TWI646395B - Chemically amplified i-line positive photoresist composition - Google Patents

Chemically amplified i-line positive photoresist composition Download PDF

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TWI646395B
TWI646395B TW106124888A TW106124888A TWI646395B TW I646395 B TWI646395 B TW I646395B TW 106124888 A TW106124888 A TW 106124888A TW 106124888 A TW106124888 A TW 106124888A TW I646395 B TWI646395 B TW I646395B
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photoresist composition
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TW201908866A (en
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李興傑
呂英豪
黃新義
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臺灣永光化學工業股份有限公司
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Abstract

本揭露關於一種增幅型I-line光阻組成物，包括：一聚羥苯乙烯衍生物樹脂；一光酸起始劑；以及一小分子促進劑，為如下式(I-1)至式(I-3)所示的任一化合物： The present disclosure relates to an amplification type I-line photoresist composition comprising: a polyhydroxystyrene derivative resin; a photoacid initiator; and a small molecule accelerator, which is of the following formula (I-1) to ( Any compound shown in I-3):

其中，X1至X7、R1至R12、n1、n2及m如說明書中所定義。 Wherein X 1 to X 7 , R 1 to R 12 , n1, n 2 and m are as defined in the specification.

Description

增幅型I-line光阻組成物 Amplified I-line photoresist composition

本揭露關於一種增幅型I-line光阻組成物，尤指一種具有優異的解析度及高感度特性的增幅型I-line光阻組成物。 The present disclosure relates to an amplitude-increasing I-line photoresist composition, and more particularly to an amplitude-increasing I-line photoresist composition having excellent resolution and high sensitivity characteristics.

於現今半導體黃光製程中，例如薄膜電晶體基板的製程中，所使用之曝光機曝光面積大，相對的透鏡面積也較大，造成低光源強度與透鏡數值孔徑(numerical aperture,N.A.值)低。因此，為了配合此機器缺點，常使用高感光型DNQ光。 In the current semiconductor yellow light process, for example, in the process of a thin film transistor substrate, the exposure machine used has a large exposure area and a relatively large lens area, resulting in low light source intensity and low numerical aperture (NA value). . Therefore, in order to cope with the disadvantages of this machine, high-sensitivity DNQ light is often used.

以目前而言，正型DNQ光阻一直是薄膜電晶體液晶顯示器(TFT-LCD)黃光製程中的重要關鍵材料，但此類光阻的製程在1.5μm的膜厚下一直受限於2μm的解析度，且所得之圖形無法具有垂直邊壁。若轉換使用增幅型光阻，不但可以進一步增加感度，減低製程時間，也可得到邊壁垂直之產品。然而，增幅型光阻需另加一道曝後烤(PEB)製程來穩定線寬與減少光阻顯影後殘留，但因曝後烤製程繁雜，幾乎無法在現有的TFT-LCD之黃光製程後多增加一道曝後烤製程來替換原本DNQ光阻。 At present, positive DNQ photoresist has always been an important key material in the thin film transistor liquid crystal display (TFT-LCD) yellow light process, but the process of such photoresist is limited to 2μm at a film thickness of 1.5μm. Resolution, and the resulting graphics cannot have vertical side walls. If the conversion uses an amplitude-increasing photoresist, not only can the sensitivity be further increased, the process time can be reduced, and the product with the vertical wall can be obtained. However, the amplified photoresist needs to be additionally subjected to a post-bake (PEB) process to stabilize the line width and reduce the residual residue after the development of the photoresist. However, due to the complicated baking process after exposure, it is almost impossible to process the yellow TFT process of the existing TFT-LCD. Add an additional post-exposure process to replace the original DNQ photoresist.

因此，若能發展出一種可無須透過曝後烤製程的增幅型光阻，則可改善原本DNQ光阻解析度受限的問題，更可避免現有增幅型光組需要曝後烤製程的限制，而更加適用於現有的半導體製程。 Therefore, if an increased-type photoresist that can be passed through the post-exposure baking process can be developed, the problem of limited resolution of the original DNQ photoresist can be improved, and the limitation of the existing post-exposure baking process can be avoided. It is more suitable for existing semiconductor processes.

本揭露之主要目的在於提供一種增幅型I-line光阻組成物，其具有優異的解析度及高感度特性。 The main object of the present disclosure is to provide an amplitude-increasing I-line photoresist composition which has excellent resolution and high sensitivity characteristics.

本揭露的增幅型I-line光阻組成物，包括：一聚羥苯乙烯衍生物樹脂；一光酸起始劑；以及一小分子促進劑，為如下式(I-1)至式(I-3)所示的任一化合物： The amplified type I-line photoresist composition of the present invention comprises: a polyhydroxystyrene derivative resin; a photoacid initiator; and a small molecule accelerator, which is represented by the following formula (I-1) to (I) -3) Any of the compounds shown:

其中，X1、X2、X3、X4、X5、X6及X7各自獨立為，且Ra為經取代或未經取代的C1-20烷基、或經取代或未經取代的C3-30環烷基，或Ra與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基；每一R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11及R12各自獨立為氫、經取代或未經取代的C1-20烷基、經取代或未經取代的C3-30環烷基、經取代或未經取代的C6-14芳基、鹵素或，其中Rf為經取代或未經取代的C1-20烷基、或經取代或未經取代的C3-30環烷基，或Rf與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基； A為一單鍵、經取代或未經取代的C1-20亞烷基、經取代或未經取代的C3-30亞 環烷基、經取代或未經取代的亞芴基或，其中Rb及Rc各自 獨立為經取代或未經取代的C1-20烷基，Rd及Re各自獨立為經，且Rg為經取代或未經取代的C1-20烷基、或經取代或未經取代的C3-30環烷基，或Rg與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基，而p1及p2各自獨立為0至4之整數；n1及n2各自獨立為1至3之整數；以及m為0至10之整數。 Wherein X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are each independently And R a is a substituted or unsubstituted C 1-20 alkyl group, or a substituted or unsubstituted C 3-30 cycloalkyl group, or a C atom adjacent to R and O, and O and The base forms a 5-membered or 6-membered heterocyclic group; each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 6-14 aryl, halogen or Wherein R f is a substituted or unsubstituted C 1-20 alkyl, or substituted or unsubstituted C 3-30 cycloalkyl, or R f and O, and O-adjacent C atoms and A The group together form a 5- or 6-membered heterocyclic group; A is a single bond, a substituted or unsubstituted C 1-20 alkylene group, a substituted or unsubstituted C 3-30 cycloalkylene group Substituted or unsubstituted fluorenylene or Wherein R b and R c are each independently a substituted or unsubstituted C 1-20 alkyl group, and R d and R e are each independently And R g is a substituted or unsubstituted C 1-20 alkyl, or substituted or unsubstituted C 3-30 cycloalkyl, or R g and O, and O-adjacent C atoms and A The base forms a 5- or 6-membered heterocyclic group, and p1 and p2 are each independently an integer of 0 to 4; n1 and n2 are each independently an integer of 1 to 3; and m is an integer of 0 to 10.

