novel molecular materials based on noria and double
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Microsoft PowerPoint - PP for Proceedings of 2010 EUV Workshop by
TN.ppt1
Novel Molecular Materials Based on Noria and Double Calixarene (Beryllus) for EB and EUV
Resist Systems
2010 International Workshop 2010 International Workshop on EUV Lithographyon EUV Lithography
Makena Beach Golf ResortMakena Beach Golf Resort June 21June 21--25, 2010, Maui, Hawaii25, 2010, Maui, Hawaii
T. Nishikubo and H. Kudo Department of Material and Life Chemistry,
Faculty of Engineering, Kanagawa University
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, Osaka University Prof. C. K. Ober’s Group, Cornell University, USA Dr. Shimokawa’s Group, JSR Co. Ltd.
AcknowledgementAcknowledgement
ContentsContents I. Background of This ResearchI. 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 Photo- curable Materials
CHCH2
1. Poly(p -hydroxystyrene)s containing t-BOC group have been used as positive-type KrF resists for the production of semiconductor devices
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
CO2 H+
Positive type KrF resists: Limitation of resolution in production line: About 100 nm
Typical Example of Chemical Amplified ResistsTypical Example of Chemical Amplified 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, 24382438, 443 (1995). 2) E. Hasegawa Ed., Organic Electronics, p. 38 (2005).
New advanced technology and novel materials are required to achieve higher resolution
Two Two PracticalPractical Immediate TechnologiesImmediate Technologies One is ArF immersion One is ArF immersion lithographylithography, which seems to have , which seems to have
35 nm resolution.35 nm resolution.
The other is double patterning method, which seems to The other is double patterning method, which seems to have 25 nm resolution.have 25 nm resolution.
Stage
Wafer
Resist
Figure. ArF Immersion LithographyFigure. ArF Immersion Lithography
Further New Technology: Further New Technology: EUV (13.5 nm) EUV (13.5 nm) lithographylithography
Development of New EUV ResistsDevelopment of New EUV Resists
The other is development of novel The other is development of novel molecular resists, as following reasonsmolecular resists, as following reasons
Two different resist system can be consideredTwo different resist system can be considered
One 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.
Concept of Molecular ResistConcept of Molecular Resist
Dev.
Dev.
Resolution improvementResolution improvement
Large Grain(ca.20nm PHS)
Molecular materials with small grain size than polymeric materials with large grain size seem to be used as high performance resists
Dev.
Large grain size polymers (High Mw)
Small grain size polymer (Low Mw)
Large grain size polymers (High Mw)
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.
CH3
CH2
OH
CH3
CH2
6 (CH3CO)2O
1) J. Fujita, Y. Ohnishi, Y. Ochiai, and S. Matsui, Appl. Phys. Lett., 68, 2438 (1995). 2) Y. Ochiai et al., J. Photopolym. Sci. Eng., 13, 413 (2000).
They succeeded to achieve less than10 nm resolution as negative-type EB-resist
The first molecular resists is Negative Type The first molecular resists is Negative Type EBEB--resist based on Calixarenesresist based on Calixarenes
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).
Past Studies Past Studies by Nishikuboby Nishikubo’’s Group:s Group: -- Synthesis of Synthesis of High Performance PhotoHigh Performance Photo--curable Materials curable Materials --
OCH2C
R
CH2
n
OH
R
CH2
n
C CH3
Calix[4]resorcinarene Derivatives
R :
OR
1a, 2a, 3a, 4a 1b, 2b, 3b, 4b 1c, 2c, 3c, 4c
( t-Butoxycarbonyl) methyl group
C O
O C(CH3)3CH2Si(CH3)3
1) T. Nishikubo et al., J. Polym. Sci. Part A. Polym. Chem., 3939, 1481 (2001).
