Study on resist performance of chemically amplified molecular resists based on cyclic oligomers

Novel resist materials are required for lithographic processing with ionization radiation such as extreme ultraviolet (EUV) and electron beam (EB) exposure tools. In this study, we synthesized positive-tone chemically amplified molecular resist materials with pendant adamantyl ester (AD) and cyclohexyl 2-propyl ether moieties based on cyclic oligomers such as noria, calixarene dimer, cyclodextrin, and pillar arene, and we examined the lithographic performances of sensitivity, etching durability, and patterning under EUV and EB exposure. We clarified that the sensitivity of the resist materials was consistent with the structure of the cyclic oligomers, i.e., the hole size of the molecular structure might be an important factor relevant to high-resolution resist materials. We found that chemically amplified molecular resists based on cyclic oligomers such as noria, calixarene dimer, cyclodextrin, and pillar arene are promising candidates for higher-resolution resist materials

Synthesis and Resist Properties of Calixarene Polymers with Pendant Haloalkyl Groups

We examined the condensation polymerization of t-butylcalix[8]arene (BCA[8]), p-t-butylcalix[4]arene (BCA[4]), and C-(4-t-butylbenz)calix[4]resorcinarene (BCRA[4]) with 1,3-adamantane dibromoacetate (ADB), yielding soluble polymers poly(BCA[8]-co-ADB), poly(BCA[4]-co-ADB), and poly(BCRA[4]-co-ADB), respectively. These polymers had good solubility, good film forming ability, and good thermal stability. It was anticipated that these polymers were applicable to positive-type resist materials. However, by the examination on the resist sensitivity using EUV exposure system, these polymers were applicable to negative type resist materials using THF as a developer. Furthermore, a negative clear resist pattern with 100nm resolution could be obtained by EB exposure system. These results indicated that poly(BCA[8]-co-ADB) and poly(BCRA[4]-co-ADB) have high potential to offer higher resolution negative pattern using EUV lithography system

Synthesis and Property of Tellurium-Containing Polymer for Extreme Ultraviolet Resist Material

Synthesis, physical properties, and resist properties of tellurium containing polymer with pendant adamantyl ester groups poly(Re-co-Te)-AD were examined, relevant to the application of resist material for extreme ultraviolet laser photolithography (EUVL) system. A tellurium containing polymer with pendant hydroxyl groups poly(Re-co-Te) was synthesized by the condensation reaction of resorcinol (Re) and tellurium tetrachloride (TeCl4), followed by the condensation reaction with adamantyl bromo acetate to give a corresponding polymer poly(Re-co-Te)-AD. Their physical properties (solubility, film-forming ability, thermal stability) and resist properties (thickness loss property after soaking in 2.38 wt% TMAH aq. solution, out-gassing on EUV exposure tool, and resist sensitivity under EUV exposure tool) were also examined

Synthesis and Resist Properties of Hyperbranched Polyacetals

The synthesized noria-AD offered 40 nm resolution resist pattern with LWR = 9.5 nm in the case of EB exposure tool and a clear 26 nm resolution pattern with LWR = 8.3 nm by means of EUV exposure tool. These results indicate that the present poly(THPE-co-BVOC) would have higher potential to offer higher resolution pattern using EUV lithography system

Inhibition of Rho-associated coiled-coil containing protein kinase enhances the activation of epidermal growth factor receptor in pancreatic cancer cells

<p>Abstract</p> <p>Background</p> <p>Rho-associated coiled-coil containing protein kinase (Rho-kinase/ROCK) is involved in various cellular functions including cell proliferation, and is generally considered to be oncogenic, while some studies show that ROCK functions as a negative regulator of cancer progression. As a result, the precise role of ROCK remains controversial. We have previously reported that Rho-kinase/ROCK negatively regulates epidermal growth factor (EGF)-induced cell proliferation in SW480 colon cancer cells. In the present study, we investigated the role of ROCK in EGF receptor (EGFR) signaling in the pancreatic cancer cell lines, Panc1, KP3 and AsPc1.</p> <p>Results</p> <p>In these cells, Y27632, a specific ROCK inhibitor, enhanced EGF-induced BrdU incorporation. The blockade of EGF stimulation utilizing anti-EGFR-neutralizing antibodies suppressed Panc1 cell proliferation. EGF induced RhoA activity, as well as the phosphorylation of cofilin and myosin light chain (MLC), both targets of ROCK signaling, and Y27632 suppressed both of these processes, indicating that the phosphorylation of cofilin and MLC by EGF occurs through ROCK in Panc1 cells. EGF-induced phosphorylation of EGFR at tyrosine residues was augmented when the cells were pretreated with Y27632 or were subjected to gene silencing using ROCK-siRNA. We also obtained similar results using transforming growth factor-α. In addition, EGF-induced phosphorylation of p44/p42 mitogen-activated protein kinase and Akt were also enhanced by Y27632 or ROCK-siRNA. Moreover, an immunofluorescence microscope study revealed that pretreatment with Y27632 delayed EGF-induced internalization of EGFR. Taken together, these data indicate that ROCK functions to switch off EGFR signaling by promoting the internalization of the EGFR.</p> <p>Conclusions</p> <p>While EGF first stimulates the activation of the EGFR and subsequently increases cancer cell proliferation, EGF concurrently induces the activation of ROCK, which then turns off the activated EGFR pathway via a negative feedback system.</p

