Development of New Negative -tone Molecular Resists Based ...
Transcript of Development of New Negative -tone Molecular Resists Based ...
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Development of New NegativeDevelopment of New Negative--tone Molecular tone Molecular Resists Based on Phenylcalix[4] Resists Based on Phenylcalix[4] resorcinareneresorcinarenefor EUVL.for EUVL.
Investigation of correlation with the Investigation of correlation with the octanoloctanol water water partition coefficient and the sensitivity of negativepartition coefficient and the sensitivity of negative--tone molecular resiststone molecular resists
Masatoshi Echigo, Masako Yamakawa, Yumi Ochiai,Yu Okada and Masaaki Takasuka
Mitsubishi Gas Chemical Company, Inc.
2012.10.1 2012 International Symposium on Extreme Ultraviolet Lithography 2
Motivation for NMotivation for Negativeegative‐‐TTone one ResistResist
NNegativeegative‐‐tone tone resists are limitedly influenced by flare.resists are limitedly influenced by flare.We believe NegativeWe believe Negative--tone resist can achieve these required properties.tone resist can achieve these required properties.
MPU gate in resist length (nm)
2007 ITRS Roadmap
LWR (3sigma) <8% of CD 1.7
21
2.4
30MPU gate in resist length (nm)MPU gate in resist length (nm)
2007 ITRS Roadmap
LWR (3sigma) <8% of CD 1.7
21
2.4
30
2012.10.1 2012 International Symposium on Extreme Ultraviolet Lithography 3
Aromatic aldehyde
Resorcinol
ConceptsDemands
Low molecular weightLow molecular weightUniformityUniformity
Branch structure
Easy manufactureEasy to get raw materialsNo metal contamination
Chemical amplified type
High density of C atom
High resolutionSmaller LER
High sensitivity
High Tg
Coating ability(amorphous)
Etching durability
New New PhenylcalixPhenylcalix[4]resorcinarene [4]resorcinarene
DerivativesDerivatives
Manufactured by the reactionbetween Aromatic aldehyde
and Resorcinol
Materials
Productivity
Suppressedoutgassing
Rigid cyclic structureRigid cyclic structure(as a (as a CalixareneCalixarene))
HydrophobicityHydrophobicity(No swelling)(No swelling)
Design Concepts for New NegativeDesign Concepts for New Negative--tone tone Molecular Resist MaterialMolecular Resist Material
2012.10.1 2012 International Symposium on Extreme Ultraviolet Lithography 4
Motivation for negativeMotivation for negative‐‐tone molecular resisttone molecular resist
Polymer Molecular Resist
Low LERLarge LER
40nmhp
LER(3σ)= 1.5nmLER(3σ)= 7.3nm
90nmhp
-- Phenylcalix[4]resorcinarenes are smallPhenylcalix[4]resorcinarenes are small--size and highsize and high--TgTg molecules,molecules,enough for patterning highenough for patterning high--resolution and lowresolution and low--LER.LER.
Our proposal for molecular resist materials.Our proposal for molecular resist materials.Our proposal for molecular resist materials.Our proposal for molecular resist materials.M. Echigo et al., 5th International EUV Symposium, 01010101‐‐‐‐RERERERE‐‐‐‐27 27 27 27 (2006)
OH
n
Mw = 8000
OH
OHOH
HO
Mw = 692
EBEB
2012.10.1 2012 International Symposium on Extreme Ultraviolet Lithography 5
Previous Data Previous Data (Negative(Negative--tone resist using MGR108)tone resist using MGR108)
-- Patterns were well defined at Patterns were well defined at ≦≦30 30 nmhpnmhp. .
