Novel Molecular Materials Based on Noria and Double Calixarene (Beryllus) for EB and EUV Resist Systems

Transcription

1 2010 International Workshop on EUV Lithography Makena Beach Golf Resort June 21-25, 25, 2010, Maui, Hawaii Novel Molecular Materials Based on Noria and Double Calixarene (Beryllus) for EB and EUV Resist Systems T. Nishikubo and H. Kudo Department of Material and Life Chemistry, Faculty of Engineering, Kanagawa University 1

2 Acknowledgement Coworkers: Prof. H. Kudo (Kanagawa University) Prof. T. Yokozawa (Kanagawa University) Dr. N. C. Kasuga (Kanagawa University) Mr. K. Mitani (JSR Co. Ltd.) Miss. R. Hayashi (Hitachi Chemical Co. Ltd.) Mr. D. Watanabe (Shinji Tech Co. Ltd.) Mr. H. Seki (Kanagawa University) Mr. Y. Suyama (Kanagawa University) Ms. M. Jinguji (Kanagawa University) Co-operations: (Evaluation as EB- and EUV-resists) Drs. T. Itani s Group (Selete) Prof. S. Tagawa s Group, saka University Prof. C. K. ber s Group, Cornell University, USA Dr. Shimokawa s Group, JSR Co. Ltd.

3 Contents I. Background of This Research II. Synthesis of Ladder Cyclic Compound Noria and Double Calixarene Compound Beryllus based on DCC System III. Chemical Modification of Noria and Beryllus for EUV-Resists, EB-Resists and Photo-curable Materials IV. Evaluation of Noria and Beryllus Derivatives as EUV-Resists, EB-Resists and Photocurable Materials

4 Typical Example of Chemical Amplified Resists 1. Poly(p -hydroxystyrene)s containing t-bc group have been used as positive-type KrF resists for the production of semiconductor devices CH n C Photoacid generator C(CH 3 ) 3 t-bc group CH H n CH 3 C 2 C H + CH 3 Positive type KrF resists: Limitation of resolution in production line: About 100 nm 1) C. G. Willson, H. Ito, J. M. J. Frechet, T. G. Tessier, F. M. Houlihan, J. Electrochem. Soc., 133, 181(1986). 2. Copolymers containing both adamantane and lactone groups have been used as positive-type ArF resists Positive Type ArF resists: Limitation of resolution in production line: About 45 nm 1) K. Nakano, K. Maeda, S. Iwasa, and E. Hasegawa, Proc. SPIE, 2438, 443 (1995). 2) E. Hasegawa Ed., rganic Electronics, p. 38 (2005). New advanced technology and novel materials are required to achieve higher resolution

5 Two Practical Immediate Technologies ne is ArF immersion lithography,, which seems to have 35 nm resolution. The other is double patterning method, which seems to have 25 nm resolution. Lens Liquid recover Liquid supply Immersion medium Resist Wafer Scanning movement Stage Figure. ArF Immersion Lithography

6 Further New Technology: EUV (13.5 nm) lithography -Development of New EUV Resists- Two different resist system can be considered ne is development of EUV-resist based on KrF resists, which are protected poly(p-hydroxy)styrenes, or based on ArF resists, which are poly(methacrylate)s containing pendant adamantyl groups. The other is development of novel molecular resists, as following reasons

7 Concept of Molecular Resist Resolution improvement Large grain(ca.20nm PHS) Small Grain (low molecular?) Exposure Dev. Dev. Small grain size polymer (Low Mw) High resolution Large grain size polymers (High Mw) Poor resolution LWR improvement Small Grain (low molecular?) Exposure Large Grain(ca.20nm PHS) Dev. Dev. Small grain size polymer (Low Mw) Small LWR Large grain size polymers (High Mw) Large LWR Molecular materials with small grain size than polymeric materials with large grain size seem to be used as high performance resists

8 However, some physical properties such as film forming property, mechanical property, Tg, and thermal stability of molecular resists decrease with molecular weight in general. Therefore, how to overcome these problems is very important for the development of molecular resists. This is a challenging research subject for good Engineer and Scientist.

9 The first molecular resists is Negative Type EB-resist based on Calixarenes CH 3 CH 3 H p-methylcalix[6]arene 6 (CH 3 C) 2 Acetic anhydride in pyridine C CH 3 p -Methylcalix[6]arenehexaacetate 6 They succeeded to achieve less than10 nm resolution as negative-type EB-resist 1) J. Fujita, Y. hnishi, Y. chiai, and S. Matsui, Appl. Phys. Lett., 68, 2438 (1995). 2) Y. chiai et al., J. Photopolym. Sci. Eng., 13, 413 (2000).