Past Studies of PositivePast Studies of Positive--type Molecular Resists type Molecular Resists based on Calixarenes by Nishikubobased on Calixarenes by Nishikubo’’s Groups Group
Synthesis andSynthesis and PhotoPhoto--initiated Deprotection of New CRA initiated Deprotection of New CRA Derivatives Derivatives (CRAPh)(CRAPh) with tertwith tert--Butyl ester (tButyl ester (t--BAc) GroupsBAc) Groups
0
1 0 0
0 1 0 2 0 3 0 4 0 5 0 6 0
C on
ve rs
io n(
% )
Heating time ( min ) Figure . Photoinduced deprotection of CRA derivatives containing tert-butyl ester moieties. UV irradiation ( 15 mW/cm2 at 365 nm ) for 5 min using 5 mol% DPSP and heating at 150 oC
4i
4a
O
O
O
CH3
4
4
4a
4i
4h
4
4i is a new CRA derivative4i is a new CRA derivative with 12 twith 12 t--BAc groupsBAc groups
1) H. Kudo and T. Nishikubo et al., Bull. Chem. Soc. Jpn., 77, 819 (2004).
CRAPh(4i) showed higher photoCRAPh(4i) showed higher photo--reactivity reactivity than other CRA derivativesthan other CRA derivatives
(DI=100%)
(DI=100%)
(DI=100%)
PB:130 oC/90sec PEB:130 oC/90sec Dev.TMAH 2.38 wt%,60sec
Process Conditions Vacc=50 keV Substrate on bare-Si Resist thickness:0.3μm EB Dose:13.5μC/cm2
15 0
nm 15
0 nm
10 0
nm 10
0 nm
OO O
High Resolution and High Sensibility
1) CRAph (4i) filmCRAph (4i) film with 100% with 100% tt--BacBac groupsgroups 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%)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 3) We considered that CA and CRA derivatives can not be used as positiveas positive--type EB type EB resists with high resolution, because these derivatives resists with high resolution, because these derivatives do not have enough do not have enough mechanical property. This is good mistake mechanical property. This is good mistake forfor further progress of the research.further progress of the research.
Patterning Property of Calixarene (CRA) Derivative Patterning Property of Calixarene (CRA) Derivative as Positiveas Positive-- type EBtype EB--ResResistist
4i (DI=100%)
That is, CA and CRA derivatives do not have enough physical properties as positive-type molecular EB-resists.
How to dissolve this technical problemHow to dissolve this technical problem
The first approach is a functionalization of The first approach is a functionalization of cyclodextrins (CD)s for the application as cyclodextrins (CD)s for the application as positivepositive--type molecular resists.type molecular resists.
First Application of CD Derivative as a Molecular ResistFirst Application of CD Derivative as a Molecular Resist
O
Photo-induced Deprotection
H or
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 heatingwith PAG followed by heating
β-CD β-CD derivative
1) H. Kudo et. al. Bull. Chem. Soc. Jpn., 78, 731 (2005).
The Patterning Property of the The Patterning Property of the ββ--CD DerivativeCD Derivative
Figure. SEM images of obtained with β-CD derivative. Exposure dose: 72mJ/cm2
Resin PAG
Sample
System PB PEB Dev. Mask
: NIKON S306C(ArF) : 130 / 90s : 100 / 90s : 20 s(2.38% TMAHaq) : 100 nm 1L1S
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
Synthesis of Noria by DCCSynthesis of Noria by DCC OHHO HCl
OHC-(CH2)3-CHO+
OHHO
HO
Waterwheel at my hometown Kumano-shi
1) H. Kudo and T. Nishikubo et al., Angew. Chem. Int. Ed., 4545, (47), 7948-7952 (2006).
