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KR-102960986-B1 - METHOD FOR FORMING PATTERN USING ANTIREFLECTIVE COATING COMPOSITION INCLUDING PHOTOACID GENERATOR

KR102960986B1KR 102960986 B1KR102960986 B1KR 102960986B1KR-102960986-B1

Abstract

An anti-reflective coating composition comprising a polymer, a photo-generating agent having a crosslinking group, a compound capable of crosslinking the polymer and the photo-generating agent, a thermal acid generating agent, and an organic solvent.

Inventors

  • 이정준
  • 안재윤
  • 심재환
  • 임재봉
  • 이매드 아퀘드
  • 김명열

Assignees

  • 듀폰 일렉트로닉 머티어리얼즈 인터내셔널, 엘엘씨
  • 듀폰스페셜티머터리얼스코리아 유한회사

Dates

Publication Date
20260512
Application Date
20231013
Priority Date
20190722

Claims (10)

  1. As an anti-reflective coating composition for negative tone development, A polymer comprising a cyanurate structural unit derived from a compound represented by the following chemical formula 5; A photocatalyst containing a crosslinking group; A compound capable of crosslinking the above polymer and the above photogenerator; thermal acid generator; and Includes an organic solvent; and The above photogenerator is an onium salt having the chemical formula G + A - , wherein G + has the following chemical formula 1 and A - is a non-polymerizable organic anion, Anti-reflective coating composition: [Chemical Formula 1] In the above chemical formula 1, Y is S, and Each R1 is independently a substituted or unsubstituted C1-30 alkyl group, a substituted or unsubstituted polycyclic or monocyclic C3-30 cycloalkyl group, or a substituted or unsubstituted polycyclic or monocyclic C6-30 aryl group, and one of the R1s is optionally attached to one adjacent R1 by a single bond or a crosslinking group, and However, at least one R1 is a polycyclic or monocyclic C6-30 aryl group having a hydroxyl group attached via a substituted or unsubstituted -OC1 - C30 alkylene group, and z is 3 and; [Chemical Formula 5] In the above chemical formula 5, R2 , R3 , R4 , and each X are independently hydrogen, a substituted or unsubstituted C1-30 alkyl group, a substituted or unsubstituted C2-30 alkenyl group, a substituted or unsubstituted C2-30 alkynyl group, a substituted or unsubstituted C2-30 alkanoyl group, a substituted or unsubstituted C1 - C30 alkoxy group, a substituted or unsubstituted C1 - C30 alkylthio group, a substituted or unsubstituted C1 - C30 alkylsulfinyl group, a substituted or unsubstituted C1 - C30 alkylsulfonyl group, -COOH, a substituted or unsubstituted C2 - C30 alkoxycarbonyl group, a substituted or unsubstituted C7 - C30 alkylaryl group, a substituted or unsubstituted C6 - C30 aryl group, a substituted or unsubstituted C3 - C30 heterodicyclic group, or a substituted or unsubstituted C3 - C30 It is a heteroaromatic group, and Each m1 is independently an integer from 1 to 10; Here, the term "substitution" refers to substitution by one or more substituents selected from alkyl groups, alkoxy groups, carboxylic acid groups, cycloalkyl groups, alkenyl groups, aryl groups, aryloxy groups, and combinations thereof.
  2. An anti-reflective coating composition according to claim 1, wherein G + is represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, Each R a is independently hydrogen, halogen, cyano group, nitro group, amino group, substituted or unsubstituted C1-30 alkyl group, substituted or unsubstituted C2-30 alkenyl group, substituted or unsubstituted C2-30 alkynyl group, substituted or unsubstituted C1 - C30 alkoxy group, substituted or unsubstituted C3 - C30 cycloalkyl group, substituted or unsubstituted C3 - C30 cycloalkenyl group, substituted or unsubstituted C6 - C30 aryl group, substituted or unsubstituted C6 - C30 aryloxy group, substituted or unsubstituted C6 - C30 arylthio group, substituted or unsubstituted C7 - C30 arylalkyl group, and Each Rb is a substituted or unsubstituted C1-30 alkyl group, a substituted or unsubstituted polycyclic or monocyclic C3-30 cycloalkyl group, a substituted or unsubstituted polycyclic or monocyclic C6-30 aryl group, and the Rb groups are optionally attached to each other by single bonds or crosslinking