以往的增幅型光阻需另加一道曝後烤製程來穩定線寬與減少光阻顯影後殘留。本揭露的增幅型I-line光阻組成物包括聚羥苯乙烯(poly(hydroxystyrene))衍生物樹脂、具保護基之小分子促進劑、及光酸起始劑；其中具保護基之小分子促進劑的結構中包含多個醇基位接枝上保護基，在未曝光區作為一溶解抑制劑，而該保護基於曝光後受到光酸作用切除，進而幫助樹脂溶解，增加溶解速率，在曝光區作為一溶解促進劑，藉此可提升黃光微影製程中聚羥苯乙烯衍生物樹脂(增幅型正行光阻)的敏感性及解析度，故可免除後續之曝後烤製程以減少製程時間及成本，並連帶加強曝光區之對比度。此外，於半導體製程中，本揭露的增幅型I-line光阻組成物在低數值孔徑(numerical aperture,N.A.值)之FPD曝光機下具有高感光度、高解析度。再者，本揭露的增幅型I-line光阻組成物更與導電ITO玻璃基材具良好附著性、耐草酸濕式蝕刻等特性。因此，本揭露的增幅型I-line光阻組成物可運用於生產於更高解析度之半導體製程上。 In the past, the increased-type photoresist needs to be additionally subjected to an exposure and post-baking process to stabilize the line width and reduce the residue after development of the photoresist. The amplified I-line photoresist composition of the present disclosure comprises a poly(hydroxystyrene) derivative resin, a small molecule promoter having a protective group, and a photoacid initiator; wherein the protective molecule is a small molecule The structure of the accelerator comprises a plurality of alcohol groups grafted with a protecting group in the unexposed area as a dissolution inhibitor, and the protection is removed by photoacid action after exposure, thereby helping the resin to dissolve and increasing the dissolution rate during exposure. As a dissolution promoter, the region can improve the sensitivity and resolution of the polyhydroxystyrene derivative resin (amplified positive photoresist) in the yellow photolithography process, thereby eliminating the subsequent post-exposure baking process to reduce the process time and Cost, and in conjunction with enhanced contrast in the exposure zone. In addition, in the semiconductor process, the amplified I-line photoresist composition of the present invention has high sensitivity and high resolution under a low numerical aperture (N.A. value) FPD exposure machine. Furthermore, the amplified I-line photoresist composition of the present invention has better adhesion to the conductive ITO glass substrate and is resistant to oxalic acid wet etching. Thus, the inventive amplified I-line photoresist composition can be used in semiconductor processes of higher resolution.

於本揭露的一實施例中，小分子促進劑為式(I-1)所示的小分子促進劑。 In an embodiment of the present disclosure, the small molecule promoter is a small molecule promoter represented by formula (I-1).

於本揭露的一實施例中，式(I-1)中的X1與X2可相同或不同，R1與R2可相同或不同，且n1與n2可相同或不同；或X1與X2相同，R1與R2相同，且n1與n2相同。 In an embodiment of the present disclosure, X 1 and X 2 in formula (I-1) may be the same or different, R 1 and R 2 may be the same or different, and n1 and n2 may be the same or different; or X 1 and X 2 is the same, R 1 is the same as R 2 , and n1 is the same as n2.

於本揭露的一實施例中，式(I-1)中的R1與R2可各自獨立為氫、甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、叔丁基、苯基、環 己基、氟、氯、或 In an embodiment of the present disclosure, R 1 and R 2 in the formula (I-1) may each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl. , isobutyl, tert-butyl, phenyl, cyclohexyl, fluorine, chlorine, or

於本揭露的一實施例中，式(I-1)中的A可為一單鍵、經苯基取代的C1-20亞烷基、未經取代的C1-20亞烷基、經甲基或乙基取代的C5-6亞環烷基、未經取代的C5-6亞環烷基、或未經取代的亞芴基。 In an embodiment of the present disclosure, A in the formula (I-1) may be a single bond, a phenyl substituted C 1-20 alkylene group, an unsubstituted C 1-20 alkylene group, Methyl or ethyl substituted C 5-6 cycloalkylene, unsubstituted C 5-6 cycloalkylene, or unsubstituted anthracenylene.

於本揭露的一實施例中，小分子促進劑為式(I-2)所示的小分子促進劑。 In an embodiment of the present disclosure, the small molecule promoter is a small molecule promoter represented by formula (I-2).

於本揭露的一實施例中，式(I-2)中，X3與X4可相同或不同，R3、R4、R5及R6可相同或不同，且R7、R8與R9可相同或不同；或X3與X4相同，R3、R4與R5相同，R6與R3、R4及R5相同或不同，且R7、R8與R9相同。 In an embodiment of the present disclosure, in the formula (I-2), X 3 and X 4 may be the same or different, and R 3 , R 4 , R 5 and R 6 may be the same or different, and R 7 and R 8 are R 9 may be the same or different; or X 3 is the same as X 4 , R 3 , R 4 are the same as R 5 , R 6 is the same or different from R 3 , R 4 and R 5 , and R 7 , R 8 are the same as R 9 .

於本揭露的一實施例中，式(I-2)中的R3、R4與R5為甲基或乙基，R6為經取代的苯基，而R7、R8與R9為氫。 In one embodiment of the present disclosure, R 3 , R 4 and R 5 in formula (I-2) are methyl or ethyl, R 6 is substituted phenyl, and R 7 , R 8 and R 9 It is hydrogen.

於本揭露的一實施例中，小分子促進劑為式(I-3)所示的小分子促進劑。 In an embodiment of the present disclosure, the small molecule promoter is a small molecule promoter represented by formula (I-3).

於本揭露的一實施例中，式(I-3)中，X5、X6與X7可相同或不同，R10、R11與R12可相同或不同，且m為1或2：或X5、X6與X7相同，R10、R11與R12相同，且m為1或2。 In an embodiment of the present disclosure, in the formula (I-3), X 5 , X 6 and X 7 may be the same or different, and R 10 , R 11 and R 12 may be the same or different, and m is 1 or 2: Or X 5 , X 6 are the same as X 7 , R 10 , R 11 are the same as R 12 , and m is 1 or 2.

於本揭露的一實施例中，式(I-3)中的R10、R11與R12為氫。 In an embodiment of the present disclosure, R 10 , R 11 and R 12 in the formula (I-3) are hydrogen.

於本揭露的一實施例中，小分子促進劑不限於使用單一小分子促進劑，可多種小分子促進劑合併使用。舉例來說，可將式(I-1)與式(I-2)的小分子促進劑合併使用。 In an embodiment of the present disclosure, the small molecule promoter is not limited to the use of a single small molecule promoter, and a plurality of small molecule promoters may be used in combination. For example, a small molecule accelerator of the formula (I-1) and the formula (I-2) can be used in combination.