Spin about Y axis Spin about X axis
Yield: 83%Yield: 83%
formula : C222H288O72CHCl3hexane M = 4137.72 Cryst syst : triclinic Space group : P-1 T = -180.0 oC a = 17.416, b = 19.589, c = 20.00 α= 107.992, β= 106.86, γ= 94.700o
Z = 1 Dc = 1.21 g cm-3
μ = 13.16 cm-1
XX--ray Crystallography and Elemental ray Crystallography and Elemental Analysis of Analysis of ““NoriaNoria””
Elemental Analysis (C222H288O72· CHCl3· hexane) Measured Value ; C: 63.96 %, H: 0.14 % Calculated Value ; C: 63.77 %, H: 0.07 %
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 III. Chemical Modification of Noria and Beryllus for EUVfor EUV-- and EBand EB--ResistsResists
IV. Evaluation of Noria and Beryllus Derivatives as EUV-Resists and EB- Resists
Noria has many characteristic properties 1.1. Noria has ladder cyclic structure. This means that
Noria has strong mechanical property. 2. Noria2. Noria has one one hydrophobic center-hole. 3. Noria3. Noria has 6 hydrophilic outside cavities 4. Noria4. Noria has 24 reactive hydroxyl groups. This means that
many photo-reactive groups can be introduced into “Noria” molecule.
Spin about Y axis Spin about X axis
Chemical Modification of Chemical Modification of NoriaNoria
OR1R1O
R1O
OR OR
1) H. Kudo, R. Hayashi, and T. Nishikubo, Macromolecules, in press (2010).
Synthesis of NegativeSynthesis of Negative--Type Noria DerivativesType Noria Derivatives
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 III. Chemical Modification of Noria and Beryllus for EUVfor EUV-- and EBand EB--ResistsResists
IV. Evaluation of Noria and Beryllus Derivatives as EUV-Resists and EB-Resists
OR1R1O
R1O
Exposed by Electron Beam
H. Kudo, D. Watanabe, T. Nishikubo, K. Maruyama, D. Shimizu, T. Kai, T. Shimokawa and C. K. Oer., J Mater. Chem., 18, 3588 (2008)
X. André, J.-K Lee, A. D. Silva, N. Felix, C. K. Ober, H. B. Cao, H Deng, H. Kudo, D. Watanabe, T. Nishikubo., Proc. of SPIE, 6519, 65194B (2007)
Patterning Properties of NoriaPatterning Properties of Noria--Boc and NoriaBoc and Noria––BAc by BAc by EBLEBL
10 pA 300um ×300 um (240,000 dot ×240,000 dot)
150 nm pitch
100 nm pitch
Evaluated by Professor TagawaEvaluated by Professor Tagawa’’s group, Osaka Universitys group, Osaka University
Patterning Properties of NoriaPatterning Properties of Noria--Ad by EB Ad by EB Lithography (SEM Image)Lithography (SEM Image)
Small Size Exposure Tool (SEFT) on Selete, Tsukuba, Japan
EUV Exposure tools setup on Selete, JapanEUV Exposure tools setup on Selete, Japan
SourceSource
Wafer trackWafer track
28 nmL/S 32 nmL/S 30 nmL/S 22 nmL/S26 nmL/S 24 nmL/S45nmL/S
6.5 nm 12.5 mJ/cm2 13.5 mJ/cm2 14.0 mJ/cm2 14.5 mJ/cm2 14.5 mJ/cm2 14.5 mJ/cm2 14.5 mJ/cm2
25 nmL/S 24 nmL/S 20 nmL/S21 nmL/S22 nmL/S23 nmL/S
15.5 mJ/cm2 16 mJ/cm2 16 mJ/cm2 16 mJ/cm2 16 mJ/cm2 16 mJ/cm2
26 nmL/S
15.5mJ/cm2
Thickness : 50 nm Prebake: 130 / 60 sec Exposure Tool: SFET (XSlit). PEB: 130 / 60 sec Dev.: TMAH 2.38 wt% 60 sec. CDSEMS9380II
Substrate: Si. Thickness: 50nm SFET (Annular0.3/0.7). Dev.: TMAH 2.38 wt% 60 sec
Evaluated by Selete, JapanEvaluated by Selete, Japan
by Annular Method using EUVL (SEFT)by Annular Method using EUVL (SEFT)
by Xby X-- Slit Method using EUVL (SEFT) Slit Method using EUVL (SEFT)
Patterning Properties of NoriaPatterning Properties of Noria--AdAd2323 by by EUV Lithography (SEM Image)EUV Lithography (SEM Image)
Noria-Ad
OR1R1O
R1O
O
Ad
1) T. Nishikubo, H. Kudo, Y. 1) T. Nishikubo, H. Kudo, Y. SuyamaSuyama, H. , H. OizumiOizumi, and T. , and T. ItaniItani, , J. J. PhotopolyPhotopoly. Sci. Tech. Sci. Tech., ., 2222, 73 (2009)., 73 (2009). 2) H. Kudo, Y. 2) H. Kudo, Y. SuyamaSuyama, H. , H. OizumiOizumi, T. , T. ItaniItani, and T. Nishikubo, , and T. Nishikubo, J. Mater. ChemJ. Mater. Chem.,., 2020, 4445 (2010)., 4445 (2010).