groups, and Each L is a single bond, a substituted or unsubstituted C1 - C30 alkylene group, a substituted or unsubstituted C2 - C30 alkenylene group, a substituted or unsubstituted C2 - C30 alkynylene group, a substituted or unsubstituted C3 - C30 cycloalkenylene group, a substituted or unsubstituted C3 - C30 cycloalkynylene group, a substituted or unsubstituted C6 - C30 arylene group, or a substituted or unsubstituted C6 - C30 heteroarylene group, and at least one non-adjacent -CH2- group in each group is optionally replaced with -SO2- , -C(=O)-, -O-, -S-, -SO-, -C(=O)O-, -OC(=O)-, -C(=O)NR-, or -NRC(=O)-, and R is hydrogen or a C1 - C10 alkyl group, or a combination thereof; n1 is an integer from 1 to 5, and n2 is an integer from 0 to 4, and However, the sum of n1 and n2 does not exceed 5, and Here, the term "substitution" refers to substitution by one or more substituents selected from alkyl groups, alkoxy groups, carboxylic acid groups, cycloalkyl groups, alkenyl groups, aryl groups, aryloxy groups, and combinations thereof.
  3. An anti-reflective coating composition according to claim 1, wherein G + is represented by the following chemical formula 3: [Chemical Formula 3] In the above chemical formula 3, Each R a is hydrogen, halogen, cyano group, nitro group, amino group, substituted or unsubstituted C1-30 alkyl group, substituted or unsubstituted C2-30 alkenyl group, substituted or unsubstituted C2-30 alkynyl group, substituted or unsubstituted C1 - C30 alkoxy group, substituted or unsubstituted C3 - C30 cycloalkyl group, substituted or unsubstituted C3 - C30 cycloalkenyl group, substituted or unsubstituted C6 - C30 aryl group, substituted or unsubstituted C6 - C30 aryloxy group, substituted or unsubstituted C6 - C30 arylthio group, substituted or unsubstituted C7 - C30 arylalkyl group, and the R a groups are optionally attached to each other by single bonds or crosslinking groups, and R b is independently a substituted or unsubstituted C1-30 alkyl group, a substituted or unsubstituted polycyclic or monocyclic C3-30 cycloalkyl group, a substituted or unsubstituted polycyclic or monocyclic C6-30 aryl group, and Each L is a single bond, a substituted or unsubstituted C1 - C30 alkylene group, a substituted or unsubstituted C2 - C30 alkenylene group, a substituted or unsubstituted C2 - C30 alkynylene group, a substituted or unsubstituted C3 - C30 cycloalkenylene group, a substituted or unsubstituted C3 - C30 cycloalkynylene group, a substituted or unsubstituted C6 - C30 arylene group, or a substituted or unsubstituted C6 - C30 heteroarylene group, and at least one non-adjacent -CH2- group in each group is optionally replaced with -SO2- , -C(=O)-, -O-, -S-, -SO-, -C(=O)O-, -OC(=O)-, -C(=O)NR-, or -NRC(=O)-, and R is hydrogen or a C1 - C10 alkyl group, or a combination thereof; Each n1 is an integer from 1 to 5, and Each n2 is an integer from 0 to 4, and However, the sum of n1 and n2 respectively does not exceed 5, and Here, the term "substitution" refers to substitution by one or more substituents selected from alkyl groups, alkoxy groups, carboxylic acid groups, cycloalkyl groups, alkenyl groups, aryl groups, aryloxy groups, and combinations thereof.
  4. An anti-reflective coating composition according to claim 1, wherein G + is represented by the following chemical formula 4: [Chemical Formula 4] In the above chemical formula 4, Each R a is hydrogen, halogen, cyano group, nitro group, amino group, substituted or unsubstituted C1-30 alkyl group, substituted or unsubstituted C2-30 alkenyl group, substituted or unsubstituted C2-30 alkynyl group, substituted or unsubstituted C1 -C30 alkoxy group, substituted or unsubstituted C3 - C30 cycloalkyl group, substituted or unsubstituted C3 - C30 cycloalkenyl group, substituted or unsubstituted C6 - C30 aryl group, substituted or unsubstituted C6 - C30 aryloxy group, substituted or unsubstituted C6 - C30 arylthio group, substituted or unsubstituted C7 - C30 arylalkyl group, and Each L is a single bond, a substituted or unsubstituted C1 - C30 alkylene group, a substituted or unsubstituted C2 - C30 alkenylene group, a substituted