於本揭露的一實施例中，X1、X2、X3、X4、X5、X6及X7各自獨立為，其中Ra可為未經取代的C1-3烷基、經C1-3烷氧基取代的C1-3烷基、或未經取代的C5-7環烷基，或Ra與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基；或Ra可為未經取代的C2-3烷基、經C1-3烷氧基取代的C2-3烷基、或未經取代的環己基，或Ra與O、和O相鄰的C原子及甲基一同形成一5員或6員的未經取代的雜環基。於本揭露中，X1、X2、X3、X4、X5、X6及X7的具體例子 包括，但不限於，或 In an embodiment of the present disclosure, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , and X 7 are each independently Wherein R a may be an unsubstituted C 1-3 alkyl group, a C 1-3 alkyl group substituted with a C 1-3 alkoxy group, or an unsubstituted C 5-7 cycloalkyl group, or R a The C atom and the methyl group adjacent to O and O together form a 5- or 6-membered heterocyclic group; or R a may be an unsubstituted C 2-3 alkyl group, a C 1-3 alkoxy group. substituted C 2-3 alkyl, or unsubstituted cyclohexyl group, or R a and O, and O-methyl-adjacent C atoms together and formed without a 5 or 6-membered substituted heterocyclic group. In the disclosure, specific examples of X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 include, but are not limited to, or

於本揭露的一實施例中，中的Rf可為未經取代的C1-3烷基、經C1-3烷氧基取代的C1-3烷基、或未經取代的C5-7環烷基，或Rf與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基；或Rf可為未經取代的C2-3烷基、經C1-3烷氧基取代的C2-3烷基、或未經取代的環己基，或Rf與O、和O相鄰的C原子及甲基一同形成一5員或6員的未經取代的雜環基。 In an embodiment of the present disclosure, R f in the group may be an unsubstituted C 1-3 alkyl group, a C 1-3 alkyl group substituted with a C 1-3 alkoxy group, or an unsubstituted C 5-7 cycloalkyl group, or R f The C atom and the methyl group adjacent to O and O together form a 5- or 6-membered heterocyclic group; or R f may be an unsubstituted C 2-3 alkyl group, a C 1-3 alkoxy group. substituted C 2-3 alkyl, or unsubstituted cyclohexyl group, or R f and O, and O-methyl-adjacent C atoms together and formed without a 5 or 6-membered substituted heterocyclic group.

於本揭露的一實施例中，中的Rg可為未經取代的C1-3烷基、經C1-3烷氧基取代的C1-3烷基、或未經取代的C5-7環烷基，或Rg與O、和O 相鄰的C原子及甲基一同形成一5員或6員的雜環基；或Rg可為未經取代的C2-3烷基、經C1-3烷氧基取代的C2-3烷基、或未經取代的環己基，或Rg與O、和O相鄰的C原子及甲基一同形成一5員或6員的未經取代的雜環基。 In an embodiment of the present disclosure, The R g in the group may be an unsubstituted C 1-3 alkyl group, a C 1-3 alkyl group substituted with a C 1-3 alkoxy group, or an unsubstituted C 5-7 cycloalkyl group, or R g The C atom and the methyl group adjacent to O and O together form a 5- or 6-membered heterocyclic group; or R g may be an unsubstituted C 2-3 alkyl group, a C 1-3 alkoxy group. substituted C 2-3 alkyl, or unsubstituted cyclohexyl group, or R g and O, and O-methyl-adjacent C atoms together and formed without a 5 or 6-membered substituted heterocyclic group.

於本揭露中，小分子促進劑可選自由如下式(1)至(26)所組成之群組： In the present disclosure, the small molecule promoter may be selected from the group consisting of the following formulas (1) to (26):

於式(1)至式(26)中，X1、X2、X3、X4、X5、X6及X7各自獨立為或，而 為或 In the formulae (1) to (26), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are each independently or ,and for or

本揭露的小分子促進劑的具體例子包括，但不限於： Specific examples of the small molecule accelerators disclosed herein include, but are not limited to:

於本揭露的一實施例中，聚羥苯乙烯衍生物樹脂之重量平均分子量可介於3000至25000之間。 In an embodiment of the present disclosure, the polyhydroxystyrene derivative resin may have a weight average molecular weight of between 3,000 and 25,000.

於本揭露的一實施例中，聚羥苯乙烯衍生物樹脂可包括如下式(II-1)及(II-2)的重複單元： In an embodiment of the present disclosure, the polyhydroxystyrene derivative resin may include repeating units of the following formulas (II-1) and (II-2):

其中，Rh為經取代或未經取代的C1-20烷基、或經取代或未經取代的C3-30環烷基，或Rh與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基。 Wherein R h is a substituted or unsubstituted C 1-20 alkyl group, or a substituted or unsubstituted C 3-30 cycloalkyl group, or a C atom adjacent to R h and O, and O and The base forms a 5- or 6-membered heterocyclic group.

其中，式(II-1)重複單元與式(II-2)的重複單元於該聚羥苯乙烯衍生物樹脂中的莫爾比可介於1：1至1：4之間。 Wherein, the molar ratio of the repeating unit of the formula (II-1) to the repeating unit of the formula (II-2) in the polyhydroxystyrene derivative resin may be between 1:1 and 1:4.

其中，Rh可為未經取代的C1-20烷基，或Rh與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基。於本揭露的一實施例中，Rh可為未經取代的C1-3烷基、經C1-3烷氧基取代的C1-3烷基、或未經取代的C5-7環烷基，或Rh與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基；或Rh可為未經取代的C2-3烷基、經C1-3烷氧基取代的C2-3烷基、或未經取代的環己基，或Rh與O、和O相鄰的C原子及甲基一同形成一5員或6員的未經取代的雜環基。 Wherein, R h may be an unsubstituted C 1-20 alkyl, or R h and O, and O-methyl-adjacent C atoms and together form a 5 or 6-membered heterocyclic group. In an embodiment of the present disclosure, R h may be an unsubstituted C 1-3 alkyl group, a C 1-3 alkyl group substituted with a C 1-3 alkoxy group, or an unsubstituted C 5-7 cycloalkyl, or R h and O, and O-methyl-adjacent C atoms and together form a 5 or 6-membered heterocyclic group; or R h can be unsubstituted C 2-3 alkyl, a C 1-3 alkoxy-substituted C 2-3 alkyl, or unsubstituted cyclohexyl group, or R h and O, and O-methyl-adjacent C atoms and not together form a 5 or 6-membered Substituted heterocyclic group.

於本揭露中，聚羥苯乙烯衍生物樹脂的式(II-1)重複單元的具體例子包括，但不限於： In the present disclosure, specific examples of the repeating unit of the formula (II-1) of the polyhydroxystyrene derivative resin include, but are not limited to:

於本揭露中，前述式(II-1a)至式(II-1e)可單獨或合併使用。舉例來說，聚羥苯乙烯衍生物樹脂可同時包括式(II-1a)、式(II-1c)及式(II-2)的重複單元。 In the present disclosure, the above formula (II-1a) to formula (II-1e) may be used singly or in combination. For example, the polyhydroxystyrene derivative resin may include a repeating unit of the formula (II-1a), the formula (II-1c), and the formula (II-2).