45nm 35nm40nm
R:100/TPS-NF:10/TOA:1.25(wt ratio) 2.2wt% PGMEA: Si, UL-A
Process conditions PAB: 90-60s PEB: 90-60s DEP: 2.38%TMAH 30s
Patterning Properties of NoriaPatterning Properties of Noria--CHVECHVE4343 by by EUVL (SEM Image)EUVL (SEM Image)
OR
ORRO
RO
CH3Noria-CHVE
1) H. Kudo, M. Jinguji, T. Nishikubo, H. Oizumi, T. Itani, J. Photopolym. Sci. Technol., 23, 657-664 (2010).
SummarySummary 1. We successfully synthesized novel ladder cyclic 1. We successfully synthesized novel ladder cyclic
compound compound ““NoriaNoria”” and double calixarene and double calixarene compound compound ““BeryllusBeryllus”” based on DCC system.based on DCC system.
2. We examined chemical modification of 2. We examined chemical modification of ““NoriaNoria”” for the application of EUVfor the application of EUV-- and EBand EB--resists, and it resists, and it was found that Noria derivatives with appropriate was found that Noria derivatives with appropriate protecting groups achieved 22protecting groups achieved 22--225 nm resolution 5 nm resolution as a positiveas a positive--type EUVtype EUV--resist.resist.
Novel Molecular Materials Based on Noria and Double Calixarene (Beryllus) for EB and EUV
Resist Systems
2010 International Workshop 2010 International Workshop on EUV Lithographyon EUV Lithography
Makena Beach Golf ResortMakena Beach Golf Resort June 21June 21--25, 2010, Maui, Hawaii25, 2010, Maui, Hawaii
T. Nishikubo and H. Kudo Department of Material and Life Chemistry,
Faculty of Engineering, Kanagawa University
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, Osaka University Prof. C. K. Ober’s Group, Cornell University, USA Dr. Shimokawa’s Group, JSR Co. Ltd.
AcknowledgementAcknowledgement
ContentsContents I. Background of This ResearchI. 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 Photo- curable Materials
CHCH2
1. Poly(p -hydroxystyrene)s containing t-BOC group have been used as positive-type KrF resists for the production of semiconductor devices
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
CO2 H+
Positive type KrF resists: Limitation of resolution in production line: About 100 nm
Typical Example of Chemical Amplified ResistsTypical Example of Chemical Amplified 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, 24382438, 443 (1995). 2) E. Hasegawa Ed., Organic Electronics, p. 38 (2005).
New advanced technology and novel materials are required to achieve higher resolution
Two Two PracticalPractical Immediate TechnologiesImmediate Technologies One is ArF immersion One is ArF immersion lithographylithography, which seems to have , which seems to have
35 nm resolution.35 nm resolution.
The other is double patterning method, which seems to The other is double patterning method, which seems to have 25 nm resolution.have 25 nm resolution.
Stage
Wafer
Resist
Figure. ArF Immersion LithographyFigure. ArF Immersion Lithography
Further New Technology: Further New Technology: EUV (13.5 nm) EUV (13.5 nm) lithographylithography
Development of New EUV ResistsDevelopment of New EUV Resists
The other is development of novel The other is development of novel molecular resists, as following reasonsmolecular resists, as following reasons
Two different resist system can be consideredTwo different resist system can be considered
One 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.
