TWI519512B - Photoacid compound,photoacid generator and preparation method thereof,and resist composition comprising photoacid generator - Google Patents
Photoacid compound,photoacid generator and preparation method thereof,and resist composition comprising photoacid generator Download PDFInfo
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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Description
本發明是有關於一種新的光酸發生劑以及包含該光酸發生劑的抗蝕劑組成物,其在抗蝕膜的形成過程中調節從曝光區域到非曝光區域的酸擴散,從而能夠減少非曝光表面和曝光表面上的線邊緣粗糙度。 The present invention relates to a novel photoacid generator and a resist composition comprising the photoacid generator, which regulates acid diffusion from an exposed region to a non-exposed region during formation of a resist film, thereby being capable of reducing Line edge roughness on non-exposed and exposed surfaces.
應用於包括光微影製程的半導體精細加工中的化學增幅型陽性抗蝕劑組成物含有光酸發生劑(photoacid generator),該光酸發生劑包含通過光照來生成酸的化合物。 The chemically amplified positive resist composition applied to semiconductor fine processing including photolithography processes contains a photoacid generator containing a compound which generates an acid by light irradiation.
作為所述光酸發生劑,主要使用鎓鹽,其陽離子部分被分解(degradation)成自由基的形態並以其他形態的分子存在,陰離子部分在生成酸並照射後對晶圓進行烘焙時,使酸在抗蝕膜上擴散。在此過程中,由於例如吸收光的能力、光的吸收而生成的酸的發生效率、陰離子生成的酸的擴散能力、陰離子的酸的強度等原因,光酸發生劑對抗蝕劑的解析度和線邊緣粗糙度等產生直接 的影像。 As the photoacid generator, a sulfonium salt is mainly used, and a cation portion thereof is degraded into a radical form and exists as a molecule of another form, and when an anion portion is baked after the acid is formed and irradiated, the wafer is baked. The acid diffuses on the resist film. In this process, the resolution of the photoacid generator to the resist is due to, for example, the ability to absorb light, the efficiency of generation of acid generated by light, the diffusion ability of an acid generated by an anion, the strength of an anion acid, and the like. Line edge roughness, etc. directly Image.
近來,光微影技術正在積極進行採用ArF液浸(液浸曝光)技術的大批量製造(HVM:high volumn manufacturing),主要進行實現50nm以下線寬的技術開發。如此,隨著需要實現的線寬逐漸變小,抗蝕劑需要具備高解析度、可適用於製程上的充分的保障(能量保障、焦距保障)、線寬的減小以及與之對應的能夠應對厚度減小的充分的耐蝕刻性等性能,其中,特別要求改善線邊緣粗糙度的特性。 Recently, photolithography technology is actively pursuing high-volume manufacturing (HVM) using ArF liquid immersion (immersion exposure) technology, and mainly develops technologies for achieving line widths of 50 nm or less. Thus, as the line width to be realized becomes smaller, the resist needs to have high resolution, sufficient protection for the process (energy support, focal length guarantee), line width reduction, and corresponding energy. It is necessary to cope with properties such as sufficient etch resistance of thickness reduction, and among them, it is particularly required to improve the characteristics of line edge roughness.
線邊緣粗糙度意味著曝光區域和非曝光區域之間的表面的均勻度,近來對ArF液浸曝光方式的線邊緣粗糙度的要求精細到2nm至3nm左右。 The line edge roughness means the uniformity of the surface between the exposed area and the non-exposed area, and the requirement for line edge roughness of the ArF immersion exposure method is recently fine to about 2 nm to 3 nm.
如上所述,影響線邊緣粗糙度的原因很多,而其中,光酸發生劑由於對曝光引起酸生成後曝光時或曝光後烘焙(Post Exposure Bake,PEB)時的酸的擴散距離以及酸的強度產生影響,因此被視為影響線邊緣粗糙度的主要原因,因此,主要進行通過調節光酸發生劑的酸的擴散來獲得更好的線邊緣粗糙度特性的研究。另外,隨著人們認識到與酸擴散快時相比,酸擴散慢時在非曝光和曝光的鄰接區域上能夠減少酸擴散引起的線邊緣粗糙度,作為減少酸擴散的方法,通過擴大陰離子的大小來調節生成酸時的擴散的方式正在被大量研究。 As described above, there are many reasons for affecting the edge roughness of the wire, and among them, the diffusion distance of the acid and the acidity of the photoacid generator due to exposure to acid after exposure or Post Exposure Bake (PEB) The influence is therefore considered as a main factor affecting the roughness of the line edge, and therefore, research for obtaining better line edge roughness characteristics by adjusting the diffusion of the acid of the photoacid generator is mainly performed. In addition, as it is recognized that the acid diffusion is slower than when the acid diffusion is slow, the edge roughness caused by acid diffusion can be reduced in the non-exposed and exposed adjacent regions, as a method of reducing acid diffusion, by expanding the anion The way in which the size regulates the diffusion when acid is formed is being studied extensively.
專利文獻1:韓國專利公開第2010-0014433號(2010.08.27公開) Patent Document 1: Korean Patent Publication No. 2010-0014433 (published on 2010.08.27)
專利文獻2:韓國專利公開第2006-0030950號(2006.10.13公開) Patent Document 2: Korean Patent Publication No. 2006-0030950 (published on June 31, 2013)
專利文獻3:韓國專利公開第2010-7022640號(2010.12.02公開) Patent Document 3: Korean Patent Publication No. 2010-7022640 (published on 2010.12.02)
專利文獻4:韓國專利公開第2010-0051591號(2011.12.07公開) Patent Document 4: Korean Patent Publication No. 2010-0051591 (2011.12.07 publication)
本發明的目的在於,提供一種光酸發生劑(photoacid generator;以下稱“PAG”),其在抗蝕膜形成過程中,通過防止從曝光區域到非曝光區域的酸的擴散,從而能夠減少非曝光表面和曝光表面上的線邊緣粗糙度。 An object of the present invention is to provide a photoacid generator (hereinafter referred to as "PAG") which can reduce non-acid diffusion from an exposed region to a non-exposed region during formation of a resist film. Line edge roughness on exposed and exposed surfaces.
本發明的另一目的在於,提供一種包含所述光酸發生劑的抗蝕劑組成物。 Another object of the present invention is to provide a resist composition comprising the photoacid generator.
為了實現上述目的,本發明的一實施例涉及的光酸發生劑是具有下述化學式1的結構的化合物。 In order to achieve the above object, a photoacid generator according to an embodiment of the present invention is a compound having the structure of the following Chemical Formula 1.
所述化學式1中,Q1和Q1’是各自獨立為鹵素基;Q2和Q2’是各自獨立為氫原子或鹵素基;R是氫原子或碳原子數為1-4的烷基;V1和V2是各自獨立為氧原子(O)或硫原子(S); W1和W2各自獨立地選自由碳原子數為1-10的烷基、碳原子數為3-30的環烷基、碳原子數為3-30的芳基、碳原子數為1-10的烷氧基以及它們的組合所組成的群組中;X選自由伸烷基、伸烯基、NR'、S、O、CO以及它們的組合所組成的群組中,R'是氫原子或碳原子數為1-4的烷基;a是1至4的整數,b是0至5的整數,c是1至3的整數,d是1至3的整數;A+是有機抗衡離子。 In the chemical formula 1, Q 1 and Q 1 ' are each independently a halogen group; Q 2 and Q 2 ' are each independently a hydrogen atom or a halogen group; and R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; ; V 1 and V 2 are each independently an oxygen atom (O) or a sulfur atom (S); W 1 and W 2 are each independently selected from an alkyl group having 1 to 10 carbon atoms and having 3 to 30 carbon atoms; a group consisting of a cycloalkyl group, an aryl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a combination thereof; and X is selected from an alkyl group, an alkenyl group, and an NR group. In the group consisting of ', S, O, CO, and a combination thereof, R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; a is an integer of 1 to 4, and b is an integer of 0 to 5. c is an integer from 1 to 3, d is an integer from 1 to 3; A+ is an organic counter ion.
優選,所述化學式1中的X是羰基(CO)。 Preferably, X in the chemical formula 1 is a carbonyl group (CO).
更優選,所述化學式1中Q1和Q1’是各自獨立為氟基,Q2和Q2’是各自獨立為氫原子或氟基,R是氫原子或甲基,V1和V2是各自獨立為氧原子或硫原子,W1和W2各自獨立地選自由甲基、乙基、環丙基、苯基、甲氧基以及乙氧基所組成的群組中,X是羰基,a是1至3的整數,b是0至2的整數,c是1或2的整數,d是1或2的整數。 More preferably, in the chemical formula 1, Q 1 and Q 1 ' are each independently a fluorine group, and Q 2 and Q 2 ' are each independently a hydrogen atom or a fluorine group, and R is a hydrogen atom or a methyl group, and V 1 and V 2 are respectively Each is independently an oxygen atom or a sulfur atom, and W 1 and W 2 are each independently selected from the group consisting of methyl, ethyl, cyclopropyl, phenyl, methoxy, and ethoxy, and X is a carbonyl group. , a is an integer from 1 to 3, b is an integer from 0 to 2, c is an integer of 1 or 2, and d is an integer of 1 or 2.
更優選,所述化學式1中的陰離子部分可以選自由下述化學式2a至化學式2f所組成的群組中。 More preferably, the anion moiety in Chemical Formula 1 may be selected from the group consisting of Chemical Formula 2a to Chemical Formula 2f below.