於本揭露中，光酸起始劑的種類並無特殊限制，只要能促使聚羥苯乙烯衍生物樹脂進行聚合反應即可。於本揭露的一實施例中，光酸起始劑可如下式(III)所示： In the present disclosure, the kind of the photoacid initiator is not particularly limited as long as the polyhydroxystyrene derivative resin is allowed to undergo polymerization. In an embodiment of the present disclosure, the photoacid initiator can be represented by the following formula (III):

其中Rx為C1-20烷基。 Wherein R x is a C 1-20 alkyl group.

於本揭露的一實施例中，光酸起始劑如下式(III-1)所示： In an embodiment of the present disclosure, the photoacid initiator is represented by the following formula (III-1):

於本揭露中，聚羥苯乙烯衍生物樹脂、小分子促進劑及光酸起始劑的含量並無特殊限制，可依據製程條件來做變更。於本揭露的一實施例中，增幅型I-line光阻組成物可包括：大於或等於10重量分且小於或等於30重量分之聚羥苯乙烯衍生物樹脂；大於0重量分且小於或等於10重量分之小分子促進劑；以及大於或等於0.5重量分且小於或等於3重量分之光酸起始劑。 In the present disclosure, the content of the polyhydroxystyrene derivative resin, the small molecule accelerator, and the photoacid initiator is not particularly limited and may be changed depending on the process conditions. In an embodiment of the present disclosure, the amplified I-line photoresist composition may include: a polyhydroxystyrene derivative resin of greater than or equal to 10 parts by weight and less than or equal to 30 parts by weight; greater than 0 parts by weight and less than or A small molecule accelerator equal to 10 parts by weight; and a photoacid starter greater than or equal to 0.5 parts by weight and less than or equal to 3 parts by weight.

於本揭露的增幅型I-line光阻組成物中，烷基、亞烷基、環烷基、亞環烷基、芳基、亞芳基可選擇性的被一取代基所取代或為取代，其中該取代基可為烷基、環烷基、鹵素、烷氧基、烯基、雜環基、芳基、酯基、胺基、或羧基，但烷基不會再被烷基所取代。 In the amplified I-line photoresist composition of the present disclosure, an alkyl group, an alkylene group, a cycloalkyl group, a cycloalkylene group, an aryl group or an arylene group may be optionally substituted or substituted with a substituent. Wherein the substituent may be an alkyl group, a cycloalkyl group, a halogen, an alkoxy group, an alkenyl group, a heterocyclic group, an aryl group, an ester group, an amine group, or a carboxyl group, but the alkyl group is no longer substituted by an alkyl group. .

於本揭露的增幅型I-line光阻組成物中，所謂之「鹵素」包括氟、氯、溴、及碘，較佳為氟、氯、或溴。於本揭露中，所謂之「(亞)烷基」包括直 鏈及支鏈之(亞)烷基，較佳為包括直鏈及支鏈之C1-20(亞)烷基，再佳為包括直鏈及支鏈之C1-12(亞)烷基，且更佳為包括直鏈及支鏈之(亞)C1-6烷基；且其具體例子包括，但不限於：(亞)甲基、(亞)乙基、(亞)丙基、(亞)異丙基、(亞)丁基、(亞)異丁基、(亞)第二丁基、(亞)叔丁基。所謂之「(亞)芳基」包括6員碳單環、10碳雙環、14員三環芳香族環系統，其具體例子包括，但不限於：(亞)苯基、(亞)萘基、(亞)芘基、(亞)蒽基及(亞)菲基，且較佳為(亞)苯基。所謂之「(亞)環烷基」一詞係指單價或雙價飽和環狀碳氫基團，其包含3至30個碳原子(如C3-C12)，其具體例子包含，但不限於：(亞)環丙基、(亞)環丁基、(亞)環戊基、(亞)環己基、1,4-亞環己基、(亞)環庚基、(亞)環辛基。 In the expanded type I-line resist composition of the present disclosure, the "halogen" includes fluorine, chlorine, bromine, and iodine, preferably fluorine, chlorine, or bromine. In the present disclosure, the term "(alkylene)" includes straight-chain and branched (alkylene) alkyl groups, preferably including straight-chain and branched C 1-20 (alkylene) alkyl groups, and more preferably Included are straight-chain and branched C 1-12 (alkylene) alkyl groups, and more preferably include straight-chain and branched (sub)C 1-6 alkyl groups; and specific examples thereof include, but are not limited to: ) methyl, (i)ethyl, (i)propyl, (i)isopropyl, (butylene), (i)isobutyl, (sub)dibutyl, (sub)tert-butyl . The "(sub)aryl group" includes a 6-membered carbon monocyclic ring, a 10-carbon bicyclic ring, and a 14-membered tricyclic aromatic ring system, and specific examples thereof include, but are not limited to, (phenylene), (y)naphthyl, (Sub)indolyl, (sub)indenyl and (i)phenanthrenyl, and preferably (phenylene)phenyl. The term "(sub)cycloalkyl" means a monovalent or divalent saturated cyclic hydrocarbon group containing from 3 to 30 carbon atoms (eg, C 3 -C 12 ), specific examples of which include, but not Limited to: (sub)cyclopropyl, (i)cyclobutyl, (i)cyclopentyl, (sub)cyclohexyl, 1,4-cyclohexylene, (sub)cycloheptyl, (sub)cyclooctyl .

於本揭露的增幅型I-line光阻組成物中，除了聚羥苯乙烯衍生物樹脂、小分子促進劑及光酸起始劑外，更可包括一溶劑。其中，溶劑的種類及含量並無特殊限制，只要能使溶質能有良好溶解性即可。於本揭露的一實施例中，溶劑的具體例子可為丙二醇單甲醚醋酸酯(Propylene Glycol Monomethyl Ether Acetate,PGMEA)，但本揭露並不僅限於此。此外，於本揭露的一實施例中，溶劑的含量可為大於或等於60重量分且小於或等於80重量分。 In addition to the polyhydroxystyrene derivative resin, the small molecule accelerator, and the photoacid initiator, the amplified I-line photoresist composition of the present disclosure may further comprise a solvent. The type and content of the solvent are not particularly limited as long as the solute has good solubility. In an embodiment of the present disclosure, a specific example of the solvent may be Propylene Glycol Monomethyl Ether Acetate (PGMEA), but the disclosure is not limited thereto. Furthermore, in an embodiment of the present disclosure, the solvent may be included in an amount of greater than or equal to 60 parts by weight and less than or equal to 80 parts by weight.

此外，於本揭露的增幅型I-line光阻組成物中，除了聚羥苯乙烯衍生物樹脂、小分子促進劑及光酸起始劑外，更可選擇性的包括其他添加劑，例如：酸抑制劑、附著添加劑、介面活性劑等。 In addition, in the amplified I-line photoresist composition of the present disclosure, in addition to the polyhydroxystyrene derivative resin, the small molecule accelerator and the photoacid initiator, other additives such as acid are more selectively included. Inhibitors, adhesion additives, surfactants, and the like.