Concept of Molecular ResistConcept of Molecular Resist
Dev.
Dev.
Resolution improvementResolution improvement
Large Grain(ca.20nm PHS)
Molecular materials with small grain size than polymeric materials with large grain size seem to be used as high performance resists
Dev.
Large grain size polymers (High Mw)
Small grain size polymer (Low Mw)
Large grain size polymers (High Mw)
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.
CH3
CH2
OH
CH3
CH2
6 (CH3CO)2O
1) J. Fujita, Y. Ohnishi, Y. Ochiai, and S. Matsui, Appl. Phys. Lett., 68, 2438 (1995). 2) Y. Ochiai et al., J. Photopolym. Sci. Eng., 13, 413 (2000).
They succeeded to achieve less than10 nm resolution as negative-type EB-resist
The first molecular resists is Negative Type The first molecular resists is Negative Type EBEB--resist based on Calixarenesresist based on Calixarenes
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).
Past Studies Past Studies by Nishikuboby Nishikubo’’s Group:s Group: -- Synthesis of Synthesis of High Performance PhotoHigh Performance Photo--curable Materials curable Materials --
OCH2C
R
CH2
n
OH
R
CH2
n
C CH3
Calix[4]resorcinarene Derivatives
R :
OR
1a, 2a, 3a, 4a 1b, 2b, 3b, 4b 1c, 2c, 3c, 4c
( t-Butoxycarbonyl) methyl group
C O
O C(CH3)3CH2Si(CH3)3
1) T. Nishikubo et al., J. Polym. Sci. Part A. Polym. Chem., 3939, 1481 (2001).
Past Studies of PositivePast Studies of Positive--type Molecular Resists type Molecular Resists based on Calixarenes by Nishikubobased on Calixarenes by Nishikubo’’s Groups Group
Synthesis andSynthesis and PhotoPhoto--initiated Deprotection of New CRA initiated Deprotection of New CRA Derivatives Derivatives (CRAPh)(CRAPh) with tertwith tert--Butyl ester (tButyl ester (t--BAc) GroupsBAc) Groups
0
1 0 0
0 1 0 2 0 3 0 4 0 5 0 6 0
C on
ve rs
io n(
% )
Heating time ( min ) Figure . Photoinduced deprotection of CRA derivatives containing tert-butyl ester moieties. UV irradiation ( 15 mW/cm2 at 365 nm ) for 5 min using 5 mol% DPSP and heating at 150 oC
4i
4a
O
O
O
CH3
4
4
4a
4i
4h
4
4i is a new CRA derivative4i is a new CRA derivative with 12 twith 12 t--BAc groupsBAc groups
1) H. Kudo and T. Nishikubo et al., Bull. Chem. Soc. Jpn., 77, 819 (2004).
CRAPh(4i) showed higher photoCRAPh(4i) showed higher photo--reactivity reactivity than other CRA derivativesthan other CRA derivatives
(DI=100%)
(DI=100%)
(DI=100%)
PB:130 oC/90sec PEB:130 oC/90sec Dev.TMAH 2.38 wt%,60sec
Process Conditions Vacc=50 keV Substrate on bare-Si Resist thickness:0.3μm EB Dose:13.5μC/cm2
15 0
nm 15
0 nm
10 0
nm 10
0 nm
OO O
High Resolution and High Sensibility
1) CRAph (4i) filmCRAph (4i) film with 100% with 100% tt--BacBac groupsgroups 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%)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 3) We considered that CA and CRA derivatives can not be used as positiveas positive--type EB type EB resists with high resolution, because these derivatives resists with high resolution, because these derivatives do not have enough do not have enough mechanical property. This is good mistake mechanical property. This is good mistake forfor further progress of the research.further progress of the research.
Patterning Property of Calixarene (CRA) Derivative Patterning Property of Calixarene (CRA) Derivative as Positiveas Positive-- type EBtype EB--ResResistist
4i (DI=100%)
That is, CA and CRA derivatives do not have enough physical properties as positive-type molecular EB-resists.