10 Past Studies by Nishikubo s s Group: - Synthesis of High Performance Photo-curable Materials - CH 3 C CCl C R C CH 3 C n CH CH C Br TBAB / KH n R CH H R Pa : R=CH 3 Pc : R=C(CH 3 ) 3 n CH TBAB / NaH Cs 2 C 3 R 2 1) K. Iyo, T. Nishikubo et al., J. Polym. Sci. Part A. Polym. Chem, 37, 3071 (1999). 2) T. Nishikubo, A. Kameyama et al., J. Polym. Sci. Part A. Polym. Chem. 37, 1805 (1999). 3) T. Nishikubo, A. Kameyama, K. Tsutsui, J. Polym. Sci. Part A. Polym. Chem., 39, 1169 (2001). Br S TBAB / KH CH R n Cl Br DBU R R R n n R 2 n C 2 R n

11 Past Studies of Positive-type type Molecular Resists based on Calixarenes by Nishikubo s s Group CH 3 C(CH 3 ) 3 R H 3 C R R CH 3 R H 3 C R R R CH 3 (H 3 C) 3 C R R R C(CH 3 ) 3 R H 3 C R CH 3 R R R R R H 3 C CH 3 (H 3 C) 3 C R R C(CH 3 ) 3 R R R (H 3 C) 3 C C(CH 3 ) 3 CH 3 C(CH 3 ) 3 Calix[4]resorcinarene p-methylcalix[6]arene p-tert-butylcalix[8]arene Derivatives 1a, 2a, 3a, 4a Derivatives 1b, 2b, 3b, 4b Derivatives 1c, 2c, 3c, 4c R: C C(CH 3 ) 3 Si(CH 3 ) 3 C C(CH 3 ) 3 t-butoxycarbonyl (t-boc) group Trimethylsilyl (TMS) group Cyclohexenyl (CHX) group (t-butoxycarbonyl) methyl group 1) T. Nishikubo et al., J. Polym. Sci. Part A. Polym. Chem., 39, 1481 (2001).

12 Synthesis and Photo-initiated Deprotection of New CRA Derivatives (CRAPh) with tert-butyl ester (t-bac) Groups 100 4i 4 (DI=100%) 80 4a CH 3 Conversion(%) a 4h 4 C 16 H 33 (DI=100%) 20 4h Heating time ( min ) Figure. Photoinduced deprotection of CRA derivatives containing tert-butyl ester moieties. UV irradiation ( 15 mw/cm 2 at 365 nm ) for5minusing5mol%dpspandheatingat150 o C CRAPh(4i) showed higher photo-reactivity than other CRA derivatives 4i is a new CRA derivative with 12 t-bac t groups 1) H. Kudo and T. Nishikubo et al., Bull. Chem. Soc. Jpn., 77, 819 (2004). 4 4i (DI=100%)

13 Composition CH n 4 (90 wt%) Reference Patterning Property of Calixarene (CRA) Derivative as Positive- type EB-Res Resist (10 wt%) CH n (100 wt%) 4i 4i (DI=100%) 150 nm 100 nm 150 nm Poly(p-(tert-butoxycarbonyl)methoxy) styrene) 100 nm Process Conditions Vacc=50 kev Substrate on bare-si Resist thickness:0.3μm EB Dose:13.5μC/cm 2 PB:130 o C/90sec PEB:130 o C/90sec Dev.TMAH 2.38 wt%,60sec High Resolution and High Sensibility 1) CRAph (4i) film with 100% t-bac groups could not make suitable resist pattern, because this compound does not have enough mechanical property. 2) The film prepared from polymer (90 w%) with 4i (10%) has good resolution on 150 nm. However, this film could not achieve 100 nm resolution as shown here. 3) We considered that CA and CRA derivatives can not be used as positive-type type EB resists with high resolution, because these derivatives do not have enough mechanical property. This is good mistake for further progress of the research.

14 That is, CA and CRA derivatives do not have enough physical properties as positive-type molecular EB-resists. How to dissolve this technical problem The first approach is a functionalization of cyclodextrins (CD)s for the application as positive-type type molecular resists.

15 First Application of CD Derivative as a Molecular Resist 1. Synthesis of β-cd derivative with tert-butyl ester groups by the reaction of β- CD with α-trifluoromethyl tert-butyl methacrylate using appropriate catalyst. 2. Photo-induced deprotection of β-cd derivative with PAG followed by heating H H H H H H H H H H H H H H H H HH H H H β-cd CF 3 R R H H H H H H R R H H H H H H HH R R R : H or R β-cd derivative hν /PAG The Patterning Property of the β-cd Derivative Sample Resin : β-cd derivative 10 wt% solution in 2-Heptanone PAG : triphenylsulfonium fluoro-sulfonate 0.5 wt% in 2-Heptanone CF 3 H + Δ Photo-induced Deprotection System PB PEB Dev. Mask : NIKN S306C(ArF) : 130 / 90s : 100 / 90s : 20 s(2.38% TMAHaq) : 100 nm 1L1S Figure. SEM images of obtained with β-cd derivative. Exposure dose: 72mJ/cm nm 0.0μm 72mJ/cm 2 1) H. Kudo et. al. Bull. Chem. Soc. Jpn., 78, 731 (2005).