圖1為本揭露製備例1的化合物(1-a)的1H NMR光譜圖。 Fig. 1 is a 1H NMR spectrum chart of the compound (1-a) of Preparation Example 1.

圖2為本揭露製備例2的化合物(1-b)的1H NMR光譜圖。 2 is a 1H NMR spectrum chart of the compound (1-b) of Preparation Example 2.

圖3為本揭露製備例3的化合物(1-c)的1H NMR光譜圖。 Fig. 3 is a 1H NMR spectrum chart of the compound (1-c) of Preparation Example 3 of the present invention.

圖4為本揭露製備例4的化合物(1-d)的1H NMR光譜圖。 4 is a 1H NMR spectrum chart of the compound (1-d) of Preparation Example 4.

圖5為本揭露製備例5的化合物(1-e)的1H NMR光譜圖。 Fig. 5 is a 1H NMR spectrum chart of the compound (1-e) of Preparation Example 5 of the present invention.

圖6為本揭露製備例6的化合物(1-f)的1H NMR光譜圖。 Fig. 6 is a 1H NMR spectrum chart of the compound (1-f) of Preparation Example 6 of the present invention.

以下係藉由特定的具體實施例說明本揭露之實施方式，熟習此技藝之人士可由本說明書所揭示之內容輕易地了解本揭露之其他優點與功效。本揭露亦可藉由其他不同的具體實施例加以施行或應用，本說明書中的各項細節亦可針對不同觀點與應用，在不悖離本創作之精神下進行各種修飾與變更。 The embodiments of the present disclosure are described by way of specific examples, and those skilled in the art can readily appreciate the other advantages and advantages of the disclosure. The present disclosure can also be implemented or applied by other different embodiments. The details of the present specification can also be applied to various viewpoints and applications, and various modifications and changes can be made without departing from the spirit of the present invention.

除非文中另有說明，否則說明書及所附申請專利範圍中所使用之單數形式「一」及「該」包括一或複數個體。 The singular forms "a", "the" and "the"

除非文中另有說明，否則說明書及所附申請專利範圍中所使用之術語「或」通常包括「及/或」之含義。 The term "or" as used in the specification and the scope of the appended claims generally includes the meaning of "and/or" unless otherwise indicated.

本文所使用之術語「重量平均分子量」，係利用凝膠滲透層析(GPC)溶劑：四氫呋喃(THF)，所測定之換算成聚苯乙烯之重量平均分子量(Mw)的值。 The term "weight average molecular weight" as used herein is a value measured by gel permeation chromatography (GPC) solvent: tetrahydrofuran (THF), which is converted into a weight average molecular weight (Mw) of polystyrene.

製備例1-製備化合物(1-a) Preparation Example 1 - Preparation of Compound (1-a)

雙酚Z(Bisphenol Z)(4,4'-環亞己基雙苯酚(4,4'-Cyclohexylidenebisphenol),MW=268,2.0g,7.46mmol)溶於THF(15mL)，在冰浴下將甲苯-4-磺酸(toluene-4-sulfonic acid)(MW=190,0.14g,0.75mmol,0.1 eq)直接加入反應溶液中，再逐滴加入保護基乙基乙烯基醚(ethyl vinyl ether)(MW=72,2.426mL,0.0254mol,3.4eq)攪拌三十分鐘之後，加入三乙基胺終止反應。使用旋轉濃縮機去除THF及三乙基胺，進行管柱層析純化，先己烷：三乙基胺=4：1與矽膠充分攪拌混和後配置成管柱，再以己烷作為沖提液純化，將純化後產物溶於己烷，在0℃下進行再結晶，可得到白色小分子產物。其中，白色小分子產物的1H NMR光譜如圖1所示。 Bisphenol Z (Bisphenol Z) (4,4 ' - cyclohexylidene bisphenol (4,4' -Cyclohexylidenebisphenol), MW = 268,2.0g, 7.46mmol) was dissolved in THF (15mL), under ice Toluene Toluene-4-sulfonic acid (MW=190, 0.14 g, 0.75 mmol, 0.1 eq) was directly added to the reaction solution, and ethyl vinyl ether (ethyl vinyl ether) was added dropwise ( MW = 72, 2.426 mL, 0.0254 mol, 3.4 eq) After stirring for thirty minutes, the reaction was quenched by the addition of triethylamine. The THF and triethylamine were removed by a rotary concentrator and purified by column chromatography. The hexane:triethylamine=4:1 was mixed with the cerium gel and mixed into a column, and then hexane was used as the extract. After purification, the purified product was dissolved in hexane and recrystallized at 0 ° C to obtain a white small molecule product. Among them, the 1H NMR spectrum of the white small molecule product is shown in FIG.

製備例2-製備化合物(1-b) Preparation Example 2 - Preparation of Compound (1-b)

雙酚Z(MW=268,2.0g,7.46mmol)溶於THF(15mL)，在冰浴下將甲苯-4-磺酸(MW=190,0.14g,0.75mmol,0.1eq)直接加入反應溶液中，再逐滴加入保護基3,4-二氫-2H-哌喃(3,4-dihydro-2H-pyran)(MW=84.12,6.8mL,7.46mmol,10eq)攪拌三十分鐘之後，加入三乙基胺終止反應。使用旋轉濃縮機去除THF及三乙基胺，進行管柱層析純化，先以己烷：三乙基胺=4：1與矽膠充分攪拌混和後配置成管柱，再以己烷作為沖提液純化，將純化後產物溶於己烷，在0℃下進行再結晶，可得到白色小分子產物。其中，白色小分子產物的1H NMR光譜如圖2所示。 Bisphenol Z (MW = 268, 2.0 g, 7.46 mmol) was dissolved in THF (15 mL), and toluene-4-sulfonic acid (MW = 190, 0.14 g, 0.75 mmol, 0.1 eq) was directly added to the reaction solution in an ice bath. Then, the protective group 3,4-dihydro-2H-pyran (MW=84.12, 6.8 mL, 7.46 mmol, 10 eq) was added dropwise thereto for 30 minutes, and then added. The reaction was terminated by triethylamine. The THF and triethylamine were removed by a rotary concentrator, and purified by column chromatography. The mixture was firstly stirred and mixed with hexane:triethylamine=4:1 and cerium, and then placed into a column, and then hexane was used as a rinsing. The liquid was purified, and the purified product was dissolved in hexane and recrystallized at 0 ° C to obtain a white small molecule product. Among them, the 1H NMR spectrum of the white small molecule product is shown in Fig. 2.