[化學式2b]
另外,優選,所述化學式1中的A+可以是選自由硫鎓類、碘 鎓類、磷鎓類、重氮鹽類、吡啶嗡類及醯亞胺類所組成的群組中的有機抗衡離子,更優選,所述A+是下述化學式3a或化學式3b表示的有機抗衡離子。 Further, preferably, A+ in the chemical formula 1 may be selected from the group consisting of thioindigo and iodine. More preferably, the organic counter ion in the group consisting of anthraquinones, phosphoniums, diazonium salts, pyridiniums, and quinones is an organic counter ion represented by the following chemical formula 3a or chemical formula 3b. .
所述化學式3a和化學式3b中,X1、X2、Y1及Y2是各自獨立地選自由氫原子、碳原子數為1-10的烷基、烯丙基、碳原子數為1-10的全氟烷基、苄基、碳原子數為6-30的芳基以及它們的組合所組成的群組中的任一個,X1和X2及Y1和Y2可以彼此連接形成碳原子數為3-30的飽和或不飽和烴環;X3、X4、X5、Y3、Y4和Y5可以是各自獨立地選自氫原子、碳原子數為1-30的烷基、鹵素基、碳原子數為1-30的烷氧基、碳原 子數為6-30的芳基、硫代苯氧基(thiophenoxy)、碳原子數為1-30的硫代烷氧基(thioalkoxy)、碳原子數為1-20的烷氧基羰基甲氧基(alkoxycarbonylmethoxy)以及它們的組合所組成的群組中的任一個。 In the chemical formula 3a and the chemical formula 3b, X 1 , X 2 , Y 1 and Y 2 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, and 1 to 1 carbon atom. Any one of the group consisting of a perfluoroalkyl group of 10, a benzyl group, an aryl group having 6 to 30 carbon atoms, and a combination thereof, X 1 and X 2 and Y 1 and Y 2 may be bonded to each other to form a carbon. a saturated or unsaturated hydrocarbon ring having an atomic number of 3 to 30; X 3 , X 4 , X 5 , Y 3 , Y 4 and Y 5 may be an alkane each independently selected from a hydrogen atom and having 1 to 30 carbon atoms a group, a halogen group, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a thiophenoxy group, and a thioalkoxy group having 1 to 30 carbon atoms Any of a group consisting of (thioalkoxy), an alkoxycarbonylmethoxy having 1 to 20 carbon atoms, and a combination thereof.
進一步更優選,A+可以是具有下述化學式4a至化學式4v表示的結構的有機抗衡離子。 Still more preferably, A+ may be an organic counter ion having a structure represented by the following Chemical Formula 4a to Chemical Formula 4v.
根據本發明的另一實施例,提供所述化學式1的光酸發生劑的製備方法,其包括如下步驟:使下述化學式7的化合物與 選自羰基二咪唑(carbonyl diimidazole)、N-鹵代丁二醯亞胺(N-halosuccinic imide)、碘化鉀(potassium iodide)、亞硫醯氯(thionyl chloride)以及由它們的混合物組成的群組中的化合物反應而製備下述化學式9的化合物的步驟;使如上步驟製備的化學式9的化合物與下述化學式10的化合物反應而製備下述化學式11的化合物的步驟;以及使如上步驟製備的化學式11的化合物與下述化學式12的化合物反應的步驟。 According to another embodiment of the present invention, there is provided a process for producing the photoacid generator of Chemical Formula 1, which comprises the steps of: reacting a compound of the following Chemical Formula 7 with Selected from the group consisting of carbonyl diimidazole, N-halosuccinic imide, potassium iodide, thionyl chloride, and mixtures thereof a step of preparing a compound of the following chemical formula 9 by reacting a compound; a step of preparing a compound of the following chemical formula 11 by reacting a compound of the chemical formula 9 prepared as described above with a compound of the following chemical formula 10; and a chemical formula 11 prepared by the above step The step of reacting a compound with a compound of the following Chemical Formula 12.
[化學式11]
[化學式12]A+Z- [Chemical Formula 12] A+Z-
所述化學式7及化學式9至化學式12中,Q1和Q1’是各自獨立為鹵素基;Q2和Q2’是各自獨立為氫原子或鹵素基;R是氫原子或碳原子數為1-4的烷基;V1和V2是各自獨立為氧原子(O)或硫原子(S);W1和W2各自獨立地選自由碳原子數為1-10的烷基、碳原子數為3-30的環烷基、碳原子數為3-30的芳基、碳原子數為1-10的烷氧基以及它們的組合所組成的群組中;X選自由伸烷基、伸烯基、NR'、S、O、CO以及它們的組合所組成的群組中,R'是氫原子或碳原子數為1-4的烷基;a是1至4的整數,b是0至5的整數,c是1至3的整數,d是1至3的整數;A+是有機抗衡離子;M+是選自由Li+、Na+以及K+所組成的群組中的任一個;Q3選自由咪唑基、氟、氯、溴以及碘所組成的群組中;以及Z-是選自由(OSO2CF3)-、(OSO2C4F9)-、(OSO2C8F17)-、(N(CF3)2)-、(N(C2F5)2)-、(N(C4F9)2)-、(C(CF3)3)-、(C(C2F5)3)-、(C(C4F9)3)-、F-、Cl-、Br-、I-、BF4-、AsF6-及PF6-所組成的群組 中的任一個。 In the chemical formula 7 and the chemical formula 9 to the chemical formula 12, Q 1 and Q 1 ' are each independently a halogen group; Q 2 and Q 2 ' are each independently a hydrogen atom or a halogen group; R is a hydrogen atom or the number of carbon atoms is An alkyl group of 1 to 4; V 1 and V 2 are each independently an oxygen atom (O) or a sulfur atom (S); and W 1 and W 2 are each independently selected from an alkyl group having 1 to 10 carbon atoms, carbon. a group consisting of a cycloalkyl group having 3 to 30 atoms, an aryl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a combination thereof; X is selected from an alkyl group In the group consisting of alkenyl groups, NR', S, O, CO, and combinations thereof, R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; a is an integer of 1 to 4, b Is an integer from 0 to 5, c is an integer from 1 to 3, d is an integer from 1 to 3; A+ is an organic counter ion; M+ is any one selected from the group consisting of Li+, Na+, and K+; Q 3 Selected from the group consisting of imidazolyl, fluorine, chlorine, bromine and iodine; and Z- is selected from (OSO 2 CF 3 )-, (OSO 2 C 4 F 9 )-, (OSO 2 C 8 F 17 )-, (N(CF 3 ) 2 )-, (N(C 2 F 5 ) 2 )-, (N(C 4 F 9 ) 2 )-, (C(CF 3 ) 3 )-, (C( C 2 F 5 ) 3 )-, (C(C 4 F 9 ) 3 )-, F-, Cl-, Br-, I-, BF 4 -, AsF 6 - and PF 6 - One.
本發明的另一實施例提供下述化學式11的光酸化合物。 Another embodiment of the present invention provides the photoacid compound of the following Chemical Formula 11.
所述化學式11中,Q1和Q1’是各自獨立為鹵素基;Q2和Q2’是各自獨立為氫原子或鹵素基;R是氫原子或碳原子數為1-4的烷基;V1和V2是各自獨立為氧原子(O)或硫原子(S);W1和W2各自獨立地選自由碳原子數為1-10的烷基、碳原子數為3-30的環烷基、碳原子數為3-30的芳基、碳原子數為1-10的烷氧基以及它們的組合所組成的群組中;X選自由伸烷基、伸烯基、NR'、S、O、CO以及它們的組合所組成的群組中,此時,R'是氫原子或碳原子數為1-4的烷基;a是1至4的整數,b是0至5的整數,c是1至3的整數,d是1至3的整數;M+是選自由Li+、Na+以及K+所組成的群組中的任一個。 In the formula 11, Q 1 and Q 1 ' are each independently a halogen group; Q 2 and Q 2 ' are each independently a hydrogen atom or a halogen group; and R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; ; V 1 and V 2 are each independently an oxygen atom (O) or a sulfur atom (S); and W 1 and W 2 are each independently selected from an alkyl group having 1 to 10 carbon atoms and having 3 to 30 carbon atoms; a group consisting of a cycloalkyl group, an aryl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a combination thereof; and X is selected from an alkyl group, an alkenyl group, and an NR group. In the group consisting of ', S, O, CO, and a combination thereof, R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; a is an integer of 1 to 4, and b is 0 to An integer of 5, c is an integer of 1 to 3, d is an integer of 1 to 3; and M+ is any one selected from the group consisting of Li+, Na+, and K+.
本發明的另一實施例提供包含所述光酸發生劑的抗蝕劑組成物。 Another embodiment of the present invention provides a resist composition comprising the photoacid generator.
本發明的其他實施例的具體事項包含在下述說明中。 Specific matters of other embodiments of the present invention are included in the following description.
本發明的光酸發生劑在抗蝕膜形成過程中,通過防止從 曝光區域到非曝光區域的酸的擴散,從而能夠減少非曝光表面和曝光表面上的線邊緣粗糙度。 The photoacid generator of the present invention prevents the slave during the formation of the resist film The diffusion of acid from the exposed area to the non-exposed area enables the line edge roughness on the non-exposed surface and the exposed surface to be reduced.