or unsubstituted C2 - C30 alkynylene group, a substituted or unsubstituted C3 - C30 cycloalkenylene group, a substituted or unsubstituted C3 - C30 cycloalkynylene group, a substituted or unsubstituted C6 - C30 arylene group, or a substituted or unsubstituted C6 - C30 heteroarylene group, and at least one non-adjacent -CH2- group in each group is optionally replaced with -SO2- , -C(=O)-, -O-, -S-, -SO-, -C(=O)O-, -OC(=O)-, -C(=O)NR-, or -NRC(=O)-, and R is hydrogen or a C1 - C10 alkyl group, or a combination thereof; Each n1 is an integer from 1 to 5, and Each n2 is an integer from 0 to 4, and However, the sum of n1 and n2 respectively does not exceed 5, and Here, the term "substitution" refers to substitution by one or more substituents selected from alkyl groups, alkoxy groups, carboxylic acid groups, cycloalkyl groups, alkenyl groups, aryl groups, aryloxy groups, and combinations thereof.
  5. In claim 1, an anti-reflective coating composition in which a light-generating agent is selected from the following: .
  6. An anti-reflective coating composition according to claim 1, wherein the polymer further comprises a structural unit derived from a compound represented by the following chemical formula 6: [Chemical Formula 6] In the above chemical formula 6, Each X' is independently hydrogen, a substituted or unsubstituted C1-30 alkyl group, a substituted or unsubstituted C2-30 alkenyl group, a substituted or unsubstituted C2-30 alkynyl group, a substituted or unsubstituted C2-30 alkanoyl group, a substituted or unsubstituted C1 - C30 alkoxy group, a substituted or unsubstituted C1 - C30 alkylthio group, a substituted or unsubstituted C1 - C30 alkylsulfinyl group, a substituted or unsubstituted C1 - C30 alkylsulfonyl group, -COOH, a substituted or unsubstituted C2 - C30 alkoxycarbonyl group, a substituted or unsubstituted C7 - C30 alkylaryl group, a substituted or unsubstituted C6 - C30 aryl group, a substituted or unsubstituted C3 - C30 heterodicyclic group, or a substituted or unsubstituted C3 - C30 heteroaromatic group, and Each m2 is independently an integer from 1 to 10, and Here, the term "substitution" refers to substitution by one or more substituents selected from alkyl groups, alkoxy groups, carboxylic acid groups, cycloalkyl groups, alkenyl groups, aryl groups, aryloxy groups, and combinations thereof.
  7. An anti-reflective coating composition according to claim 1, wherein a compound capable of crosslinking a photocatalytic agent and a polymer is represented by the following chemical formula 7: [Chemical Formula 7] In the above chemical formula 7, Each X", each R5 , R6 , and R7 is independently hydrogen, a halogen, a hydroxyl group, a substituted or unsubstituted C1-30 alkyl group, a substituted or unsubstituted C1 - C30 alkoxy group, a substituted or unsubstituted C3 - C30 cycloalkyl group, a substituted or unsubstituted C7 - C30 arylalkyl group, and Each m3 is independently an integer from 2 to 10, and Here, the term "substitution" refers to substitution by one or more substituents selected from alkyl groups, alkoxy groups, carboxylic acid groups, cycloalkyl groups, alkenyl groups, aryl groups, aryloxy groups, and combinations thereof.
  8. (a) a substrate; and (b) a layer of an anti-reflective coating composition of any one of claims 1 to 7 disposed on the substrate; comprising a coated substrate.
  9. A method for forming a pattern, comprising: (a) applying a layer of an anti-reflective coating composition according to any one of claims 1 to 7 onto a substrate; (b) curing the applied anti-reflective coating composition to form an anti-reflective layer; (c) forming a photoresist layer on the anti-reflective layer; and (d) patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the anti-reflective layer.
  10. In claim 9, the step of patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the anti-reflection layer comprises: (d)(1) a step of exposing the photoresist layer and the anti-reflection layer to active radiation, and (d)(2) a step of developing the exposed photoresist layer and the anti-reflection layer with an organic solvent developer.