製備例3-製備化合物(1-c) Preparation Example 3 - Preparation of Compound (1-c)

9,9-二(3-甲基-4-羥基苯基)芴(Biscresolfluorene,BCF,MW=378.46,2.0g,5.28mmol)溶於THF(10.5mL)，在冰浴下將甲苯-4-磺酸(MW=190,0.2g,1.05mmol,0.2eq)直接加入反應溶液中，再逐滴加入保護基乙基乙烯基醚(MW=72,1.259mL,0.0132mol,2.5eq)攪拌十分鐘之後，加入三乙基胺終止反應。使用旋轉濃縮機去除THF及三乙基胺，進行管柱層析純化，先以己烷：三乙基胺=4：1與矽膠充分攪拌混和後配置成管柱，再以己烷作為沖提液純化，將純化後產物溶於己烷，在0℃下進行再結晶，可得到白色小分子產物。其中，白色小分子產物的1H NMR光譜如圖3所示。 9,9-bis(3-methyl-4-hydroxyphenyl)indole (Biscresolfluorene, BCF, MW=378.46, 2.0 g, 5.28 mmol) was dissolved in THF (10.5 mL) and toluene-4- The sulfonic acid (MW = 190, 0.2 g, 1.05 mmol, 0.2 eq) was added directly to the reaction solution, and the protective group ethyl vinyl ether (MW = 72, 1.259 mL, 0.0132 mol, 2.5 eq) was added dropwise for ten minutes. Thereafter, the reaction was terminated by the addition of triethylamine. The THF and triethylamine were removed by a rotary concentrator, and purified by column chromatography. The mixture was firstly stirred and mixed with hexane:triethylamine=4:1 and cerium, and then placed into a column, and then hexane was used as a rinsing. The liquid was purified, and the purified product was dissolved in hexane and recrystallized at 0 ° C to obtain a white small molecule product. Among them, the 1H NMR spectrum of the white small molecule product is shown in FIG.

製備例4-製備化合物(1-d) Preparation Example 4 - Preparation of Compound (1-d)

BCF(MW=378.46,2.0g,5.28mmol)溶於THF(10.5mL)，在冰浴下將甲苯-4-磺酸(MW=190,0.2g,1.05mmol,0.2eq)直接加入反應溶液中，再逐滴加入保護基3,4-二氫-2H-哌喃(MW=84.12,4.816mL,0.0528mol,10eq)攪拌十分鐘之後，加入三乙基胺終止反應。使用旋轉濃縮機去除THF及三乙基胺，進行管柱層析純化，先以己烷：三乙基胺=4：1與矽膠充分攪拌混和後配置成管柱，再以己烷作為沖提液純化，將純化後產物溶於己烷，在0℃下進行再結晶，可得到白色小分子產物。其中，白色小分子產物的1H NMR光譜如圖4所示。 BCF (MW=378.46, 2.0 g, 5.28 mmol) was dissolved in THF (10.5 mL), and toluene-4-sulfonic acid (MW=190, 0.2 g, 1.05 mmol, 0.2 eq) was directly added to the reaction solution under ice bath. Then, the protective group 3,4-dihydro-2H-pyran (MW = 84.12, 4.816 mL, 0.0528 mol, 10 eq) was added dropwise thereto for 10 minutes, and then the reaction was terminated by the addition of triethylamine. The THF and triethylamine were removed by a rotary concentrator, and purified by column chromatography. The mixture was firstly stirred and mixed with hexane:triethylamine=4:1 and cerium, and then placed into a column, and then hexane was used as a rinsing. The liquid was purified, and the purified product was dissolved in hexane and recrystallized at 0 ° C to obtain a white small molecule product. Among them, the 1H NMR spectrum of the white small molecule product is shown in FIG.

製備例5-製備化合物(1-e) Preparation Example 5 - Preparation of Compound (1-e)

三(4-羥基苯基)甲烷(Tris(4-hydroxyphenyl)methane,BIP-PHBZ,MW=292.33,2.0g,6.84mmol)溶於THF(13.7mL)，在冰浴下將甲苯-4-磺酸(MW=190,0.388g,2.04mmol,0.3eq)直接加入反應溶液中，再逐滴加入保護基乙基乙烯基醚(MW=72,2.944mL,0.0307mol,4.5eq)攪拌十分鐘之後，加入三乙基胺終止反應。使用旋轉濃縮機去除THF及三乙基胺，進行管柱層析純化，先以己烷：三乙基胺=4：1與矽膠充分攪拌混和後配置成管柱，再以己烷作為沖提液純化，將純化後產物溶於己烷，在0℃下進行再結晶，可得到淡黃色小分子產物。其中，淡黃色小分子產物的1H NMR光譜如圖5所示。 Tris(4-hydroxyphenyl)methane (Tris(4-hydroxyphenyl)methane, BIP-PHBZ, MW=292.33, 2.0 g, 6.84 mmol) was dissolved in THF (13.7 mL). The acid (MW = 190, 0.388 g, 2.04 mmol, 0.3 eq) was directly added to the reaction solution, followed by dropwise addition of the protective ethyl vinyl ether (MW = 72, 2.944 mL, 0.0307 mol, 4.5 eq) for ten minutes. The reaction was terminated by the addition of triethylamine. The THF and triethylamine were removed by a rotary concentrator, and purified by column chromatography. The mixture was firstly stirred and mixed with hexane:triethylamine=4:1 and cerium, and then placed into a column, and then hexane was used as a rinsing. The liquid was purified, and the purified product was dissolved in hexane and recrystallized at 0 ° C to obtain a pale yellow small molecule product. Among them, the 1H NMR spectrum of the pale yellow small molecule product is shown in FIG.

製備例6-製備化合物(1-f) Preparation Example 6 - Preparation of Compound (1-f)

BIP-PHBZ(MW=292.33,2.0g,6.84mmol)溶於THF(13.7mL)，在冰浴下將甲苯-4-磺酸(MW=190,0.388g,2.04mol,0.3eq)直接加入反應溶液中，再逐滴加入保護基3,4-二氫-2H-哌喃(MW=84.12,6.24mL,0.0684mol,10eq)攪拌十分鐘之後，加入三乙基胺終止反應。使用旋轉濃縮機去除THF及三乙基胺，進行管柱層析純化，先以己烷：三乙基胺=4：1與矽膠充分攪拌混和後配 置成管柱，再以己烷作為沖提液純化，將純化後產物溶於己烷，在0℃下進行再結晶，可得到淡黃色小分子產物。其中，淡黃色小分子產物的1H NMR光譜如圖6所示。 BIP-PHBZ (MW = 292.33, 2.0 g, 6.84 mmol) was dissolved in THF (13.7 mL), and toluene-4-sulfonic acid (MW = 190, 0.388 g, 2.04 mol, 0.3 eq) was directly added to the reaction in an ice bath. In the solution, a protective group of 3,4-dihydro-2H-pyran (MW = 84.12, 6.24 mL, 0.0684 mol, 10 eq) was added dropwise thereto for 10 minutes, and then triethylamine was added to terminate the reaction. The THF and triethylamine were removed by a rotary concentrator and purified by column chromatography. The mixture was stirred and mixed with hexane:triethylamine=4:1. The column was placed and purified by using hexane as a solvent. The purified product was dissolved in hexane and recrystallized at 0 ° C to obtain a pale yellow small molecule product. Among them, the 1H NMR spectrum of the pale yellow small molecule product is shown in Fig. 6.