圖1是表示合成例1中製備的三甲基二噁烷甲酸(i)的1H NMR觀察結果的曲線圖。 Fig. 1 is a graph showing the results of 1H NMR observation of trimethyldioxanecarboxylic acid (i) prepared in Synthesis Example 1.
圖2是表示通過實施例1的步驟1製備的化合物(iii)的1H NMR觀察結果的曲線圖。 2 is a graph showing the results of 1H NMR observation of the compound (iii) prepared in the first step of Example 1.
圖3是表示通過實施例1的步驟2製備的化合物(v)的1H NMR觀察結果的曲線圖。 Fig. 3 is a graph showing the results of 1H NMR observation of the compound (v) prepared in the second step of Example 1.
圖4是表示通過實施例1的步驟3製備的固體化合物(vii)的1H NMR觀察結果的曲線圖。 4 is a graph showing the results of 1H NMR observation of the solid compound (vii) prepared in the third step of Example 1.
下面,詳細說明本發明的實施例。然而,這些僅作為示例而提出的,本發明並不限定於此,本發明的保護範圍應以申請專利範圍的記載為準。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the scope of the present invention should be determined by the scope of the patent application.
除非本說明書中另有說明,鹵素基是指選自由氟、氯、溴和碘所組成的群組中的任一個。 Unless otherwise stated in the specification, a halogen group means any one selected from the group consisting of fluorine, chlorine, bromine and iodine.
除非本說明書中另有說明,烷基是指碳原子數為1-30的直鏈或支鏈烷基,所述烷基包括一級烷基、二級烷基和三級烷基。作為所述烷基的具體例,可以舉出甲基、乙基、丙基、異丙基、丁基、異丁基、第3丁基等,但並不限定於此。 Unless otherwise stated in the specification, an alkyl group means a straight or branched alkyl group having 1 to 30 carbon atoms, and the alkyl group includes a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a third butyl group. However, the present invention is not limited thereto.
除非本說明書中另有說明,環烷基是指碳原子數為3-30的環烷基,包括一環式、二環式、三環式和四環式。此外,包括金剛烷基、降冰片基及含有降冰片基的多環式環烷基。 Unless otherwise specified in the specification, a cycloalkyl group means a cycloalkyl group having 3 to 30 carbon atoms, and includes a monocyclic, bicyclic, tricyclic or tetracyclic ring. Further, it includes an adamantyl group, a norbornyl group, and a polycyclic cycloalkyl group having a norbornyl group.
除非本說明書中另有說明,芳基是指含有苯環的化合物及其衍生物,例如,可以是在苯環上連接有烷基側鏈的甲苯或二甲苯等、兩個以上的苯環以單鍵結合的聯苯等、兩個以上的苯環以環烷基或雜環烷基作為媒介結合的茀、黃嘌呤或蒽醌等、兩個以上的苯環縮合的萘或蒽等。除非本說明書中另有說明,所述芳基為碳原子數為6-30的芳基。 Unless otherwise specified in the specification, the aryl group means a compound containing a benzene ring and a derivative thereof, and for example, may be a toluene or xylene having an alkyl side chain attached to a benzene ring, or two or more benzene rings. A single-bonded biphenyl or the like, two or more benzene rings, a naphthyl or an anthracene having a cycloalkyl group or a heterocycloalkyl group as a medium, two or more benzene rings condensed naphthalene or an anthracene. Unless otherwise stated in the specification, the aryl group is an aryl group having 6 to 30 carbon atoms.
除非本說明書中另有說明,所有化合物或取代基可以是被取代或未被取代的。在此,被取代是指氫由選自由鹵素原子、烷基、全氟烷基、全氟烷氧基、羥基、羧基、羰基、氰基、腈基、硝基、胺基、硫基、烷硫基、烷氧基、醯基、醛基、環烷基、雜環基、烯丙基、芳基、它們的衍生物及它們的組合組成的群組中選擇的1種取代。 Unless otherwise stated in the specification, all compounds or substituents may be substituted or unsubstituted. Here, substituted means that hydrogen is selected from the group consisting of a halogen atom, an alkyl group, a perfluoroalkyl group, a perfluoroalkoxy group, a hydroxyl group, a carboxyl group, a carbonyl group, a cyano group, a nitrile group, a nitro group, an amine group, a thio group, an alkane group. A substitution selected from the group consisting of a thio group, an alkoxy group, a decyl group, an aldehyde group, a cycloalkyl group, a heterocyclic group, an allyl group, an aryl group, a derivative thereof, and a combination thereof.
此外,除非本說明書中另有說明,它們的組合是指兩個以上的取代基通過單鍵結合或連接基團結合或兩個以上的取代基縮合連接的。 Further, unless otherwise stated in the specification, a combination thereof means that two or more substituents are condensed and bonded by a single bond or a linker group or two or more substituents.
本發明與現有的光酸發生劑通過依賴陰離子的大小來減少在非曝光和曝光的鄰接區域因酸的擴散引起的線邊緣粗糙度的方式不同,陰離子的一部分因光照後生成的酸進行分解並生成醇基,這種醇基通過與酸的氫鍵結合,能夠明顯地降低酸的擴散,從而減少線邊緣粗糙度。 The present invention and the existing photoacid generator reduce the line edge roughness caused by acid diffusion in the adjacent regions of non-exposure and exposure by depending on the size of the anion, and a part of the anion is decomposed by the acid generated after the light irradiation. The alcohol group is formed, and this alcohol group can significantly reduce the diffusion of the acid by hydrogen bonding with the acid, thereby reducing the line edge roughness.
即,本發明的一實施例的光酸發生劑能夠以下述化學式 1表示。 That is, the photoacid generator of one embodiment of the present invention can have the following chemical formula 1 indicates.
在所述化學式1的陰離子部分,Q1和Q1’可以是各自獨立為鹵素基,優選可以是各自獨立為氟基;Q2和Q2’可以是各自獨立為氫原子或鹵素基,優選可以是各自獨立為氫原子或氟基;R可以是氫原子或碳原子數為1-4的烷基,優選可以是氫原子或甲基;V1和V2可以是各自獨立為氧原子(O)或硫原子(S),優選可以是氧原子;W1和W2可以各自獨立地選自由碳原子數為1-10的烷基、碳原子數為3-30的環烷基、碳原子數為3-30的芳基、碳原子數為1-10的烷氧基以及它們的組合所組成的群組中,優選可以各自獨立地選自由甲基、乙基、環丙基、苯基、甲氧基以及乙氧基所組成的群組中;X可以是選自由伸烷基、伸烯基、NR'、S、O、CO以及它們的組合所組成的群組中的任一個,此時,R'是氫原子或碳原子數為1-4的烷基。優選X是羰基(CO);另外,a可以是1至4的整數,b可以是0至5的整數,c可 以是1至3的整數,d可以是1至3的整數,優選a可以是1至3的整數,b可以是0至2的整數,c可以是1或2的整數,d可以是1或2的整數;優選,所述化學式1中下述化學式1a的陰離子部分可以選自由下述化學式2a至化學式2f所組成的群組中。 In the anion portion of the chemical formula 1, Q 1 and Q 1 ' may each independently be a halogen group, preferably may each independently be a fluorine group; and Q 2 and Q 2 ' may each independently be a hydrogen atom or a halogen group, preferably Each may be independently a hydrogen atom or a fluorine group; R may be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group; and V 1 and V 2 may each independently be an oxygen atom ( O) or a sulfur atom (S), preferably may be an oxygen atom; W 1 and W 2 may each independently be selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and carbon. The group consisting of an aryl group having 3 to 30 atoms, an alkoxy group having 1 to 10 carbon atoms, and a combination thereof may preferably be independently selected from a methyl group, an ethyl group, a cyclopropyl group, and a benzene group. a group consisting of a group consisting of a methoxy group and an ethoxy group; X may be any one selected from the group consisting of an alkyl group, an alkenyl group, an NR', an S, an O, a CO, and a combination thereof. In this case, R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Preferably, X is a carbonyl group (CO); in addition, a may be an integer of 1 to 4, b may be an integer of 0 to 5, c may be an integer of 1 to 3, d may be an integer of 1 to 3, preferably a may be An integer of 1 to 3, b may be an integer of 0 to 2, c may be an integer of 1 or 2, and d may be an integer of 1 or 2; preferably, the anion portion of the following chemical formula 1a in Chemical Formula 1 may be selected from It is a group consisting of the following Chemical Formula 2a to Chemical Formula 2f.
所述化學式1a中的各個取代基的定義與前述的定義相同。 The definition of each substituent in the chemical formula 1a is the same as defined above.
此外,所述化學式1的陽離子部分,所述A+是有機抗衡離子,具體可以是選自由硫鎓類、碘鎓類、鎓鹽類、重氮鎓鹽、 吡啶嗡類以及醯亞胺類所組成的群組中的陽離子。 Further, in the cationic portion of Chemical Formula 1, the A+ is an organic counter ion, and specifically may be selected from the group consisting of thioindigos, iodoniums, phosphonium salts, diazonium salts, a cation in a group consisting of pyridinium and quinone.
當所述A+是硫鎓類有機抗衡離子時,所述A+優選可以是下述化學式3a或化學式3b表示的有機陽離子。 When the A+ is a sulfonium-based organic counter ion, the A+ may preferably be an organic cation represented by the following Chemical Formula 3a or Chemical Formula 3b.