44
MGR108
HO OH
12.86.124.026
Esize(mJ/cm2)LWR (nm)
CD (nm)
nZ(32)
EUV
LS Pattern
By courtesy of SEMATECH
EB 30nm hp,60nmtLER=--nm,52μC/cm2
2012.10.1 2012 International Symposium on Extreme Ultraviolet Lithography 6
Previous Data Previous Data (Negative(Negative--tone resist using CRAtone resist using CRA--02)02)
44HO OR1
OH
CRA-02
EBEBEBEBEBEBEBEB 40nm hp,55nmt40nm hp,55nmt40nm hp,55nmt40nm hp,55nmt40nm hp,55nmt40nm hp,55nmt40nm hp,55nmt40nm hp,55nmtLERLERLERLERLERLERLERLER=3.4nm,90=3.4nm,90=3.4nm,90=3.4nm,90=3.4nm,90=3.4nm,90=3.4nm,90=3.4nm,90μμμμμμμμC/cmC/cmC/cmC/cmC/cmC/cmC/cmC/cm22222222
EBEBEBEBEBEBEBEB 30nm hp,55nmt30nm hp,55nmt30nm hp,55nmt30nm hp,55nmt30nm hp,55nmt30nm hp,55nmt30nm hp,55nmt30nm hp,55nmtLERLERLERLERLERLERLERLER=3.0nm,90=3.0nm,90=3.0nm,90=3.0nm,90=3.0nm,90=3.0nm,90=3.0nm,90=3.0nm,90μμμμμμμμC/cmC/cmC/cmC/cmC/cmC/cmC/cmC/cm22222222
EBEBEBEBEBEBEBEB 25nm hp,55nmt25nm hp,55nmt25nm hp,55nmt25nm hp,55nmt25nm hp,55nmt25nm hp,55nmt25nm hp,55nmt25nm hp,55nmtLERLERLERLERLERLERLERLER=4.1nm,90=4.1nm,90=4.1nm,90=4.1nm,90=4.1nm,90=4.1nm,90=4.1nm,90=4.1nm,90μμμμμμμμC/cmC/cmC/cmC/cmC/cmC/cmC/cmC/cm22222222
-- Patterns were well defined at 40Patterns were well defined at 40--25 25 nmhpnmhp. .
2012.10.1 2012 International Symposium on Extreme Ultraviolet Lithography 7
The purpose of this studyThe purpose of this study
Investigation of correlation with Investigation of correlation with the the octanoloctanol water partitionwater partitioncoefficient (coefficient (ClogPClogP)) and and the sensitivity at a dose of 50 the sensitivity at a dose of 50 nmhpnmhp of of negativenegative--tone molecular resists.tone molecular resists.
The values of the The values of the octanoloctanol water partition coefficient werewater partition coefficient were measured measured by by ChemPropChemProp Pro for Pro for ChemChem 3D3D..
The octanol water partition coefficient logP is used in QSAR studies and rational drug design as a
measure of molecular hydrophobicity. Hydrophobicity affects drug absorption, bioavailability,
hydrophobic drug-receptor interactions, metabolism of molecules, as well as their toxicity.
LogP has become also a key parameter in studies of the environmental fate of chemicals.
2012.10.1 2012 International Symposium on Extreme Ultraviolet Lithography 8
General synthesis of HPGeneral synthesis of HP--CRACRA
H+
+
44HO OR1
OH
CHO
OH n
HO OR1HO OH R1-BrOH
OH n
n = 0 or 1
Six HPSix HP--CRA derivatives as a mixture of various isomers were CRA derivatives as a mixture of various isomers were synthesized in high yields(99%).synthesized in high yields(99%).
2012.10.1 2012 International Symposium on Extreme Ultraviolet Lithography 9
General synthesis of APGeneral synthesis of AP--CRACRA
H+
+
44HO OH
R2
R2
CHO
HO OH
H+
+
44HO OH
R2
R2
CHO
HO OH
Two APTwo AP--CRA derivatives as a mixture of various isomers were CRA derivatives as a mixture of various isomers were synthesized in high yields(99%).synthesized in high yields(99%).