How to dissolve this technical problemHow to dissolve this technical problem
The first approach is a functionalization of The first approach is a functionalization of cyclodextrins (CD)s for the application as cyclodextrins (CD)s for the application as positivepositive--type molecular resists.type molecular resists.
First Application of CD Derivative as a Molecular ResistFirst Application of CD Derivative as a Molecular Resist
O
Photo-induced Deprotection
H or
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 heatingwith PAG followed by heating
β-CD β-CD derivative
1) H. Kudo et. al. Bull. Chem. Soc. Jpn., 78, 731 (2005).
The Patterning Property of the The Patterning Property of the ββ--CD DerivativeCD Derivative
Figure. SEM images of obtained with β-CD derivative. Exposure dose: 72mJ/cm2
Resin PAG
Sample
System PB PEB Dev. Mask
: NIKON S306C(ArF) : 130 / 90s : 100 / 90s : 20 s(2.38% TMAHaq) : 100 nm 1L1S
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
Synthesis of Noria by DCCSynthesis of Noria by DCC OHHO HCl
OHC-(CH2)3-CHO+
OHHO
HO
Waterwheel at my hometown Kumano-shi
1) H. Kudo and T. Nishikubo et al., Angew. Chem. Int. Ed., 4545, (47), 7948-7952 (2006).
Spin about Y axis Spin about X axis
Yield: 83%Yield: 83%
formula : C222H288O72CHCl3hexane M = 4137.72 Cryst syst : triclinic Space group : P-1 T = -180.0 oC a = 17.416, b = 19.589, c = 20.00 α= 107.992, β= 106.86, γ= 94.700o
Z = 1 Dc = 1.21 g cm-3
μ = 13.16 cm-1
XX--ray Crystallography and Elemental ray Crystallography and Elemental Analysis of Analysis of ““NoriaNoria””
Elemental Analysis (C222H288O72· CHCl3· hexane) Measured Value ; C: 63.96 %, H: 0.14 % Calculated Value ; C: 63.77 %, H: 0.07 %
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 III. Chemical Modification of Noria and Beryllus for EUVfor EUV-- and EBand EB--ResistsResists
IV. Evaluation of Noria and Beryllus Derivatives as EUV-Resists and EB- Resists
Noria has many characteristic properties 1.1. Noria has ladder cyclic structure. This means that
Noria has strong mechanical property. 2. Noria2. Noria has one one hydrophobic center-hole. 3. Noria3. Noria has 6 hydrophilic outside cavities 4. Noria4. Noria has 24 reactive hydroxyl groups. This means that
many photo-reactive groups can be introduced into “Noria” molecule.
Spin about Y axis Spin about X axis
Chemical Modification of Chemical Modification of NoriaNoria
OR1R1O
R1O
OR OR
1) H. Kudo, R. Hayashi, and T. Nishikubo, Macromolecules, in press (2010).