所述化學式3a和化學式3b中,X1、X2、Y1及Y2是各自獨立地選自由氫原子、碳原子數為1-10的烷基、烯丙基、碳原子數為1-10的全氟烷基、苄基、碳原子數為6-30的芳基以及它們的組合所組成的群組中的任一個,X1和X2及Y1和Y2可以彼此連接形成碳原子數為3-30的飽和或不飽和烴環;X3、X4、X5、Y3、Y4和Y5可以是各自獨立地選自由氫原子、碳原子數為1-30的烷基、鹵素基、碳原子數為1-30的烷氧基、碳 原子數為6-30的芳基、硫代苯氧基(thiophenoxy)、碳原子數為1-30的硫代烷氧基(thioalkoxy)、碳原子數為1-20的烷氧基羰基甲氧基(alkoxycarbonylmethoxy)以及它們的組合所組成的群組中的任一個;進一步更優選,所述A+可以是具有下述化學式4a至化學式4v表示的結構的有機抗衡離子。 In the chemical formula 3a and the chemical formula 3b, X 1 , X 2 , Y 1 and Y 2 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, and 1 to 1 carbon atom. Any one of the group consisting of a perfluoroalkyl group of 10, a benzyl group, an aryl group having 6 to 30 carbon atoms, and a combination thereof, X 1 and X 2 and Y 1 and Y 2 may be bonded to each other to form a carbon. a saturated or unsaturated hydrocarbon ring having an atomic number of 3 to 30; X 3 , X 4 , X 5 , Y 3 , Y 4 and Y 5 may be independently selected from a hydrogen atom and an alkane having 1 to 30 carbon atoms. a group, a halogen group, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a thiophenoxy group, and a thioalkoxy group having 1 to 30 carbon atoms Any one of a group consisting of (thioalkoxy), an alkoxycarbonylmethoxy having 1 to 20 carbon atoms, and a combination thereof; further preferably, the A+ may have the following chemical formula 4a The organic counter ion of the structure represented by the chemical formula 4v.
另外,當所述A+是碘鎓類有機抗衡離子時,所述A+優選可以是下述化學式5a或化學式5b表示的有機陽離子。 Further, when the A+ is an iodonium-based organic counter ion, the A+ may preferably be an organic cation represented by the following Chemical Formula 5a or Chemical Formula 5b.
所述化學式5a和化學式5b中,R11至R13及R21至R23可以是各自獨立地選自由氫原子、碳原子數為1-10的烷基、烯丙基、碳原子數為1-10的全氟烷基、碳原子數為6-30的芳基以及它們的組合所組成的群組中的任一個;R14和R24可以是各自獨立地選自由鹵素基、碳原子數為1-30的烷基、碳原子數為1-30的烷氧基、碳原子數為6-30的芳基、硫代苯氧基、碳原子數為1-30的硫代烷氧基、碳原子數為1-20的烷氧基羰基甲氧基以及它們的組合所組成的群組中的任一個;更優選,所述A+是具有下述化學式6a至化學式6i表示的結構的有機抗衡離子。 In the chemical formula 5a and the chemical formula 5b, R 11 to R 13 and R 21 to R 23 may each independently be selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, and 1 carbon atom. Any one of the group consisting of -10 perfluoroalkyl group, aryl group having 6 to 30 carbon atoms, and combinations thereof; R 14 and R 24 may each independently be selected from a halogen group, a carbon number An alkyl group of 1 to 30, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a thiophenoxy group, and a thioalkoxy group having 1 to 30 carbon atoms Any one of the group consisting of an alkoxycarbonylmethoxy group having 1 to 20 carbon atoms and a combination thereof; more preferably, the A+ is an organic compound having the structure represented by the following Chemical Formula 6a to Chemical Formula 6i Counter ion.
所述有機抗衡離子中進一步更優選為硫鎓類有機抗衡離子。 Further more preferably, the organic counter ion is a sulfonium-based organic counter ion.
具備如上所述結構的本發明的一實施例的光酸發生劑可以通過如下製備步驟製備:使下述化學式7的化合物與選自由下述化學式8a的羰基二咪唑(carbonyl diimidazole)、下述化學式8b的N-鹵代丁二醯亞胺(N-halosuccinic imide)、下述化學式8c的碘化鉀(potassium iodide)、下述化學式8d的亞硫醯氯(thionyl chloride)以及它們的混合物所組成的群組中的化合物反應而製備下述化學式9的化合物的步驟(步驟1);使上述步驟中製備的化學式9的化合物與下述化學式10的化合物反應而製備下述化學式11的化合物的步驟(步驟2);以及使上述步驟中製備的化學式11的化合物與下述化學式12的化合物反應而製備下述化學式1的化合物的步驟(步驟3)。 The photoacid generator of one embodiment of the present invention having the structure as described above can be produced by the following preparation steps: a compound of the following chemical formula 7 and a carbonyl diimidazole selected from the following Chemical Formula 8a, the following chemical formula a group consisting of N-halosuccinic imide of 8b, potassium iodide of the following chemical formula 8c, thionyl chloride of the following chemical formula 8d, and a mixture thereof a step of preparing a compound of the following chemical formula 9 by reacting a compound in the group (step 1); a step of preparing a compound of the following chemical formula 11 by reacting the compound of the chemical formula 9 prepared in the above step with a compound of the following chemical formula 10 (step 2); and a step (Step 3) of preparing a compound of the following Chemical Formula 1 by reacting the compound of Chemical Formula 11 prepared in the above step with a compound of the following Chemical Formula 12.
[化學式1]
[化學式8c]K+I- [Chemical Formula 8c] K + I -
[化學式12]A+Z- [Chemical Formula 12] A+Z-
所述化學式1及化學式7至化學式12中,A+、Q1、Q1’、Q2、Q2’、V1、V2、W1、W2、R、X及a至d的定義與前述的定義相同;M+是選自由Li+、Na+及K+所組成的群組中的任一個;Q3是從化學式8a至化學式8d的化合物衍生的官能團,具體選自由咪唑基、氟、氯、溴及碘所組成的群組中;Y是選自由氟、氯、溴及碘所組成的群組中的鹵素基; Z-是選自由(OSO2CF3)-、(OSO2C4F9)-、(OSO2C8F17)-、(N(CF3)2)-、(N(C2F5)2)-、(N(C4F9)2)-、(C(CF3)3)-、(C(C2F5)3)-、(C(C4F9)3)-、F-、Cl-、Br-、I-、BF4-、AsF6-及PF6-所組成的群組中的任一個。 In the chemical formula 1 and the chemical formula 7 to the chemical formula 12, the definitions of A+, Q 1 , Q 1 ', Q 2 , Q 2 ', V 1 , V 2 , W 1 , W 2 , R, X and a to d are The foregoing definitions are the same; M+ is any one selected from the group consisting of Li+, Na+, and K+; Q 3 is a functional group derived from the compound of Chemical Formula 8a to Chemical Formula 8d, specifically selected from the group consisting of imidazolyl, fluorine, chlorine, and bromine And a group consisting of iodine; Y is a halogen group selected from the group consisting of fluorine, chlorine, bromine and iodine; Z- is selected from (OSO 2 CF 3 )-, (OSO 2 C 4 F 9 )-, (OSO 2 C 8 F 17 )-, (N(CF 3 ) 2 )-, (N(C 2 F 5 ) 2 )-, (N(C 4 F 9 ) 2 )-, (C( CF 3 ) 3 )-, (C(C 2 F 5 ) 3 )-, (C(C 4 F 9 ) 3 )-, F-, Cl-, Br-, I-, BF 4 -, AsF 6 - And any one of the groups consisting of PF 6 -.
下述反應式是用於表示本發明的一實施例的光酸發生劑的製備的反應步驟,下述反應式1僅僅是用於說明本發明的一示例,本發明並非限定於此。 The following reaction formula is a reaction step for indicating the preparation of the photoacid generator of one embodiment of the present invention, and the following Reaction Formula 1 is merely an example for explaining the present invention, and the present invention is not limited thereto.
所述反應式1中,各個化合物的取代基的定義與前述的定義相同。 In the above Reaction Scheme 1, the definition of the substituent of each compound is the same as defined above.
以下參照反應式1對各步驟進行詳細的說明。 Each step will be described in detail below with reference to Reaction Formula 1.
步驟1是使化學式7的化合物與所述化學式8a的羰基二咪唑(carbonyl diimidazole)反應而製備所述化學式9的化合物的步驟。 Step 1 is a step of preparing a compound of the chemical formula 9 by reacting a compound of Chemical Formula 7 with a carbonyl diimidazole of the Chemical Formula 8a.
所述化學式7的化合物可從市面上獲得,也可以根據公開的 方法製備。具體如反應式2,使(2,2-雙(羥甲基)丙酸)(2,2-bis(hydroxymethyl)propionic acid)等二羥基類化合物(13),在對甲苯磺酸(p-toluene sulfonic acid,p-TSA)等酸催化劑的作用下,與2,2-二甲氧基丙烷(2,2-dimethoxy propane)等二烷氧基鏈烷化合物(14)反應而可製備化學式7的化合物(7a)。 The compound of the chemical formula 7 is commercially available or can be used according to the disclosure. Method preparation. Specifically, as in Reaction Scheme 2, a dihydroxy compound (13) such as (2,2-bis(hydroxymethyl)propionic acid) is used in p-toluenesulfonic acid (p- By the action of an acid catalyst such as toluene sulfonic acid, p-TSA), it can be reacted with a dialkoxy alkane compound (14) such as 2,2-dimethoxypropane to prepare a chemical formula 7 Compound (7a).