於本揭露的下述實施例及比較例中，所使用的成分、結構、分子量及重量百分比如下表1所示。 In the following examples and comparative examples disclosed herein, the components, structures, molecular weights, and weight percentages used are shown in Table 1 below.

實施例1-4及比較例 Examples 1-4 and Comparative Examples

依據下表2，將前述成分溶於溶劑中，則可得到實施例1-4及比較例的增幅型I-line光阻組成物。 According to the following Table 2, when the above components were dissolved in a solvent, the amplified I-line resist compositions of Examples 1-4 and Comparative Examples were obtained.

將前述實施例1-4及比較例的光阻組成物塗佈於14cm x 14cm的ITO玻璃上(ITO玻璃經HMDS塗底)，而後於90℃下軟烤90秒，得到厚度為1.5μm的光阻層。 The photoresist compositions of the above Examples 1-4 and Comparative Examples were coated on 14 cm x 14 cm ITO glass (ITO glass was coated with HMDS), and then soft baked at 90 ° C for 90 seconds to obtain a thickness of 1.5 μm. Photoresist layer.

將光阻層以Ultratech 1500 stepper(Boardband；NA=0.31)進行曝光，並選擇性地進行曝後烤製程(PEB)(110℃，90秒)；於23℃下以2.38% TMAH進行顯影30秒，並在25℃下以去離子水清洗30秒。最後，評估曝光顯影後的光阻圖案。 The photoresist layer was exposed with an Ultratech 1500 stepper (Boardband; NA = 0.31) and selectively subjected to post-exposure baking (PEB) (110 ° C, 90 seconds); development at 2.3 ° TMAH for 30 seconds at 23 ° C And rinse with deionized water for 30 seconds at 25 °C. Finally, the photoresist pattern after exposure development was evaluated.

若曝光顯影後，ITO玻璃表面無光阻殘留，則判定為OK；若有光阻殘留，則判定為NG。結果如下表3所示。 If there is no photoresist remaining on the surface of the ITO glass after exposure and development, it is judged as OK; if there is a photoresist remaining, it is judged as NG. The results are shown in Table 3 below.

如表3結果顯示，本揭露實施例1-4的光阻組成物配方，即便未經過曝後烤製程，經曝光顯影後基板表面也不會有殘留物。然而，比較例的光阻組成物配方，則必須經過曝後烤製程，才能緩解基板表面有殘留物的情形。 As shown in the results of Table 3, the photoresist composition of Examples 1-4 of the present disclosure did not have any residue on the surface of the substrate after exposure and development even after the post-exposure baking process. However, in the photoresist composition of the comparative example, it is necessary to pass the post-exposure baking process to alleviate the residue on the substrate surface.

此外，更比較曝光顯影後的光阻圖案。結果顯示，本揭露實施例1-4的光阻組成物配方，在低NA值之曝光機表現邊壁還是非常垂直。然而，習知DNQ光阻及比較例的光阻組成物配方，在低NA值之曝光機曝光顯影後所得到的圖形，則較不垂直且有梯形產生。 In addition, the photoresist pattern after exposure and development is more compared. The results show that the photoresist composition formulations of Examples 1-4 of the present disclosure exhibit a side wall that is very vertical at low NA values. However, the conventional DNQ photoresist and the photoresist composition of the comparative example have a pattern obtained by exposure and development of a low NA value exposure machine, which is less vertical and trapezoidal.

綜上所述，本揭露的增幅型I-line光阻組成物，藉由使用一小分子促進劑可提升黃光微影製程中聚羥苯乙烯衍生物樹脂(增幅型正行光阻)的敏感性及解析度，故可免除後續之曝後烤製程以減少製程時間及成本，並連帶加強曝光區之對比度。特別是，本揭露的增幅型I-line光阻組成物在低數值孔徑(numerical aperture,N.A.值)之FPD曝光機下具有高感光度、高解析度，此為現今的光阻組成物所無法達成的功效。 In summary, the amplified I-line photoresist composition of the present disclosure can improve the sensitivity of the polyhydroxystyrene derivative resin (amplified positive-line photoresist) in the yellow lithography process by using a small molecule accelerator. The resolution is eliminated, so that the subsequent exposure and baking process can be eliminated to reduce the processing time and cost, and the contrast of the exposed area is enhanced. In particular, the amplitude-increasing I-line photoresist composition of the present invention has high sensitivity and high resolution under a low numerical aperture (NA value) FPD exposure machine, which is impossible for today's photoresist composition. The effect achieved.

上述實施例僅係為了方便說明而舉例而已，本揭露所主張之權利範圍自應以申請專利範圍所述為準，而非僅限於上述實施例。 The above-mentioned embodiments are merely examples for convenience of description, and the scope of the claims is intended to be limited to the above embodiments.

Claims (15)