Synthesis of NegativeSynthesis of Negative--Type Noria DerivativesType Noria Derivatives
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 III. Chemical Modification of Noria and Beryllus for EUVfor EUV-- and EBand EB--ResistsResists
IV. Evaluation of Noria and Beryllus Derivatives as EUV-Resists and EB-Resists
OR1R1O
R1O
Exposed by Electron Beam
H. Kudo, D. Watanabe, T. Nishikubo, K. Maruyama, D. Shimizu, T. Kai, T. Shimokawa and C. K. Oer., J Mater. Chem., 18, 3588 (2008)
X. André, J.-K Lee, A. D. Silva, N. Felix, C. K. Ober, H. B. Cao, H Deng, H. Kudo, D. Watanabe, T. Nishikubo., Proc. of SPIE, 6519, 65194B (2007)
Patterning Properties of NoriaPatterning Properties of Noria--Boc and NoriaBoc and Noria––BAc by BAc by EBLEBL
10 pA 300um ×300 um (240,000 dot ×240,000 dot)
150 nm pitch
100 nm pitch
Evaluated by Professor TagawaEvaluated by Professor Tagawa’’s group, Osaka Universitys group, Osaka University
Patterning Properties of NoriaPatterning Properties of Noria--Ad by EB Ad by EB Lithography (SEM Image)Lithography (SEM Image)
Small Size Exposure Tool (SEFT) on Selete, Tsukuba, Japan
EUV Exposure tools setup on Selete, JapanEUV Exposure tools setup on Selete, Japan
SourceSource
Wafer trackWafer track
28 nmL/S 32 nmL/S 30 nmL/S 22 nmL/S26 nmL/S 24 nmL/S45nmL/S
6.5 nm 12.5 mJ/cm2 13.5 mJ/cm2 14.0 mJ/cm2 14.5 mJ/cm2 14.5 mJ/cm2 14.5 mJ/cm2 14.5 mJ/cm2
25 nmL/S 24 nmL/S 20 nmL/S21 nmL/S22 nmL/S23 nmL/S
15.5 mJ/cm2 16 mJ/cm2 16 mJ/cm2 16 mJ/cm2 16 mJ/cm2 16 mJ/cm2
26 nmL/S
15.5mJ/cm2
Thickness : 50 nm Prebake: 130 / 60 sec Exposure Tool: SFET (XSlit). PEB: 130 / 60 sec Dev.: TMAH 2.38 wt% 60 sec. CDSEMS9380II
Substrate: Si. Thickness: 50nm SFET (Annular0.3/0.7). Dev.: TMAH 2.38 wt% 60 sec
Evaluated by Selete, JapanEvaluated by Selete, Japan
by Annular Method using EUVL (SEFT)by Annular Method using EUVL (SEFT)
by Xby X-- Slit Method using EUVL (SEFT) Slit Method using EUVL (SEFT)
Patterning Properties of NoriaPatterning Properties of Noria--AdAd2323 by by EUV Lithography (SEM Image)EUV Lithography (SEM Image)
Noria-Ad
OR1R1O
R1O
O
Ad
1) T. Nishikubo, H. Kudo, Y. 1) T. Nishikubo, H. Kudo, Y. SuyamaSuyama, H. , H. OizumiOizumi, and T. , and T. ItaniItani, , J. J. PhotopolyPhotopoly. Sci. Tech. Sci. Tech., ., 2222, 73 (2009)., 73 (2009). 2) H. Kudo, Y. 2) H. Kudo, Y. SuyamaSuyama, H. , H. OizumiOizumi, T. , T. ItaniItani, and T. Nishikubo, , and T. Nishikubo, J. Mater. ChemJ. Mater. Chem.,., 2020, 4445 (2010)., 4445 (2010).
45nm 35nm40nm
R:100/TPS-NF:10/TOA:1.25(wt ratio) 2.2wt% PGMEA: Si, UL-A
Process conditions PAB: 90-60s PEB: 90-60s DEP: 2.38%TMAH 30s
Patterning Properties of NoriaPatterning Properties of Noria--CHVECHVE4343 by by EUVL (SEM Image)EUVL (SEM Image)
OR
ORRO
RO
CH3Noria-CHVE
1) H. Kudo, M. Jinguji, T. Nishikubo, H. Oizumi, T. Itani, J. Photopolym. Sci. Technol., 23, 657-664 (2010).
SummarySummary 1. We successfully synthesized novel ladder cyclic 1. We successfully synthesized novel ladder cyclic
compound compound ““NoriaNoria”” and double calixarene and double calixarene compound compound ““BeryllusBeryllus”” based on DCC system.based on DCC system.
2. We examined chemical modification of 2. We examined chemical modification of ““NoriaNoria”” for the application of EUVfor the application of EUV-- and EBand EB--resists, and it resists, and it was found that Noria derivatives with appropriate was found that Noria derivatives with appropriate protecting groups achieved 22protecting groups achieved 22--225 nm resolution 5 nm resolution as a positiveas a positive--type EUVtype EUV--resist.resist.