16 I. Background of This Research II. Synthesis of Noria and Beryllus based on DCC System The second stage of molecular design to synthesize high performance molecular materials III. Chemical Modification of Noria and Beryllus for EUV-Resists and EB-Resists IV. Evaluation of Noria and Beryllus Derivatives as EUV-Resists, EB-Resists and Photo-curable Materials

17 Synthesis of Noria by DCC H H Resorcinol + HC-( ) 3 -CH 1,5-Pentanedial HCl 80 o C, 48 h in Ethanol H H H H H H H H H H H H H H H H H H H H H H H H Noria Yield: 83% Spin about Y axis Spin about X axis Waterwheel at my hometown Kumano-shi 1) H. Kudo and T. Nishikubo et al., Angew. Chem. Int. Ed., 45, (47), (2006).

18 X-ray Crystallography and Elemental Analysis of Noria R R R R R R H R Crystal data : formula : C 222 H CHCl 3 hexane M = Cryst syst : triclinic Space group : P-1 T = o C a = , b = , c = 20.00A α= , β= , γ= o Z = 1 D c = 1.21 g cm -3 μ = cm -1 R 1, R w2 = 0.097, 0.21 R R R R R H R R R R Noria-Boc R R R R R R R : C(CH 3 ) 3 Elemental Analysis (C 222 H CHCl 3 hexane) Measured Value ; C: %, H: 0.14 % Calculated Value ; C: %, H: 0.07 %

19 I. Background of This Research II. Synthesis of Cyclic Ladder Compound Noria and DCRA Beryllus based on DCC System The second stage of molecular design to synthesize high performance material. III. Chemical Modification of Noria and Beryllus for EUV- and EB-Resists IV. Evaluation of Noria and Beryllus Derivatives as EUV-Resists and EB- Resists

20 Chemical Modification of Noria Spin about Y axis Spin about X axis Noria has many characteristic properties 1. Noria has ladder cyclic structure. This means that Noria has strong mechanical property. 2. Noria has one hydrophobic center-hole. 3. Noria has 6 hydrophilic outside cavities 4. Noria has 24 reactive hydroxyl groups. This means that many photo-reactive groups can be introduced into Noria molecule.

21 Synthesis of Positive-Type Noria Derivatives H H H H H H H H R 1 R 1 R 1 R 1 R 1 R 1 R 1 R 1 R 2 R 2 R 2 R 2 R 2 R 2 RR 22 H H H H H H H H Chemical modification R 1 R 1 R 1 R 1 R 1 R 1 R 1 R 1 hv/ photo-acid generator R 2 R 2 R 2 R 2 R 2 R 2 R 2 R 2 H H H H H Noria H H H R 1 R 1 R 1 R R 1 R 1 1 R 1 Noria-Boc; Noria-BAc; Noria-Ad; R 1 R 1 Noria-Acetal; R R 2 R 2 R 2 R 2 R 2 R 2 R 2 R 2 R 2 Noria; Noria-BAA; H H R 3 R 3 R 3 R 3 R 3 R R 3 R 3 3 R 3 R 3 RR 3 3 R 3 R 3 R 3 R 3 Chemical modification R 4 R 4 R 4 R 4 R 4 R 4 R 4 R 4 R 4 R 4 RR 44 R 4 R 4 R 4 R 4 hv photo-acid generator R 5 R 5 R 5 R 5 R 5 R 5 R 5 R 5 RR 5 5 RR 55 R 5 R 5 R 5 R 5 R 3 R 3 R 3 R 3 R 3 R 3 R 3 R 3 R 3 Noria-BAA; H R 4 R 4 R 4 R 4 R 4 R 4 Noria-Acetal; R 4 R 4 R 4 R 5 R 5 R 5 R 5 R 5 R 5 R 5 R 5 R 5 Noria-BAA; H

22 Synthesis of Negative-Type Noria Derivatives R R R R R R R R R R R R R R R R R R R R R R R R Noria-MA : R : Noria-X : R : Noria-HPMA : R : H Noria-HE : R : H Noria-VE : R : Noria-EMA : R : Noria-AE : R : Noria-PE : R : 1) H. Kudo, R. Hayashi, and T. Nishikubo, Macromolecules, in press (2010).