作為所述化學式7的化合物,具體可以使用三甲基二噁烷甲酸(trimethyl dioxane carboxylic acid)等。 Specific examples of the compound of Chemical Formula 7 include trimethyl dioxane carboxylic acid and the like.
另外,所述反應式1的步驟1中,可使用例如N-溴代丁二醯亞胺(N-bromosuccinic imide)等N-鹵代丁二醯亞胺、碘化鉀(potassium iodide)、亞硫醯氯(thionyl chloride)或它們的混合物來代替所述化學式8a的羰基二咪唑。 Further, in the step 1 of the reaction formula 1, for example, N-halogenated diimenimine such as N-bromosuccinic imide, potassium iodide or sulfoxide may be used. Instead of the carbonyl diimidazole of the chemical formula 8a, thionyl chloride or a mixture thereof.
在精煉或產率的提高方面,在上述反應步驟1的過程中,優選化學式7的化合物與可反應的化學式8a至化學式8d的化合物以1:1至1:1.2的莫耳比進行反應,上述步驟1的反應可在四氫呋喃(tetrahydrofuran,THF)等溶劑中進行。 In terms of refining or improvement in yield, in the above reaction step 1, it is preferred that the compound of Chemical Formula 7 reacts with the reactable compound of Chemical Formula 8a to Chemical Formula 8d at a molar ratio of 1:1 to 1:1.2, as described above. The reaction of the step 1 can be carried out in a solvent such as tetrahydrofuran (THF).
上述步驟1的反應過程中產生二氧化碳氣體,而且,作為上述反應結果獲得的反應物中,化學式9的化合物與咪唑一起包含在其內。由此,可通過一般的方法對結果反應物進行附加的 分離及精煉步驟來分離出生成的化學式9的化合物,或者,也可以不經過附加分離步驟,可將步驟1的反應物直接用於下一步驟的反應中。 Carbon dioxide gas is generated during the reaction of the above step 1, and the compound of Chemical Formula 9 is contained together with the imidazole in the reactant obtained as a result of the above reaction. Thus, the resulting reactants can be attached by a general method. The separation and refining steps are carried out to separate the resulting compound of Chemical Formula 9, or the reactant of Step 1 can be used directly in the reaction of the next step without additional separation steps.
步驟2是使步驟1中製備的化學式9的化合物與化學式10的化合物反應而製備化學式11的化合物的步驟。 Step 2 is a step of preparing a compound of Chemical Formula 11 by reacting the compound of Chemical Formula 9 prepared in Step 1 with the compound of Chemical Formula 10.
作為所述化學式10的化合物,具體可使用1,1-二氟甲基-2-羥基乙磺酸(1,1-difluoromethyl-2-hydroxy-ethanesulfonic acid)、1,1-二氟甲基-2-羥基丙磺酸(1,1-difluoromethyl-2-hydroxy-propanesulfonic acid)、或1,1-二氟甲基-2-羥基丁磺酸(1,1-difluoromethyl-2-hydroxy-butanesulfonic acid)等鋰鹽、鈉或鈉鹽等。 As the compound of the chemical formula 10, specifically, 1,1-difluoromethyl-2-hydroxy-ethanesulfonic acid, 1,1-difluoromethyl- 1,1-difluoromethyl-2-hydroxy-propanesulfonic acid, or 1,1-difluoromethyl-2-hydroxy-butanesulfonic acid Lithium salt, sodium or sodium salt, etc.
上述步驟2的反應可在溶劑中進行,此時,溶劑可使用選自由酯類、醚類、內酯類、酮類、醯胺類、醇類及它們的組合所組成的群組中的任一個,優選所述溶劑可以是選自由二氯甲烷、氯仿、二氯乙烷、乙腈、甲苯及它們的組合所組成的群組中的任一個。 The reaction of the above step 2 can be carried out in a solvent. In this case, the solvent can be any one selected from the group consisting of esters, ethers, lactones, ketones, guanamines, alcohols, and combinations thereof. One, preferably the solvent may be any one selected from the group consisting of dichloromethane, chloroform, dichloroethane, acetonitrile, toluene, and combinations thereof.
為了容易精煉,優選所述化學式9的化合物與所述化學式10的化合物以1:1至1:1.2的莫耳比進行反應。 For ease of refining, it is preferred that the compound of the formula 9 is reacted with the compound of the formula 10 in a molar ratio of 1:1 to 1:1.2.
步驟3是使步驟2中製備的化學式11的化合物與化學式12的化合物反應而製備化學式1的步驟。 Step 3 is a step of preparing the chemical formula 1 by reacting the compound of Chemical Formula 11 prepared in Step 2 with the compound of Chemical Formula 12.
作為所述化學式12的化合物,具體可使用三苯基硫三氟甲烷磺酸鹽、二苯基烷基苯基硫三氯甲烷磺酸鹽、三苯基硫三氯甲烷磺酸鹽等。 Specific examples of the compound of Chemical Formula 12 include triphenylsulfur trifluoromethanesulfonate, diphenylalkylphenylthiotrichloromethanesulfonate, triphenylsulfur trichloromethanesulfonate, and the like.
優選上述步驟3的反應中,所述化學式11的化合物和 所述化學式12的化合物以1:1至1:1.2的莫耳比進行反應,從而最大限度地縮短反應時間,並抑制因使用過多的反應物而引起的副反應,且以高產率製備化學式1的化合物。 Preferably, in the reaction of the above step 3, the compound of the chemical formula 11 and The compound of the chemical formula 12 is reacted at a molar ratio of 1:1 to 1:1.2, thereby minimizing the reaction time, suppressing side reactions caused by using too much reactant, and preparing the chemical formula 1 in high yield. compound of.
上述取代反應可使用再結晶法或將能充分溶解獲得的鹽的溶劑(良溶劑)和不能充分溶解獲得的鹽的溶劑(不良溶劑)混合使用使固體化後回收的方法,也可以使用利用溶劑來萃取或濃縮回收的方法。 The above-mentioned substitution reaction may be carried out by using a recrystallization method or a solvent (good solvent) capable of sufficiently dissolving the obtained salt and a solvent (poor solvent) in which the obtained salt is not sufficiently dissolved, and then recovering the solution after solidification, or using a solvent. To extract or concentrate the method of recovery.
優選,溶解在二氯甲烷和水中,形成兩個反應層後進行攪拌,使發生取代反應。這種兩層反應方法的優點在於無需用於分離產物的附加的方法。上述攪拌可能進行2小時至6小時,也可能進行2小時至4小時。當反應在上述的時間範圍內進行時,可最大限度地提高產物的產率。 Preferably, it is dissolved in dichloromethane and water to form two reaction layers, followed by stirring to cause a substitution reaction to occur. An advantage of this two-layer reaction process is that no additional methods for separating the product are needed. The above agitation may be carried out for 2 hours to 6 hours, and may also be carried out for 2 hours to 4 hours. When the reaction is carried out in the above-mentioned time range, the yield of the product can be maximized.
當通過上述過程來製備所述化學式1表示的化合物時,可用既效率又簡單的方法獲得所述化學式1表示的化合物。 When the compound represented by Chemical Formula 1 is produced by the above process, the compound represented by Chemical Formula 1 can be obtained by a method which is both efficient and simple.
將利用上述的製備方法製備的化學式1的光酸發生劑應用於抗蝕劑組成物時,如果照射充足的光,將生成酸,生成的酸會快速地擴散,而含有酸的陰離子通過這些酸進行分解,使每個分子生成兩個醇基,生成的醇基通過與其他酸的氫鍵結合,從而降低酸的擴散。其結果是,防止從非曝光區域到曝光區域的酸的滲透,從而能夠最大限度地減少線邊緣粗糙度。 When the photoacid generator of Chemical Formula 1 prepared by the above-described preparation method is applied to a resist composition, if sufficient light is irradiated, an acid is formed, and the generated acid rapidly diffuses, and an acid-containing anion passes through these acids. Decomposition is carried out to form two alcohol groups per molecule, and the resulting alcohol group is bonded to hydrogen bonds with other acids to reduce the diffusion of acid. As a result, the penetration of acid from the non-exposed area to the exposed area is prevented, so that the line edge roughness can be minimized.
下述反應式3概略地表示本發明的光酸發生劑通過曝光減少酸擴散的效果。但該反應式僅僅是用於說明本發明的一示例,本發明並非限定於此。 The following Reaction Formula 3 schematically shows the effect of reducing the acid diffusion by exposure of the photoacid generator of the present invention. However, the reaction formula is merely an example for explaining the present invention, and the present invention is not limited thereto.
