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Ring Opening Metathesis Polymerization for 157 nm Photoresists. Brian Osborn September 11, 2001. Ring Opening Metathesis Polymerization (ROMP). Advantages Low catalyst loading (< 50 ppm), therefore little residual metal (Ru) Polymerizes geminally disubstituted norbornenes - PowerPoint PPT Presentation
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The University of Texas at AustinThe California Institute of Technology
Ring Opening Metathesis Polymerization for 157 nm Photoresists
Brian OsbornSeptember 11, 2001
The University of Texas at AustinThe California Institute of Technology
Ring Opening Metathesis Polymerization (ROMP)
Advantages• Low catalyst loading (< 50 ppm), therefore little residual
metal (Ru)
• Polymerizes geminally disubstituted norbornenes
• Robust catalyst, functional group and water tolerant
• Molecular weight can be controlled
The University of Texas at AustinThe California Institute of Technology
Geminally Disubstituted Norbornenes
ROMP catalysts easily polymerize key monomers:
Problem: Tg too low (~25-30 °C) for norbornenes
n
X Y
nH2catalyst
n
X YX YFree rotation
allowed
The University of Texas at AustinThe California Institute of Technology
Routes to High Tg ROMP Polymers• The 193 nm System Approach
Incorporation of dinorbornene and carboxylic acid (-COOH) in the polymer composition increases the polymer’s Tg
• One problem, however:
Dissolution rate increases rapidly with acid loading
• The 157 nm solution:
Use dissolution inhibitors to slow dissolution rate of the base polymer and also alleviate swelling1
1Ito, H.; Allen, R. D.; Opitz, J.; Wallow, T. I; Truong, H. D.; Hofer, D. C.; Varanasi, P. R.; Jordhamo, G. M.; Jayaraman, S.; Vicari, R.; Proc. SPIE 2000, 3999, 2.
The University of Texas at AustinThe California Institute of Technology
Routes to High Tg ROMP Polymers
3263 5
OO
OO
OHO
193 nm System - Tsutomu Shimokawa, Kyle Patterson, et al.
157 nm Analogs – Many Possible!
…etc.
Tg: 132 °CHigher Tg due to hydrogen bonding
between acid and ester groups in polymer
nm o
F3C OHF3CO
F3C CF3
OO
F3C OHom nF3C
OO
HOOF3C
F3C ORF3C
The University of Texas at AustinThe California Institute of Technology
Routes to High Tg ROMP Polymers
TriCycloNonene (TCN) CopolymersCF3
COOMe
F
F
COOMeCF3
F
F95 C, 72 hrs
5FM-TCN
CF3
O
OF
F
F3CF3C OR
nm
…etc.
CF3
CF3
ORC
O
C(CH3)3
OCF3
F
F
+
The University of Texas at AustinThe California Institute of Technology
Routes to High Tg ROMP Polymers
n
n
Added stericbulk may restrict
rotation
New comonomers:Exploration of new norbornene monomers with increased steric bulk to make hydrogenated polymer backbone less flexible.
Model compounds to study first:
The University of Texas at AustinThe California Institute of Technology
Initial Synthesis Successful
• Tg is 85-90 °C after hydrogenation • Abs. @ 157 nm: 3.3 m-1 (first pass)• Absorbance is higher than expected
– Polymer requires improved purification
HOF3C CF3
m DiNorbornene HexaFluoroisopropyl Alcohol(DNHFA)
The University of Texas at AustinThe California Institute of Technology
nm
HOF3C CF3 F3C O OF3C
New Dinorbornene ROMP Polymers
m n
HOF3C CF3
F3CO
O
nm
HOF3C CF3 F3C O O
O
F3C
F3CO
O
HOF3C CF3
m n
The University of Texas at AustinThe California Institute of Technology
ROMP Summary• Dinorbornene copolymers look promising• First TCN ROMP copolymers are completed
Future Work• Fully characterize new polymers• Continue ROMP copolymer synthesis• Initial imaging experiments
The University of Texas at AustinThe California Institute of Technology
Acknowledgments• Daniel Sanders (CalTech)• Raymond Hung• Takashi Chiba• Dr. Tsutomu Shimokawa (JSR)• Dr. Kyle Patterson (Motorola)• Central Glass• Clarient• JSR• SEMATECH
The University of Texas at AustinThe California Institute of Technology
Metal Catalyzed Vinyl AdditionPolymerization for 157 nm Photoresists
Brian OsbornSeptember 11, 2001
The University of Texas at AustinThe California Institute of Technology
Metal (Pd+2) Catalyzed Vinyl Addition Polymerization – 3F-TCN Platform
CF3
COOMe
COOMe
CF395 C, 72 hrs
3FM-TCN
• Clean reaction• High yield• Easy purification• Allows use of a transparent ester as a solubility switch• Successfully polymerizes via metal catalyzed vinyl addition
Isolated yield:80-90%
Geminally disubstituted functional groups moved
away from olefin
The University of Texas at AustinThe California Institute of Technology
Synthesis of 5F-TCN MonomerCF3
COOMe
F
F
COOMeCF3
F
F95 C, 72 hrs
Isolated yield:20%
5FM-TCN
Higher fluorine content lends lower absorbance at 157 nm…but lower yields.