23 I. Background of This Research II. Synthesis of Cyclic Ladder Compound Noria based on DCC System The second stage of molecular design to synthesize high performance material. III. Chemical Modification of Noria and Beryllus for EUV- and EB-Resists IV. Evaluation of Noria and Beryllus Derivatives as EUV-Resists and EB-Resists

24 Patterning Properties of Noria-Boc and Noria BAc by EBL R 1 R 1 RR 1 R 1 R R H R 1 Exposed by Electron Beam R 1 R 1 R 1 R 1 R 1 R 1 R 1 R 1 RR 1 R 1 R 1 1 R 1 R R 1 1 R1 R 1 = Noria-Boc 100 Line and space : 50 nm X. André, J.-K Lee, A. D. Silva, N. Felix, C. K. ber, H. B. Cao, H Deng, H. Kudo, D. Watanabe, T. Nishikubo., Proc. of SPIE, 6519, 65194B (2007) R 1 R 1 RR 1 R 1 R R H R 1 Exposed by Electron Beam R 1 R 1 R 1 R 1 R 1 R 1 R 1 R 1 RR 1 R 1 R 1 1 R 1 R 1 R 1 R1 Noria-BAc 60 R 1 = Line and space : 70 nm H. Kudo, D. Watanabe, T. Nishikubo, K. Maruyama, D. Shimizu, T. Kai, T. Shimokawa and C. K. ber., J Mater. Chem., 18, 3588 (2008)

25 Patterning Properties of Noria-Ad by EB Lithography (SEM Image) Noria-Ad Ad nm pitch 260 μccm μccm nm pitch (PEB 115 ) 260 μccm μccm pa 300um 300 um (240,000 dot 240,000 dot) Evaluated by Professor Tagawa s s group, saka University

26 EUV Exposure tools setup on Selete, Japan Mask loader Exposure chamber Source Wafer loser Wafer track Small Size EUV Exposure Tool (SEFT) on Selete, Tsukuba, Japan

27 Patterning Properties of Noria-Ad EUV Lithography (SEM Image) by Annular Method using EUVL (SEFT) 45nmL/S Ad 23 by R 1 R 1 R 1 R 1 R 1 R 1 RR 1 R 1 R R RR 1 R 1 R 1 1 R 1 R 1 R 1 R1 Noria-Ad 32 nml/s 30 nml/s 28 nml/s 26 nml/s 24 nml/s 22 nml/s 12.5 mj/cm mj/cm mj/cm mj/cm mj/cm mj/cm mj/cm nm R 1 = Ad H R 1 R 1 R 1 R 1 R 1 by X-X Slit Method using EUVL (SEFT) 26 nml/s Substrate: Si. Thickness: 50nm SFET (Annular0.3/0.7). Dev.: TMAH 2.38 wt% 60 sec 25 nml/s 24 nml/s 23 nml/s 22 nml/s 21 nml/s 20 nml/s 15.5mJ/cm mj/cm 2 16 mj/cm 2 16 mj/cm 2 16 mj/cm 2 16 mj/cm 2 16 mj/cm 2 Evaluated by Selete, Japan Thickness : 50 nm Prebake: 130 / 60 sec Exposure Tool: SFET (X Slit). PEB: 130 / 60 sec Dev.: TMAH 2.38 wt% 60 sec. CD SEM:S9380 II 1) T. Nishikubo, H. Kudo, Y. Suyama,, H. izumi,, and T. Itani, J. Photopoly.. Sci. Tech., 22,, 73 (2009). 2) H. Kudo, Y. Suyama,, H. izumi,, T. Itani,, and T. Nishikubo, J. Mater. Chem., 20,, 4445 (2010).

28 Patterning Properties of Noria-CHVE 43 EUVL (SEM Image) Dose/ CD/ LWR 18/ 59.3/ nm 50nm 18/ 51.2/ nm 18/ 46.7/ nm 19/ 39.0/ nm 19/ 35.5/ 8.7 by 43 by R R R R R Noria-CHVE R H CH 3 3 Noria-CVE 43 R:100/TPS-NF:10/TA:1.25(wt ratio) 2.2wt% PGMEA: Si, UL-A 基板 Process conditions PAB: 90-60s PEB: 90-60s DEP: 2.38%TMAH 30s 19/ 33.5/ nm 30nm 28nm 1) H. Kudo, M. Jinguji, T. Nishikubo, H. izumi, T. Itani, J. Photopolym. Sci. Technol., 23, (2010).

29 Summary 1. We successfully synthesized novel ladder cyclic compound Noria and double calixarene compound Beryllus based on DCC system. 2. We examined chemical modification of Noria for the application of EUV- and EB-resists, and it was found that Noria derivatives with appropriate protecting groups achieved nm resolution as a positive-type type EUV-resist. 3. We also examined chemical modification of Beryllus for the application of EUV- and EB- resists, and it was found that Beryllus derivatives with appropriate protecting groups achieved 28 nm resolution as a positive-type type EUV-resist.