[反應式3]
作為一例,將化合物A作為本發明的光酸發生劑而用於抗蝕劑組成物時,光照使光離子被分解,陰離子生成例如B的酸。生成的酸B在光微影步驟中進行曝光後烘焙(PEB:post exposure baking)時,將經過酸B的擴散過程,最初酸的擴散速度相對緩慢,而後由於酸B自身的酸,使作為酸不穩定基團的三甲基二噁烷基(trimethyl dioxane group)被分解,從而使例如C的二醇生成在含有酸的陰離子中。此時,酸的擴散因二醇的氫鍵結合而迅速減少,通過防止從非曝光區域到曝光區域的酸的擴散,從而減少非曝光表面和曝光表面上的線邊緣粗糙度。 As an example, when Compound A is used as the photoacid generator of the present invention in a resist composition, light ions are decomposed by light, and an anion such as B acid is generated. When the generated acid B is subjected to post-exposure baking (PEB) in the photolithography step, the diffusion process of the acid B is carried out, the initial acid diffusion rate is relatively slow, and then the acid B itself is used as the acid. The trimethyl dioxane group of the labile group is decomposed so that a diol such as C is formed in the acid-containing anion. At this time, the diffusion of the acid is rapidly reduced by the hydrogen bonding of the diol, and the line edge roughness on the non-exposed surface and the exposed surface is reduced by preventing the diffusion of the acid from the non-exposed area to the exposed area.
由此,本發明的另一實施例提供包含所述光酸發生劑的抗蝕劑組成物。 Thus, another embodiment of the present invention provides a resist composition comprising the photoacid generator.
具體地,所述抗蝕劑組成物含有所述光酸發生劑、原料聚合物及溶劑。 Specifically, the resist composition contains the photoacid generator, a base polymer, and a solvent.
所述光酸發生劑如前述相同,可單獨使用也可兩種以上混合使用。此外,相對於聚合物固體成分100重量份,所述光酸發生劑的含量為0.3重量份-15重量份;優選0.5重量份-10重量份;更優選2重量份-10重量份。光酸發生劑的含量超過15重量份時,圖案的垂直性顯著降低;小於0.3重量份時,圖案的可塑度 可能會降低。 The photoacid generator may be used singly or in combination of two or more as described above. Further, the photoacid generator is contained in an amount of from 0.3 part by weight to 15 parts by weight, based on 100 parts by weight of the polymer solid component; preferably from 0.5 part by weight to 10 parts by weight; more preferably from 2 parts by weight to 10 parts by weight. When the content of the photoacid generator exceeds 15 parts by weight, the perpendicularity of the pattern is remarkably lowered; and when it is less than 0.3 parts by weight, the plasticity of the pattern May be reduced.
所述抗蝕劑用原料聚合物只要是在形成抗蝕膜時用作原料樹脂的就可以使用,不受特別的限制。具體實例有,所述抗蝕劑用原料聚合物可以選自由以下化合物組成的群組中:(甲基)丙烯酸酯聚合物;(α-三氟甲基)丙烯酸酯-馬來酸酐共聚物;環烯-馬來酸酐共聚物;聚降冰片烯;環烯的開環複分解反應得到的高分子化合物;環烯的開環複分解反應得到的聚合物添加氫而得到的高分子化合物;羥基苯乙烯和(甲基)丙烯酸酯的衍生物;選自苯乙烯、乙烯萘酯、乙烯基蒽、乙烯基芘、羥基乙烯萘酯、羥基乙烯基蒽、茚、羥基茚、苊烯、降冰片二烯類中的任意一種共聚而得的高分子化合物;酚醛樹脂及它們的混合物。 The raw material polymer for a resist can be used as long as it is used as a raw material resin in forming a resist film, and is not particularly limited. Specific examples are that the raw material polymer for resist may be selected from the group consisting of: (meth) acrylate polymer; (α-trifluoromethyl) acrylate-maleic anhydride copolymer; a cycloolefin-maleic anhydride copolymer; a polynorbornene; a polymer compound obtained by ring-opening metathesis reaction of a cycloolefin; a polymer compound obtained by adding a hydrogen to a polymer obtained by ring-opening metathesis reaction of a cycloolefin; hydroxystyrene And (meth) acrylate derivatives; selected from the group consisting of styrene, vinyl naphthalate, vinyl fluorene, vinyl hydrazine, hydroxy vinyl naphthyl ester, hydroxy vinyl hydrazine, hydrazine, hydroxy hydrazine, decene, norbornadiene A polymer compound obtained by copolymerization of any of the classes; a phenol resin; and a mixture thereof.
相對於抗蝕劑組成物總重量,所述原料聚合物可含有3重量%-20重量%。當所述聚合物的含量不足3重量%時,組成物的黏度過低,無法形成所需厚度的薄膜,並由於相對多的光酸發生劑而導致圖案損失(pattern loss)嚴重;當超過20重量%時,導致薄膜的厚度過厚,放射線的透過性降低,從而很難得到垂直圖案。 The base polymer may contain from 3% by weight to 20% by weight based on the total weight of the resist composition. When the content of the polymer is less than 3% by weight, the viscosity of the composition is too low to form a film of a desired thickness, and pattern loss is severe due to a relatively large amount of photoacid generator; When the weight is %, the thickness of the film is too thick, and the transmittance of radiation is lowered, so that it is difficult to obtain a vertical pattern.
為了得到均勻和平坦的抗蝕劑塗覆膜,優選將所述聚合物和光酸發生劑溶解在具有適當的蒸發速度和黏性的溶劑中使用。本發明中可使用的溶劑有乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、醋酸甲氧乙酯、醋酸乙氧乙酯、丙二醇單甲醚醋酸酯、丙二醇單乙醚醋酸酯、丙二醇單丙醚醋酸酯等酯類;甲基異丙酮、環己酮、2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-庚酮、乳酸乙酯、γ-丁內酯等酮類,可以選擇其中1種來單獨使用或選擇2種以上混合使用。 In order to obtain a uniform and flat resist coating film, it is preferred to dissolve the polymer and photoacid generator in a solvent having an appropriate evaporation rate and viscosity. Solvents which can be used in the present invention are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether. Esters such as acetate, propylene glycol monopropyl ether acetate; methyl isopropanone, cyclohexanone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-heptanone, ethyl lactate, γ-butyl One type of ketones such as a lactone may be used alone or in combination of two or more.
所述溶劑可以根據溶劑的物理性質,即,揮發性、黏度等適當調整其使用量,以能夠形成均勻的抗蝕膜。 The solvent can be appropriately adjusted in accordance with physical properties of the solvent, that is, volatility, viscosity, and the like, so that a uniform resist film can be formed.
此外,本發明的抗蝕劑組成物為了達到提高塗覆性等的目的,可進一步含有添加劑。 Further, the resist composition of the present invention may further contain an additive for the purpose of improving coatability and the like.
所述添加劑只要是通常用於抗蝕劑組成物中的添加劑即可,沒有特別的限制,具體地可以是鹼溶解抑制劑、酸捕捉劑、表面活性劑等,可以包含其中1種添加劑或包含混合2種以上的添加劑。 The additive is not particularly limited as long as it is an additive generally used in a resist composition, and specifically may be an alkali dissolution inhibitor, an acid scavenger, a surfactant, or the like, and may include one of the additives or Two or more kinds of additives are mixed.
所述鹼溶解抑制劑只要是通常用於抗蝕劑組成物的鹼溶解抑制劑均可以使用,具體地可以是苯酚或羧酸衍生物等。 The alkali dissolution inhibitor may be used as long as it is an alkali dissolution inhibitor which is generally used for a resist composition, and specifically may be a phenol or a carboxylic acid derivative or the like.
所述酸捕捉劑能夠阻止由於光照射而由光酸發生劑生成的酸向抗蝕膜擴散時的擴散現象,並抑制未曝光部分的化學反應。使用這種酸捕捉劑能夠提高感光樹脂組成物的儲藏穩定性,同時進一步提高抗蝕劑的解析度,還能夠抑制曝光到顯像處理之間的時間(PED)變化導致的抗蝕圖的線寬變化。 The acid scavenger can prevent the diffusion phenomenon of the acid generated by the photoacid generator from diffusing into the resist film due to light irradiation, and suppress the chemical reaction of the unexposed portion. The use of such an acid scavenger can improve the storage stability of the photosensitive resin composition, and at the same time further improve the resolution of the resist, and can also suppress the line of the resist pattern caused by the change in time (PED) between exposure processes. Wide change.