2012.10.1 2012 International Symposium on Extreme Ultraviolet Lithography 10
Experiment (Resist composition)Experiment (Resist composition)
PAGPAG--1 1 : : sulfoniumsulfonium sulfonatesulfonateHMMMHMMM : : hexamethoxymethylmelaminehexamethoxymethylmelamineQQ--11 : amine: aminePGMEPGME : propylene glycol : propylene glycol monomethylmonomethyl etherether
Q-1
Quencher
PGMEHMMMPAG-1
HP-CRA-01Resist A
HP-CRA-02Resist B
HP-CRA-03Resist C
HP-CRA-04Resist D
AP-CRA-08Resist H
AP-CRA-07Resist G
HP-CRA-06Resist F
HP-CRA-05Resist E
SolventCross-LinkerPAGMatrix
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Experiment (EB Patterning Evaluations)Experiment (EB Patterning Evaluations)
Apparatus: Apparatus: UltraUltra--High Precision EB Lithography System High Precision EB Lithography System (ELS(ELS--7500 ; Acceleration Voltage 50 7500 ; Acceleration Voltage 50 keVkeV))at Mitsubishi Gas Chemical (MGC)at Mitsubishi Gas Chemical (MGC)
Process Conditions:Process Conditions:Substrate: Organic layer (UL)Substrate: Organic layer (UL)Film Thickness: 30Film Thickness: 30--60nm 60nm PBPB&&PEB: 110PEB: 110℃℃/90s/90sDev.: TMAH 0.26N 60sDev.: TMAH 0.26N 60s
Analysis Conditions:Analysis Conditions:SEM: S4800SEM: S4800
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Characteristics of CRAs(1/2)Characteristics of CRAs(1/2)
8017.85> 50HP-CRA-04
5020.24> 50HP-CRA-03
12015.78> 50HP-CRA-02
8418.16> 50HP-CRA-01
Sensitivity
(μC/cm2)
ClogPDissolution
rate(nm/min)
Model
Structure
Matrix
44HO O
OH
44HO O
OH
44HO O
OHOH
44HO O
OHOH
44HO O
OH
44HO O
OH
44HO O
OHOH
44HO O
OHOH
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Characteristics of CRAs(2/2)Characteristics of CRAs(2/2)
7815.35> 50AP-CRA-08
4820.12> 50AP-CRA-07
6019.97> 50HP-CRA-06
2022.36> 50HP-CRA-05
Sensitivity
(μC/cm2)
ClogPDissolution
rate(nm/min)
Model
Structure
Matrix
44HO O
OH
44HO O
OH
44HO O
OHOH
44HO O
OHOH
44HO OH
44HO OH
44HO OH
44HO OH
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y = -14.647x + 347.08y = -14.647x + 347.08y = -14.647x + 347.08y = -14.647x + 347.08
RRRR2222 = 0.9874 = 0.9874 = 0.9874 = 0.9874
0000
20202020
40404040
60606060
80808080
100100100100
120120120120
140140140140
15151515 17171717 19191919 21212121 23232323
Octanol Water Partition Coefficient ; ClogPOctanol Water Partition Coefficient ; ClogPOctanol Water Partition Coefficient ; ClogPOctanol Water Partition Coefficient ; ClogP
Sensit
ivit
y (
μC
/cm
2)
Sensit
ivit
y (
μC
/cm
2)
Sensit
ivit
y (
μC
/cm
2)
Sensit
ivit
y (
μC
/cm
2)
Correlation between the Correlation between the octanoloctanol water partition water partition coefficient and the sensitivitycoefficient and the sensitivity
The sensitivity of resists were higher as the value of the The sensitivity of resists were higher as the value of the octanoloctanolwater partition coefficient got smaller.water partition coefficient got smaller.
2012.10.1 2012 International Symposium on Extreme Ultraviolet Lithography 15
Highlight Data Highlight Data ((New ResistNew Resist) ) -- Update Update --
EB 15nmhp48μC/cm2
EB 10nmhp44μC/cm2
EB 20nmhp52μC/cm2
44
calix[4]resorcinarenederivative
YO OX
Z n
-- By using new calix[4]resorcinarene derivative,By using new calix[4]resorcinarene derivative,sub 30nm hp patterns were resolvedsub 30nm hp patterns were resolved at the high sensitivity at the high sensitivity
2012.10.1 2012 International Symposium on Extreme Ultraviolet Lithography 16
SummarySummary
-- We invested of correlation with the We invested of correlation with the octanoloctanol water partition coefficient water partition coefficient and the sensitivity of negativeand the sensitivity of negative--tone molecular resists based on tone molecular resists based on calix[4]resorcinarene (CRA) by Electron Beam Lithography (EBL). calix[4]resorcinarene (CRA) by Electron Beam Lithography (EBL).
-- The sensitivity of negativeThe sensitivity of negative--tone molecular resists were higher as the tone molecular resists were higher as the value of the value of the octanoloctanol water partition coefficient got smaller. water partition coefficient got smaller.
-- It was confirmed that the It was confirmed that the octanoloctanol water partition coefficient was useful water partition coefficient was useful to the guess of sensitivity of negativeto the guess of sensitivity of negative--tone molecular resists. tone molecular resists.
-- Furthermore, we have developed new calix[4]resorcinarenes showiFurthermore, we have developed new calix[4]resorcinarenes showing ng wellwell--defined sub 20nm halfdefined sub 20nm half--pitch patterns. pitch patterns.
-- Future study is underway to improve resist performance through Future study is underway to improve resist performance through material material and process optimization to evaluate resist performance by EUV and process optimization to evaluate resist performance by EUV lithography (EUVL).lithography (EUVL).