Synthesis and Property of Tannic Acid Derivatives and Their Application for Extreme Ultraviolet Laser Lithography System

We synthesized tannic acid derivatives with pendant cyclohexyl acetal moieties (TA-CVEn), butyl acetal moieties (TA-BVEn), and adamantyl ester moieties (TA-ADn) by the reaction of tannnic acid (TA) with cyclohexyl vinyl ether (CVE), butyl vinyl ether (BVE), and adamantyl bromo acetate (AD) in various feeds ratios. The synthesized TA-CVEn, TA-BVEn, and TA-ADn had good solubility, good film-forming ability, and high thermal stability relevant to application of photolithography materials. However, only TA-BVE97 and TA-AD74 can be used as positive-type photo-resist materials using 2.38 wt% TMAH aq. as developer due to the result of thickness loss property. Furthermore, their resist-sensitivity upon EUV exposure tool and etching durability were adequate and they have high potential as next-generation resist material for EUV lithography

Synthesis of Hyperbranched Polyacetals containing C-(4-t-butylbenz)calix[4]resorcinarene; Resist Properties for Extreme Ultraviolet (EUV) Lithography

We synthesized the various hyperbranched polyacetals poly(t-BCRA[4]-co-BVOC), poly(t-BCRA[4]-co-BVOP), poly(t-BCRA[4]-co-BVOXP), poly(t-BCRA[4]-co-BVBC), and poly(t-BCRA[4]-co-TVCH) by polyaddition of C-(4-t-butylbenz)calix[4]resorcinarene (t-BCRA[4]) with 1,4-bis(4-vinyloxy)cyclohexane (BVOC), 1,3-bis(vinyloxy)propane (BVOP), 1,5-bis(vinyloxy)-3-oxapentane (BVOXP), 4,4\u27-bis(vinyloxy)-1,1\u27-bicyclohexane (BVBC), and 1,3,5-tris(vinyloxy)cyclohexane (TVCH), respectively. The resist sensitivity of the synthesized polymers using EUV exposure tool was consistent with their structures, and is in the order poly(t-BCRA[4]-co-BVOC) > poly(t-BCRA[4]-co-BVOXP) > poly(t-BCRA[4]-co-TVCH) > poly(t-BCRA[4]-co-BVOP) >> poly(t-BCRA[4]-co-BVBC). Furthermore, poly(t-BCRA[4]-co-BVOC) showed good resist properties such as out-gassing property using EUV exposure tool, film-thickness loss property, and etching durability. Overall, our results indicate that hyperbranched polyacetal poly(t-BCRA[4]-co-BVOC) has high potential as next-generation resist material for EUV photolithography