CF3
COOMe
F
F
COOMeCF3
F
F95 C, 72 hrs
Isolated yield:73% !!!
5FM-TCN
The University of Texas at AustinThe California Institute of Technology
Initial 3F-TCN-co-NBHFA Images
No dissolution inhibitor. Dissolution inhibitor added.
3F-TCN copolymer images have very poor contrast, until dissolution inhibitor (DI) added.
The University of Texas at AustinThe California Institute of Technology
120 nm 1:3 feature size
HOF3C CF3
F3C
OO
83 17
BPO-R-007-A70:30 polymer:DI blend6% TPS-Nf, 0.3% TBAH
148.9 nm poly on 81.9 nm G00.7 aperture, binary mask
PAB: 140 °C/60 s, PEB: 130 °C/90 s60 s development in 0.26 N TMAH
DOSE: 19.0 mJ/cm2 FOCUS: 0.0 nm
3F-TCN-co-NBHFA - Binary Mask A 70:30 blend of polymer and dissolution inhibitor.
1.0
O
O
O CF3
70 : 30
The University of Texas at AustinThe California Institute of Technology
3F-TCN-co-NBHFA - Phase Shift
100 nm 1 : 3
BPO-R-009-A 70:30 polymer:DI blend6% TPS-Nf, 0.3% TBAH
145.6 nm poly on 82.4 nm G00.3 aperture, phase shift mask
PAB: 140 °C/60 s, PEB: 130 °C/90 s20 s development in 0.26 N TMAH
DOSE: 39.0 mJ/cm2 FOCUS: 0.0 nm
HOF3C CF3
F3C
OO
83 171.0
O
O
O CF3
70 : 30
Changing mask to a strong phase shiftmask results in superior feature profiles,
and smaller resolution possible.
120 nm 1 : 1.5
The University of Texas at AustinThe California Institute of Technology
3F-TCN-co-NBHFA - Phase Shift
80 nm 1 : 3
PEB 130 °C, 90 s PEB 130 °C, 120 s
BPO-R-009-A70:30 polymer:DI blend
6% TPS-Nf, 0.3% TBAH145.6 nm poly on 82.4 nm G0
0.3 aperture, phase shift maskPAB: 140 °C/60 s, PEB: 130 °C/120 s
20 s development in 0.26 N TMAHDOSE: 39.0 mJ/cm2 FOCUS: 0.0 nm
HOF3C CF3
F3C
OO
83 17 1.0
O
O
O CF3
70 : 30
PEB temperaturewindow appears large90 nm 1 : 3 90 nm 1 : 3
80 nm 1 : 3
The University of Texas at AustinThe California Institute of Technology
Transparency Improvements to TCN Platform
HOF3C CF3
F3C
OO
83 17Base polymer absorbance @ 157 nm: 2.0 m-1
Formulated resist absorbance @ 157 nm: 2.7 m-1
Dissolution inhibitor has strongimpact on absorbance!
1.0
O
O
O CF3
And,6% TPS-Nf (PAG)0.3% TBAH (base)for total formulation
Base polymer Dissolutioninhibitor
The University of Texas at AustinThe California Institute of Technology
Transparency Improvements to TCN Platform
Polymer absorbance is relatively low, therefore better imaging requires use of new, more transparent dissolution inhibitors
O O
OCF3
CF3OO
O CF3
CF3
…etc.
O
CF3
CF3
O
O
CF3
F3C OO
O
O
CF3
CF3 CF3
F3C O O
OO
CF3
CF3
O
CF3
CF3
OO
The University of Texas at AustinThe California Institute of Technology
Improvement in Transparency of Resist Formulated with Dissolution Inhibitors
2
2.2
2.4
2.6
2.8
3
3.2
3.4
3.6
3.8
4
155 157 159 161 163 165 167 169 171 173 175
Wavelength (nm)
Abs
orba
nce
(um
-̂1)
BPO-R-005-A
BPO-R-016-A
BPO-R-005-A / 016-A70:30 polymer:DI blend
6% TPS-Nf, 0.3% TBAHVASE of Formulated Resists
1.0
O
O
O CF3
HOF3C CF3
OO
65 35
O O
OCF3
CF3OO
O CF3
CF3
3.4 m-1
3.0 m-1
Improvements in optical transparency possible with
newer dissolution inhibitors
The University of Texas at AustinThe California Institute of Technology
Conclusions and Future Work
• 3F-TCN-co-NBHFA platform shows very promising resolution in preliminary imaging studies,
• A limiting factor is the need to use more transparent dissolution inhibitors.
• Dissolution inhibitor strongly impacts image profile because of both improved contrast and changes in absorbance
• Recreate high yielding 5F-TCN monomer synthesis …does this mean a trip to California??
• Start imaging work on 5F-TCN-co-NBHFA copolymer • Evaluate more transparent dissolution inhibitors
The University of Texas at AustinThe California Institute of Technology
Acknowledgments• Raymond Hung• Daniel Sanders• Takashi Chiba• SEMATECH
– Daniel Miller– Will Conley– Vicki Graffenberg– Shashikant Patel– Georgia Rich
JSR
Clariant
Central Glass
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