如上所述的酸捕捉劑可以使用鹼性化合物,具體地,可以使用胺、甲胺、異丙胺、正己胺、環戊胺、亞甲基二胺、乙二胺、二甲胺、二異丙胺、二乙基二胺、N,N-二甲基甲二胺、N,N-二甲基乙二胺、三甲胺、三乙胺、N,N,N',N'-四甲基亞甲二胺、N,N,N',N'-四甲基乙二胺、N,N,N',N'-四甲基四乙基五胺、二甲基乙胺、甲基乙基丙胺、苄胺、苯基乙基胺、苄基二甲胺、四甲基氫氧化銨、苯胺、N,N-二甲基甲苯胺、三苯胺(酸捕捉劑)、對苯二胺、吡咯、噁唑、異噁唑、噻唑、異噻唑、咪唑、吡唑、吡咯啉、吡咯烷、咪唑啉衍生物、吡啶衍生物、噠嗪衍生物、嘧啶衍生物、 吡嗪衍生物、吡唑啉衍生物、吡唑烷衍生物、哌啶衍生物、哌嗪衍生物、嗎啉等胺類;胺基苯甲酸、吲哚羧酸、胺基酸衍生物(例如,煙酸、丙胺酸、精胺酸、天冬胺酸等)、3-吡啶磺酸、對甲苯磺酸吡啶、2-羥基吡啶、胺基甲基苯酚、2,4-喹啉二醇、2-(2-羥乙基)吡啶、1-(2-羥乙基)哌啶等含氮化合物;甲醯胺、N-甲基甲醯胺、N,N-二甲基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、丙醯胺、苯甲醯胺等的醯胺衍生物;或鄰苯二甲醯亞胺、琥珀醯亞胺、馬來醯亞胺等亞胺類衍生物。 As the acid scavenger as described above, a basic compound can be used, and specifically, an amine, methylamine, isopropylamine, n-hexylamine, cyclopentylamine, methylenediamine, ethylenediamine, dimethylamine, diisopropylamine can be used. , diethyldiamine, N,N-dimethyldiamine, N,N-dimethylethylenediamine, trimethylamine, triethylamine, N,N,N',N'-tetramethyl Methylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylpentamine, dimethylethylamine, methylethyl Propylamine, benzylamine, phenylethylamine, benzyldimethylamine, tetramethylammonium hydroxide, aniline, N,N-dimethyltoluidine, triphenylamine (acid scavenger), p-phenylenediamine, pyrrole , oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, pyrroline, pyrrolidine, imidazoline derivative, pyridine derivative, pyridazine derivative, pyrimidine derivative, A pyrazine derivative, a pyrazoline derivative, a pyrazolidine derivative, a piperidine derivative, a piperazine derivative, an amine such as morpholine; an aminobenzoic acid, an anthracene carboxylic acid, an amino acid derivative (for example) , niacin, alanine, arginine, aspartic acid, etc.), 3-pyridinesulfonic acid, p-toluenesulfonic acid pyridine, 2-hydroxypyridine, aminomethylphenol, 2,4-quinolinediol, a nitrogen-containing compound such as 2-(2-hydroxyethyl)pyridine or 1-(2-hydroxyethyl)piperidine; formamide, N-methylformamide, N,N-dimethylformamide, a decylamine derivative such as acetamide, N-methylacetamide, N,N-dimethylacetamide, acetamide or benzamide; or phthalimide or amber An imine derivative such as an amine or maleimide.
相對於聚合物的固體成分含量100重量份,所述酸捕捉劑的含量為0.01重量份-5重量份,優選0.1重量份-1重量份。如果酸捕捉劑的含量小於0.01重量份,隨著曝光後的延遲時間影響越大,對圖案的形狀產生影響;如果大於5重量份,解析度和光敏度會降低。 The acid scavenger is contained in an amount of from 0.01 part by weight to 5 parts by weight, based on 100 parts by weight of the solid content of the polymer, preferably from 0.1 part by weight to 1 part by weight. If the content of the acid scavenger is less than 0.01 parts by weight, the influence of the delay time after exposure is greater, which affects the shape of the pattern; if it is more than 5 parts by weight, the resolution and photosensitivity may be lowered.
所述表面活性劑是用於改善塗覆性及顯像性等,具體地可以是聚氧乙烯月桂醚(Polyoxyethylene lauryl ether)、聚氧乙烯硬脂醚(polyoxyethylene stearyl ether)、聚氧乙烯(polyoxyethylene)、聚乙二醇二月桂酸酯(polyethylene glycol dilaurate)等,但不限於此。 The surfactant is used for improving coating properties, developing properties, etc., and specifically may be polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene. ), polyethylene glycol dilaurate, etc., but is not limited thereto.
具有如上所述的組成的本發明抗蝕劑組成物含有具有酸擴散抑制效果的光酸發生劑,在形成抗蝕膜時,能夠減少非曝光/曝光鄰接部位的酸擴散導致的線邊緣粗糙度。 The resist composition of the present invention having the composition as described above contains a photoacid generator having an acid diffusion suppressing effect, and can reduce line edge roughness caused by acid diffusion of non-exposure/exposure adjacent portions when a resist film is formed. .
下面,對本發明的實施例進行詳細說明,以使本領域技術人員能夠容易地實施。但本發明可以通過多種不同的形態實施,不限於在此說明的實施例。 Hereinafter, the embodiments of the present invention will be described in detail so as to be easily implemented by those skilled in the art. However, the invention may be embodied in a variety of different forms and is not limited to the embodiments described herein.
圓底燒瓶內放入旋轉棒(spin bar)進行攪拌,將100g的2,2-雙(羥甲基)丙酸(2,2-bis(hydroxymethyl)propionic acid)溶解於500ml的丙酮後,添加116g的2,2-二甲氧基丙烷(2,2-dimethoxy propane)進行溶解。繼續攪拌由此獲得的混合物,同時將作為酸催化劑的7g的對甲苯磺酸(p-toluene sulfonic acid,p-TSA)添加到溶液裡,常溫下攪拌3小時。利用核磁共振(NMR)確認反應完成結果之後,對獲得的反應物進行減壓蒸餾,除去作為溶劑的丙酮,將由此獲得的反應物溶解到二氯甲烷(dichloromethane)內,添加10ml的氫氧化銨(NH4OH,35wt%),除去p-TSA。 The round bottom flask was placed in a spin bar and stirred, and 100 g of 2,2-bis(hydroxymethyl)propionic acid was dissolved in 500 ml of acetone, and then added. 116 g of 2,2-dimethoxy propane was dissolved. The mixture thus obtained was continuously stirred while 7 g of p-toluene sulfonic acid (p-TSA) as an acid catalyst was added to the solution, and stirred at normal temperature for 3 hours. After confirming the completion of the reaction by nuclear magnetic resonance (NMR), the obtained reactant was subjected to distillation under reduced pressure to remove acetone as a solvent, and the thus obtained reactant was dissolved in dichloromethane, and 10 ml of ammonium hydroxide was added thereto. (NH 4 OH, 35 wt%), p-TSA was removed.
用蒸餾水對獲得的反應物進行3次洗滌後,聚集有機層進行減壓蒸餾,從而獲得上述反應式中的目的化合物-三甲基二噁烷甲酸(trimethyl dioxane carboxylic acid)(i)(110g,產率:63%)。 After the obtained reactant was washed three times with distilled water, the organic layer was collected and subjected to distillation under reduced pressure to obtain the objective compound - trimethyl dioxane carboxylic acid (i) (110 g, in the above reaction formula, Yield: 63%).
利用1H NMR確認獲得的化合物的結構,並將結果顯示在圖1中。 The structure of the obtained compound was confirmed by 1H NMR, and the results are shown in Fig. 1.
1H NMR(CDCl3,內部標準:四甲基矽烷):(ppm)1.20(s,3H)、1.4(2s,6H)、3.6(d,2H)、4.2(d,2H) 1H NMR (CDCl 3 , internal standard: tetramethyl decane): (ppm) 1.20 (s, 3H), 1.4 (2s, 6H), 3.6 (d, 2H), 4.2 (d, 2H)
步驟1 step 1
將50g的所述合成例1中製備的三甲基二噁烷甲酸(i)溶解到250ml的四氫呋喃(tetrahydrofuran,THF),常溫下攪拌製備的溶液,並慢慢添加46g的羰基二咪唑(carbonyl diiamidazole)(ii)後,常溫下攪拌4小時。此時,肉眼確認二氧化碳氣體的產生。利用1H NMR確認獲得的反應物的反應進行與否,並將結果顯示在圖2中。為了步驟2的反應,未經預熱(work up),確認化合物(iii)的轉換率(conversion)後進行下一步驟的反應。 50 g of the trimethyldioxanecarboxylic acid (i) prepared in the synthesis example 1 was dissolved in 250 ml of tetrahydrofuran (THF), and the prepared solution was stirred at normal temperature, and 46 g of carbonyldiimidazole (carbonyl) was slowly added. After diiamidazole (ii), it was stirred at normal temperature for 4 hours. At this time, the generation of carbon dioxide gas was confirmed with the naked eye. The progress of the reaction of the obtained reactant was confirmed by 1H NMR, and the results are shown in Fig. 2. For the reaction of the step 2, the reaction of the next step was carried out without confirming the conversion of the compound (iii) without work up.
1H NMR(CDCl3,內部標準:四甲基矽烷):(ppm)1.4(s,3H)、1.5(2s,6H)、3.8(d,2H)、4.3(d,2H)、7.0(s,1H)、7.6(s,1H)、8.3(s,1H) 1H NMR (CDCl 3 , internal standard: tetramethyl decane): (ppm) 1.4 (s, 3H), 1.5 (2s, 6H), 3.8 (d, 2H), 4.3 (d, 2H), 7.0 (s, 1H), 7.6 (s, 1H), 8.3 (s, 1H)
步驟2 Step 2
在上述步驟1中完成的混合溶液(包含化合物(iii)和咪唑)中添 入將1,1-二氟甲基-2-羥基乙磺酸的鈉鹽(sodium 1,1-difluoromethyl-2-hydroxy-ethanesulfonic acid)(iv)溶解於水中而製備的溶液,將槽(bath)溫度提高至75℃後進行4小時的攪拌及換流。利用1H NMR確認獲得的反應物的反應進行程度(利用1H NMR確認轉換至化合物(v)的轉換率(95%)),並將結果顯示在圖3中。 Addition to the mixed solution (comprising compound (iii) and imidazole) completed in the above step 1 a solution prepared by dissolving sodium 1,1-difluoromethyl-2-hydroxy-ethanesulfonic acid (iv) in water to form a bath (bath) After the temperature was raised to 75 ° C, stirring and commutation were carried out for 4 hours. The degree of progress of the reaction of the obtained reactant was confirmed by 1H NMR (conversion rate (95%) converted to the compound (v) was confirmed by 1H NMR), and the results are shown in Fig. 3.