2017～2019年度 関西大学研究拠点形成支援経費研究成果報告書

目次・研究成果の概要・2-1　工藤 宏人・宮前 翼・上田 正人・村山 憲弘・林 順一 "ノーリア骨格をテンプレートとした空孔内に水酸基を有する架橋化合物の合成とそれらの金属イオン包接性能" ネットワークポリマー論文集 vol.41, No.2, 65 - 71 (2020).・2-2　Mitsuaki Matsuoka, Kaho Yokoyama, Kohei Okura, Norihiro Murayama, Masato Ueda, Makio Naito " Synthesis of Geopolymers from Mechanically Activated Coal Fly Ash and Improvement of Their Mechanical Properties" Minerals 9, 791- 801 (2019).・2-3　Daisuke Shimoyama, Ryo Sekiya, Hiroto Kudo, Takeharu Haino, "Feet-to-Feet Connected Trisresorcinarenes" Organic Letters 22, 352 - 356 (2019).・2-4　Masato Ueda, Masahiko Ikeda, Shigeo Mori, Kenji Doi, Hisashi Kitagaki, Shuntaro Terauchi "Mechanical Properties of Additively Manufactured Porous Titanium with Sub-Millimetre Structural Units" Materials Transactions Vol.60, No.9, 1792 - 1798 (2019).・2-5　五十井 浩平・白杉 文香・松岡 光昭・林 順一・村山 憲弘 "種々のMg-Fe系複合酸化物を用いた希薄水溶液中のホウ素およびヒ素の除去" 環境資源工学 66, 29 - 35 (2019).・2-6　Toru Maruyama, Mitsuyoshi Tamaki, Keisuke Nakamura, Gou Nakamura "EFFECT OF MOLTEN METAL TEMPERATURE ON MOLD FILLING IN EVAPORATIVE PATTERN CASTING" International Journal of Metalcasting 13, 611–617 (2019).・2-7　Ryuta Saito, Toru Maruyama, Toshiki Nakamura, Hitoshi Yanagitani, Takahiro Sakai, Kouji Nakamoto "Influence of Tellurium Addition to Spheroidal Graphite Cast Iron on the Number of Graphite Particles" International Journal of Metalcasting Vol.13, 3, 571-577 (2018).・2-8　Masato Ueda, Rika Yamaguchi, Chika Fujita, Masahiko Ikeda "Control of Cell Adhesion on Titanium Dioxide by Light Irradiation" Materials Science Forum Vol.941, 2507 - 2512 (2018).・2-9　Hiroto Kudo, Mari Fukunaga, Kohei Shiotsuki, Hiroya Takeda, Hiroki Yamamoto, Takahiro Kozawa, Takeo Watanabe "Synthesis of hyperbranched polyacetals containing C-(4-t-butylbenz)calix[4]resorcinarene: Resist properties for extreme ultraviolet (EUV) lithography" Reactive and Functional Polymers 131, 361 - 367 (2018).・2-10　大隈 修・前 一廣・林 順一 "直接液化による豪州ビクトリア褐炭の高度利用 : 改新BCLプロセスによる化学原料の生産" Journal of the Japan Institute of Energy 98, 17 - 26 (2019).・2-11　Issei Suzuki, Ayako Kakinuma, Masato Ueda, Takahisa Omata "Flux growth of β-NaGaO₂ single crystals" Journal of Crystal Growth 504, 26 -30 (2018).・2-12　上田 正人、坂本 貴則、池田 勝彦 "電気抵抗率の精密測定による純チタンの組織評価" 環境資源工学 65, 74 -76 (2018).・2-13　Satoshi Imasaka, Hiroyasu Ishii, Jun\u27ichi Hayashi, Sadao Araki, Hideki Yamamoto "Synthesis of CHA-type titanosilicate zeolites using titanium oxide as Ti source and evaluation of their physicochemical properties" Microporous and Mesoporous Materials 273, 243-248 (2019).・2-14　Hiroto Kudo, Shizuya Ohori, Hiroya Takeda, Hiroki Ogawa, Takeo Watanbe, Hiroki Yamamoto, Takahiro Kozawa "Synthesis and Property of Tannic Acid Derivatives and Their Application for Extreme Ultraviolet Laser Lithography System" Journal of Photopolymer Science and Technology Vol.31, 221 - 225 (2018).・2-15　Hiroto Kudo, Tsubasa Miyamae, Kouta Kitagawa, Kohei Isoi, Norihiro Murayama, Jun\u27ichi Hayashi " Synthesis and Metal-Complexation Ability of Cross-Linking Materials Containing Noria-Templated Cavities with Pendant Carboxylic Acid Groups" Chemistry Select 3, 2223 - 2228 (2018).・2-16　上田 正人、池田 勝彦、土井 研児、 森 重雄、北垣 壽、寺内 俊太郎、関 あずさ "骨部分置換用ポーラスチタン : ポリグリコール酸 : 炭酸カルシウム複合体の開発" 高分子論文集 Vol.75, No.1, 69 - 74 (2018).・2-17　Alexandru C Sonoc, Jacob Jeswiet, Norihiro Murayama, Junji Shibata "A study of the application of Donnan dialysis to the recycling of lithium ion batteries" Hydrometallurgy 175, 133 - 143 (2018).2-3は、著作権の関係により非公開としております。2-8は、著作権の関係により非公開としております。2-9は、著作権の関係により非公開としております。2-10は、著作権の関係により非公開としております。2-11は、著作権の関係により非公開としております。2-16は、著作権の関係により非公開としております