一種增幅型I-line光阻組成物，包括：一聚羥苯乙烯衍生物樹脂；一光酸起始劑；以及一小分子促進劑，為如下式(I-1)所示之化合物： 其中，X1、及X2各自獨立為，且Ra為經取代或未經取代的C1-20烷基、或經取代或未經取代的C3-30環烷基，或Ra與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基；每一R1、及R2各自獨立為氫、經取代或未經取代的C1-20烷基、經取代或未經取代的C3-30環烷基、經取代或未經取代的C6-14芳基、鹵素或，其中Rf為經取代或未經取代的C1-20烷基、或經取代或未經取代的C3-30環烷基，或Rf與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基；A為一單鍵、經取代或未經取代的C1-20亞烷基、經取代或未經取代的C3-30亞環烷基、經取代或未經取代的亞芴基或，其中Rb及Rc各自獨立為經取代或未經取代的C1-20烷基，Rd及Re各自獨立為，且Rg為經取代或未經取代的C1-20烷基、或經取代或未經取代 的C3-30環烷基，或Rg與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基，而p1及p2各自獨立為0至4之整數；以及n1及n2各自獨立為1至3之整數，其中，該光酸起始劑如下式(III)所示： 其中Rx為C1-20烷基。 An amplification type I-line photoresist composition comprising: a polyhydroxystyrene derivative resin; a photoacid initiator; and a small molecule accelerator, which is a compound represented by the following formula (I-1): Wherein X 1 and X 2 are each independently And R a is a substituted or unsubstituted C 1-20 alkyl group, or a substituted or unsubstituted C 3-30 cycloalkyl group, or a C atom adjacent to R and O, and O and The group together form a 5- or 6-membered heterocyclic group; each of R 1 and R 2 is independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3 -30 cycloalkyl, substituted or unsubstituted C 6-14 aryl, halogen or Wherein R f is a substituted or unsubstituted C 1-20 alkyl, or substituted or unsubstituted C 3-30 cycloalkyl, or R f and O, and O-adjacent C atoms and A The group together form a 5- or 6-membered heterocyclic group; A is a single bond, a substituted or unsubstituted C 1-20 alkylene group, a substituted or unsubstituted C 3-30 cycloalkylene group Substituted or unsubstituted fluorenylene or Wherein R b and R c are each independently a substituted or unsubstituted C 1-20 alkyl group, and R d and R e are each independently And R g is a substituted or unsubstituted C 1-20 alkyl, or substituted or unsubstituted C 3-30 cycloalkyl, or R g and O, and O-adjacent C atoms and A The base forms a 5- or 6-membered heterocyclic group, and p1 and p2 are each independently an integer of 0 to 4; and n1 and n2 are each independently an integer of 1 to 3, wherein the photoacid initiator is as follows (III): Wherein R x is a C 1-20 alkyl group. 如申請專利範圍第1項所述之增幅型I-line光阻組成物，其中於式(I-1)中，X1與X2相同，R1與R2相同，且n1與n2相同。 The amplitude-increasing I-line resist composition according to claim 1, wherein in the formula (I-1), X 1 is the same as X 2 , R 1 is the same as R 2 , and n 1 is the same as n 2 . 如申請專利範圍第1項所述之增幅型I-line光阻組成物，其中R1與R2各自獨立為氫、甲基、乙基、正丙基、異丙基、正丁基、第二丁基、 異丁基、叔丁基、苯基、環己基、氟、氯、 The amplitude-increasing I-line photoresist composition according to claim 1, wherein R 1 and R 2 are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, Dibutyl, isobutyl, tert-butyl, phenyl, cyclohexyl, fluorine, chlorine, 如申請專利範圍第2項所述之增幅型I-line光阻組成物，其中A為一單鍵、經苯基取代的C1-20亞烷基、未經取代的C1-20亞烷基、經甲基或乙基取代的C5-6亞環烷基、未經取代的C5-6亞環烷基、或未經取代的亞芴基。 An amplification type I-line photoresist composition as described in claim 2, wherein A is a single bond, a phenyl substituted C 1-20 alkylene group, an unsubstituted C 1-20 alkylene group A C 5-6 cycloalkylene group substituted with a methyl group or an ethyl group, an unsubstituted C 5-6 cycloalkylene group, or an unsubstituted fluorenylene group. 如申請專利範圍第1項所述之增幅型I-line光阻組成物，其中Ra為未經取代的C1-3烷基、經C1-3烷氧基取代的C1-3烷基、或未經取代的C5-7環烷基，或Ra與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基。 The scope of the patent application to item 1 of the amplified I-line resist composition, wherein R a is C 1-3 alkyl unsubstituted, substituted by a C 1-3 alkoxy group is a C 1-3 alkoxy group, or unsubstituted C 5-7 cycloalkyl, or R a and O, and O-methyl-adjacent C atoms and together form a 5 or 6-membered heterocyclic group. 如申請專利範圍第5項所述之增幅型I-line光阻組成物，其中X1、及 X2各自獨立為或 An amplification type I-line photoresist composition according to claim 5, wherein X 1 and X 2 are each independently or 如申請專利範圍第1項所述之增幅型I-line光阻組成物，其中該小分子促進劑選自由如下式(1)、(3)至(13)、(15)至(22)、(25)、以及(26)所組成之群組： The amplification type I-line photoresist composition according to claim 1, wherein the small molecule promoter is selected from the following formulas (1), (3) to (13), (15) to (22), Groups consisting of (25) and (26): 如申請專利範圍第7項所述之增幅型I-line光阻組成物，其中X1及X2 各自獨立為或 ，而為 An amplification type I-line photoresist composition as described in claim 7 wherein X 1 and X 2 are each independently or ,and for 如申請專利範圍第7項所述之增幅型I-line光阻組成物，其中該小分子促進劑選自由如下式(1-a)至(1-f)所組成之群組： The amplification type I-line photoresist composition according to claim 7, wherein the small molecule promoter is selected from the group consisting of the following formulae (1-a) to (1-f): 如申請專利範圍第1項所述之增幅型I-line光阻組成物，其中該聚羥苯乙烯衍生物樹脂之重量平均分子量介於3000至25000之間。 The amplitude-increasing I-line photoresist composition according to claim 1, wherein the polyhydroxystyrene derivative resin has a weight average molecular weight of from 3,000 to 25,000. 如申請專利範圍第1項所述之增幅型I-line光阻組成物，其中該聚羥苯乙烯衍生物樹脂包括如下式(II-1)及(II-2)的重複單元： 其中，Rh為經取代或未經取代的C1-20烷基、或經取代或未經取代的C3-30環烷基，或Rh與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基。 The amplification type I-line photoresist composition according to claim 1, wherein the polyhydroxystyrene derivative resin comprises repeating units of the following formulas (II-1) and (II-2): Wherein R h is a substituted or unsubstituted C 1-20 alkyl group, or a substituted or unsubstituted C 3-30 cycloalkyl group, or a C atom adjacent to R h and O, and O and The base forms a 5- or 6-membered heterocyclic group. 如申請專利範圍第11項所述之增幅型I-line光阻組成物，其中式(II-1)重複單元與式(II-2)的重複單元於該聚羥苯乙烯衍生物樹脂中的莫爾比介於1：1至1：4之間。 The amplification type I-line photoresist composition according to claim 11, wherein the repeating unit of the formula (II-1) and the repeating unit of the formula (II-2) are in the polyhydroxystyrene derivative resin. Morbi is between 1:1 and 1:4. 如申請專利範圍第11項所述之增幅型I-line光阻組成物，其中Rh為未經取代的C1-3烷基、經C1-3烷氧基取代的C1-3烷基、或未經取代的C5-7環烷基，或Rh與O、和O相鄰的C原子及甲基一同形成一5員或6員的雜環基。 An amplification type I-line photoresist composition according to claim 11, wherein Rh is an unsubstituted C 1-3 alkyl group, C 1-3 alkoxy substituted C 1-3 alkane group, or unsubstituted C 5-7 cycloalkyl, or R h and O, and O-methyl-adjacent C atoms and together form a 5 or 6-membered heterocyclic group. 如申請專利範圍第11項所述之增幅型I-line光阻組成物，其中式(II-1)為下式(II-1a)、(II-1b)、(II-1c)、(II-1d)或(II-1e)： The amplification type I-line photoresist composition according to claim 11, wherein the formula (II-1) is the following formula (II-1a), (II-1b), (II-1c), (II) -1d) or (II-1e): 如申請專利範圍第1項所述之增幅型I-line光阻組成物，其中，基於總組成物之總重量為100重量份，包括：大於或等於10重量分且小於或等於30重量分之該聚羥苯乙烯衍生物樹脂；大於0重量分且小於或等於10重量分之該小分子促進劑；以及大於或等於0.5重量分且小於或等於3重量分之該光酸起始劑。 The amplitude-increasing I-line photoresist composition according to claim 1, wherein the total weight of the total composition is 100 parts by weight, including: greater than or equal to 10 parts by weight and less than or equal to 30 parts by weight. The polyhydroxystyrene derivative resin; the small molecule accelerator of more than 0 parts by weight and less than or equal to 10 parts by weight; and the photoacid starter of 0.5 parts by weight or more and 3 parts by weight or less.
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