400 MHz, CDCl3) δ 8.17 to 8.14 (m, 6H), 7.64 to 7.58 (m, 6H), 7.50 to 7.46 (m, 3H), 1.82 (s, 6H).

[0096] Synthesis Example 1 (Synthesis of Compound 1)

[0097]

[0098] Compound 1 (triphenylbismuth bis(chloroacetate)) was obtained (448 mg, yield: 71%) using the same method as in Comparative Synthesis Example 1, except that chloroacetic acid (189 mg, 3 mmol, 3 eq) was used instead of acetic acid. For compound 1 1 H NMR was performed and specific data is described below.

[0099] 1 H NMR (400 MHz, CDCl3) δ 8.17 to 8.15 (m, 6H), 7.67 to 7.64 (m, 6H), 7.55 to 7.51 (m, 3H), 3.84 (s, 4H).

[0100] Synthesis Example 2 (Synthesis of Compound 2)

[0101]

[0102] Compound 2 (triphenylbismuth bis(bromoacetate)) was obtained (600 mg, yield: 84%) using the same method as in Comparative Synthesis Example 1, except that bromoacetic acid (277.9 mg, 2 mmol, 2 eq) was used instead of acetic acid. For compound 2 1 H NMR was performed and specific data is described below.

[0103] 1 H NMR (400 MHz, CDCl3) δ 8.17 to 8.15 (m, 6H), 7.67 to 7.63 (m, 6H), 7.54 to 7.50 (m, 3H), 3.66 (s, 4H).

[0104] Synthesis Example 3 (Synthesis of Compound 3)

[0105]

[0106] Compound 3 (triphenylbismuth bis(iodoacetate)) was obtained (580 mg, yield: 72%) using the same method as in Comparative Synthesis Example 1, except that iodoacetic acid (372 mg, 2 mmol, 2 eq) was used instead of acetic acid. For compound 3 1 H NMR was performed and specific data is described below.

[0107] 1 H NMR (400 MHz, CDCl3) δ 8.16 to 8.14 (m, 6H), 7.68 to 7.63 (m, 6H), 7.53 to 7.50 (m, 3H), 3.52 (s, 4H).

[0108] Based on the above comparative synthesis example 1 and synthesis examples 1 to 3, a person skilled in the art can easily recognize a method for synthesizing a bismuth compound for a photoresist according to chemical formula 1 of the present invention.

[0109] The spectra of the comparative compound CE1 and each of compounds 1 to 3 obtained by Fourier transform infrared spectroscopy (FT-IR) are shown in Figure 1.

[0110] Evaluation Example 1

[0111] A composition was prepared by dissolving compound CE1 in chloroform at a concentration of 50 mg / mL. The composition was spin-casted on a silicon wafer at 1500 rpm for 40 seconds and heat-treated at 120°C for 2 minutes to form a photoresist thin film. The thickness of the photoresist thin film measured using a scanning electron microscope (SEM) was 250 nm.

[0112] The above photoresist thin film was exposed to 30 kV Ebeam using Raith's ELPHY Plus equipment, and then developed using an organic solvent of dichloromethane for 60 seconds.

[0113] It was confirmed that the pattern of the above photoresist thin film was formed well without any collapse. The exposure dose of Raith's ELPHY Plus equipment was 0 μC / cm 2 Up to 2,000 μC / cm 2 Even though the evaluation was repeated while changing the range, the pattern of the photoresist thin film using compound CE1 was not formed well.

[0114] Evaluation Example 2

[0115] The same evaluation as in Evaluation Example 1 was performed except that compound CE1 was changed to each compound listed in Table 1 below, and the minimum exposure dose at which a good pattern was formed is summarized in Table 1 below.

[0116] No. Minimum exposure dose (μC / cm 2 )Comparative compound CE1 Pattern formation is not possible Compound 2150.1 Compound 390.3

[0117]

[0118]

[0119] From the above Table 1, the bismuth compound for photoresist belonging to the compound represented by the above-described chemical formula 1 has a conductivity of approximately 150 μC / cm 2 It can be confirmed that a good pattern can be formed even with a relatively small exposure dose below. On the other hand, the comparative compound CE1, which does not contain a halogen substituent and does not fall into the category of chemical formula 1, has an exposure dose of 0 μC / cm 2 Up to 2,000 μC / cm 2 Even with the exposure amount, a good pattern could not be formed. Therefore, it can be seen that the bismuth compound represented by the above-described chemical formula 1 is suitable for use as a photoresist compound using a relatively small amount of exposure.

Claims

1. A bismuth compound for photoresist, represented by the following chemical formula 1: <Chemical Formula 1> In the above chemical formula 1, R1 to R5 are independently hydrogen; deuterium; C1-C substituted or unsubstituted with at least one of deuterium, halogen and cyano group. 20 Alkyl group; C6-C substituted or unsubstituted with at least one of deuterium, halogen, and cyano group 20 Aryl group; selected from the group consisting of, C1-C, wherein at least one of R4 and R5 is substituted with at least one of a halogen and a cyano group. 20 It is an alkyl group.

2. In paragraph 1, The above bismuth compound for photoresist is a bismuth compound for photoresist, which is a negative tone.

3. In paragraph 1, R1 to R3 are each independently C1-C substituted or unsubstituted with at least one of deuterium, halogen and cyano group. 15 Alkyl group; C6-C substituted or unsubstituted with at least one of deuterium, halogen, and cyano group 10 A bismuth compound for a photoresist, selected from the group consisting of aryl groups.

4. In paragraph 1, R1 to R3 are identical bismuth compounds for photoresist.

5. In paragraph 1, A bismuth compound for photoresist, wherein any two of R1 to R3 are connected to each other and do not form a ring.

6. In paragraph 1, R4 and R5 are independently C1-C substituted with halogen. 15 Alkyl group, bismuth compound for photoresist.

7. In paragraph 1, R4 and R5 are identical bismuth compounds for photoresist.

8. In paragraph 1, A bismuth compound for photoresist, wherein the halogen is -F, -Cl, -Br or -I.

9. In paragraph 1, The bismuth compound for the photoresist is any one of the following compounds 1 to 3: .

10. A method for producing a bismuth compound for a photoresist according to claim 1, comprising the step of mixing a compound represented by the following chemical formula 2; and a compound represented by the following chemical formula 3: <Chemical Formula 2> <Chemical Formula 3> Among the above chemical formulas 2 and 3, R1 to R3 are independently hydrogen; deuterium; C1-C substituted or unsubstituted with at least one of deuterium, halogen and cyano group. 20 Alkyl group; C6-C substituted or unsubstituted with at least one of deuterium, halogen, and cyano group 20 Aryl group; selected from the group consisting of, R 10 C1-C substituted with at least one of a halogen and a cyano group 20 It is an alkyl group.

11. Bismuth compound for photoresist according to paragraph 1; and A composition for a photoresist, comprising an organic solvent.

12. A step of forming a photoresist thin film including a bismuth compound for photoresist according to claim 1 on a substrate; A step of exposing the above photoresist thin film; and A pattern forming method, including a step of developing the exposed photoresist thin film in a developer.

Images