Description

Method for forming a pattern using an antireflective coating composition including a photoacid generator The present invention generally relates to an anti-reflective coating composition for use in photoresists. Specifically, the present invention provides an anti-reflective composition for improving the pattern breakdown margin in negative tone development. A photoresist is a photosensitive composition used to transfer an image onto a substrate. After a coating layer of photoresist is formed on a substrate, it is exposed to chemical radiation through a photomask. The photomask has regions that do not allow chemical radiation to pass through and regions that do. When the photoresist coating layer is exposed to chemical radiation, photo-induced chemical modification occurs in the photoresist coating layer. As a result, the pattern of the photomask is transferred to the photoresist coating layer. Subsequently, the photoresist coating layer is developed to form a patterned image that can be selectively processed on the substrate. Generally, chemically amplified negative tone photoresists comprise a resin having acid-unstable groups and a photogenerator (PAG). When such photoresists are exposed to chemical radiation, the photogenerator forms an acid, and this formed acid separates the acid-unstable groups from the resin during the baking process after exposure. The removal of the acid-unstable groups creates a difference in solubility characteristics with respect to an aqueous alkali developer or a hydrophobic organic solvent developer between the exposed and unexposed areas. The exposed areas of the resist dissolve in the aqueous alkali developer and do not dissolve in the hydrophobic organic solvent developer. In the manufacturing process of semiconductor devices, the positive tone process uses an aqueous alkali developer and leaves only the unexposed areas of the photoresist on the substrate, whereas the negative tone process uses a hydrophobic organic solvent developer and leaves only the exposed areas of the photoresist on the substrate. Generally, photoresists are used to print micro- or nano-scale patterns on semiconductor substrates such as Si or GaAs, and these patterns are converted into a complex matrix of electronic conduction pathways (preferably micron or submicron structures) to perform circuit functions. To achieve this purpose, the details of photoresist processing and processing conditions are critical. While several operations used to process photoresists operate interdependently, one of the most critical operations for obtaining high-resolution photoresist images is the radiation exposure step. In such exposure operations, radiation reflected from the photoresist coating layer degrades the resolution of patterned features. For example, if exposure radiation is reflected at the interface between the substrate and the photoresist, spatial variations occur in the intensity of the radiation irradiated onto the photoresist coating layer, and the radiation is scattered toward areas of the photoresist that were not intentionally exposed. Consequently, radiation reflection during photoresist exposure results in a lack of pattern uniformity during development, such as uneven linewidths in printed line-space features. Furthermore, because there are differences in the amount of scattered or reflected radiation between regions, the resolution can become sensitive to the substrate topography. To solve the above problems related to reflection, an additional light-absorbing layer (i.e., an anti-reflective coating layer) is coated between the surface of the substrate and the photoresist coating layer (see U.S. Patent Nos. 5,939,236, 5,886,102, 5,851,738, 5,851,730, etc.). However, in the case of such conventional anti-reflective coating layers, pattern collapse often occurs during the negative tone development (NTD) of the photolithography process when the pattern has a small critical dimension (40 nm or less). This phenomenon has resulted in low yields due to significant difficulties in securing process margins, as well as a degradation of product quality. Recently, the pattern breakdown margin (PCM) in the NTD process has become a critical issue for achieving higher yields in ArF immersion lithography as the pattern scale decreases. The PCM in NTD depends heavily on the characteristics of the bottom anti-reflective coating (BARC) film. In particular, acidic BARC surfaces can significantly increase pattern breakdown by further amplifying the deprotection reaction of the photoresist. As an acidic catalyst in BARC, photo-generators can be one of the excellent acidity control units of BARC formulations, as they can improve pattern breakdown through acid generated only in the exposed area. However, a major drawback of this method is the reduction in PAG concentration on the BARC surface due to dissolution by the process solvent during photoresist spin coating or resist reduction (RRC) processes. There remains