1H NMR(CDCl3,內部標準:四甲基矽烷):(ppm)1.4(s,3H)、1.5(2s,6H)、3.8(d,2H)、4.3(d,2H)、4.8(t,2H) 1H NMR (CDCl 3 , internal standard: tetramethyl decane): (ppm) 1.4 (s, 3H), 1.5 (2s, 6H), 3.8 (d, 2H), 4.3 (d, 2H), 4.8 (t, 2H)
步驟3 Step 3
對上述步驟2中獲得的反應溶液(包含化合物(v)和咪唑)進行減壓蒸餾,除去THF後再次溶解到蒸餾水中。由此獲得的溶液中添入將三苯基硫三氟甲烷硫酸鹽(vi)溶解到二氯甲烷而製備的溶液後劇烈攪拌2小時。利用19F NMR對獲得的反應物進行陰離子的取代程度及反應完成情況的確認。從完成反應的反應物中分離出有機層後,用蒸餾水進行3次洗滌,聚集有機層進行減壓蒸餾,從而獲得固體粉末(vii)。 The reaction solution (containing the compound (v) and imidazole) obtained in the above step 2 was subjected to distillation under reduced pressure, and the THF was removed and dissolved again in distilled water. To the solution thus obtained, a solution prepared by dissolving triphenylsulfofyltrifluoromethane sulfate (vi) in dichloromethane was added, followed by vigorous stirring for 2 hours. The degree of substitution of the anion and the completion of the reaction were confirmed by 19F NMR. After the organic layer was separated from the reaction material in which the reaction was completed, it was washed three times with distilled water, and the organic layer was collected and distilled under reduced pressure to obtain a solid powder (vii).
利用1H NMR確認獲得的固體粉末的結構,並將結果顯示在圖4中。 The structure of the obtained solid powder was confirmed by 1H NMR, and the results are shown in Fig. 4.
1H NMR(CDCl3,內部標準:四甲基矽烷):(ppm)1.2(s,3H)、1.4(2s,6H)、3.6(d,2H)、4.2(d,2H)、4.8(t,2H)、7.7(m,15H) 1H NMR (CDCl 3 , internal standard: tetramethyl decane): (ppm) 1.2 (s, 3H), 1.4 (2s, 6H), 3.6 (d, 2H), 4.2 (d, 2H), 4.8 (t, 2H), 7.7 (m, 15H)
實驗例1 Experimental example 1
利用所述實施例1中製備的光酸發生劑形成抗蝕圖,然後對 所製備的抗蝕圖進行各種評價。 Forming a resist pattern using the photo-acid generator prepared in the above Example 1, and then The prepared resist pattern was subjected to various evaluations.
具體地,作為原料樹脂的下述化學式13所示的化合物(Mw:8500g/mol,Mw/Mn:1.75,各重複單元的莫耳比(x:y:z:w)為1:1:1:1)100重量份、按照所述實施例1中製備的作為光酸發生劑的化合物分別0.5重量份、1重量份或1.5重量份、及作為鹼性添加劑的0.5重量份的四甲基氫氧化銨(tetramethyl ammonium hydroxide)溶解在1000重量份的丙二醇單乙醚醋酸酯(propyleneglycol monoethyl ether acetate,PGMEA)中,然後用0.2μm的膜過濾器過濾,製備了對應光酸發生劑含量的抗蝕劑組成物(製備實施例1、製備實施例2及製備實施例3)。 Specifically, a compound represented by the following Chemical Formula 13 as a raw material resin (Mw: 8500 g/mol, Mw/Mn: 1.75, and molar ratio (x: y: z: w) of each repeating unit is 1:1:1). : 1) 100 parts by weight, respectively, 0.5 parts by weight, 1 part by weight or 1.5 parts by weight of the compound as the photoacid generator prepared in the above Example 1, and 0.5 parts by weight of tetramethylhydrogen as a basic additive The tetramethyl ammonium hydroxide was dissolved in 1000 parts by weight of propylene glycol monoethyl ether acetate (PGMEA), and then filtered through a 0.2 μm membrane filter to prepare a resist corresponding to the photoacid generator content. Composition (Preparation Example 1, Preparation Example 2, and Preparation Example 3).
利用旋塗機(spinor)將製得的抗蝕劑組成物塗覆到基板上,在110℃下乾燥90秒,形成厚度為0.20μm的被膜。所形成的被膜使用ArF準分子雷射步進機(棱鏡數值孔徑:0.78)進行曝光後,在110℃下熱處理90秒。接著,使用2.38重量%的四甲基氫氧化銨水溶液進行40秒的顯影,洗滌乾燥形成抗蝕圖。 The obtained resist composition was applied onto a substrate by a spiner, and dried at 110 ° C for 90 seconds to form a film having a thickness of 0.20 μm. The formed film was exposed to light using an ArF excimer laser stepper (prism numerical aperture: 0.78), and then heat-treated at 110 ° C for 90 seconds. Next, development was carried out for 40 seconds using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, followed by washing and drying to form a resist pattern.
對所製備的抗蝕圖進行各種評價,並將其結果表示在下 表1中。 Various evaluations were made on the prepared resist pattern, and the results were shown below. in FIG. 1.
下表1中的光敏度是將顯像後形成的0.10μm的線寬和間距(L/S)圖案以1比1的線寬形成的曝光量為最佳曝光量,並以該曝光量為光敏度時,顯像的最小圖案的尺寸作為解析度。 The photosensitivity in Table 1 below is the exposure amount formed by the line width and pitch (L/S) pattern of 0.10 μm formed after development at a line width of 1 to 1, which is the optimum exposure amount, and the exposure amount is In the case of photosensitivity, the size of the smallest pattern of development is taken as the resolution.
此外,針對線寬粗糙度(LWR:line width roughness),對顯像後形成的0.10μm的線寬和間距(L/S)圖案的粗度進行觀察,並測定了LWR(數值越小表示LWR越優異)。 Further, for the line width roughness (LWR), the line width and the pitch (L/S) pattern thickness of 0.10 μm formed after development were observed, and the LWR was measured (the smaller the value, the LWR) The more excellent).
如表1所示,製備實施例1至製備實施例3的抗蝕劑組成物相對於比較例的抗蝕劑組成物,在解析度和LWR方面呈現改善的特性。相反,在光敏度方面呈現低於比較例的抗蝕劑的特性。這種低光敏度是由較慢的酸的擴散速度引起的。但是,通過較慢的酸擴散速度能就夠獲得更優異的LWR。 As shown in Table 1, the resist compositions of Preparation Examples 1 to 3 exhibited improved characteristics in terms of resolution and LWR with respect to the resist composition of the comparative example. On the contrary, the characteristics of the resist lower than that of the comparative example were exhibited in terms of photosensitivity. This low sensitivity is caused by the slower rate of acid diffusion. However, a more excellent LWR can be obtained by a slower acid diffusion rate.
實驗例2 Experimental example 2
利用修正費克方程式(Modified Fick’s equation)測定利用所述實施例1中製備的光酸發生劑的抗蝕劑在形成圖案時曝光後生成的酸的擴散速度。此時,為了進行比較,用相同的方法測定在陰離子部包含作為笨重的官能團的金剛烷基的光酸發生劑-三苯基鋶金剛烷羧酸-2,2-二氟-2-磺酸乙酯(triphenylsulfonium adamantane carboxylic acid-2,2-difluoro-2-sulfo ethyl ester)的酸的擴散速度。 The diffusion rate of the acid formed after exposure by the resist of the photo-acid generator prepared in the above Example 1 at the time of pattern formation was measured by a modified Fick's equation. At this time, for comparison, a photoacid generator containing adamantyl group as a bulky functional group in the anion portion was determined by the same method - triphenylphosphonnadamanecarboxylic acid-2,2-difluoro-2-sulfonic acid The rate of acid diffusion of triphenylsulfonium adamantane carboxylic acid-2, 2-difluoro-2-sulfo ethyl ester.
測定結果,實施例1的光酸發生劑的酸擴散速度為15.6nm2/sec,而作為比較使用的光酸發生劑的酸的擴散速度為33.1nm2/sec。 As a result of the measurement, the acid diffusion rate of the photoacid generator of Example 1 was 15.6 nm 2 /sec, and the rate of diffusion of the acid as a photoacid generator for comparison was 33.1 nm 2 /sec.
如此,本發明的光酸發生劑,雖然其陰離子明顯小,卻呈現出更加緩慢的酸擴散速度,由此結果可預測到,在形成抗蝕圖案時能夠顯示更優異的LWR。 As described above, the photoacid generator of the present invention exhibits a slower acid diffusion rate although its anion is remarkably small, and as a result, it is predicted that a more excellent LWR can be exhibited when a resist pattern is formed.
以上對本發明的優選實施例進行了詳細說明,但是本發明的申請專利範圍並不限定於此,隨附的申請專利範圍中所定義的利用本發明的基本概念的各種變形及改良形態也屬於本發明的申請專利範圍。 The preferred embodiments of the present invention have been described in detail above, but the scope of the present invention is not limited thereto, and various modifications and improvements of the basic concepts of the present invention as defined in the appended claims are also included. The scope of the patent application of the invention.
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