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An Integrated Science Perspective on Driving Innovation with Materials
at the Nanoscale
Nano and Giga Challenges in Electronics and PhotonicsPhoenix, Arizona, March 12-16, 2007
Jim PrendergastVice President & Chief Technology Officer
DuPont Electronic & Communication Technologies
2
The Vision of DuPontTo be the world’s most dynamic science company,
creating sustainable solutions
essential to a better, safer, healthier life for people everywhere.
3
1802 1830 1850 1900 1925 1945 1990 2000 2050 2090
Explosives
ChemicalsPolymersFibersEnergy
BIRTH
GROWTH
MATURITY
BIRTH
GROWTH
MATURITY
BIRTH
GROWTH
MATURITY
3
ChemistryBiotechnologyMaterials ScienceElectronics Safety & Security
Transforming for Our Third Century
4
Plastics and Chemicals: 14%
Motor Vehicle: 26%
Textiles/Home Furnishings: 1%Construction Materials: 14%
Agriculture/Food: 28%
Our MarketsElectronics: 9%
Other: 8%
5
DuPont Safety &
Protection
DuPont Electronic &
Communication Technologies
DuPont Coatings & Color
Technologies
DuPont Performance
Materials
DuPont Agriculture &
Nutrition
$6.4B$6.9B
$3.8B $6.5B$5.6B
• Sales of $29 B
• Operations in >70 Countries
• ~60,000 Employees Worldwide
“…. a dynamic science company that puts science to work solving problems to make life better, safer, healthier”
DuPont Today…
6Nanoscale Science and Engineering in DuPont
Coatings on Pigmentary TiO2
Wood, ChouAnhydride Surlyn®modifier in Nylon-6
500 nm 85 nm
AFM image showing distribution of hard (bright) and soft segments in elastane fiber
Sauer, McLeanWeb structure in PTFE
membrane
“Established” nanosized materials:
- Carbon Black
- Colloidal silver and gold
- Colloidal and fumed silica
- Pigments
- Magnetic materials
- Catalysts
All that is “Nano” is not New to DuPont…
7
Market-Focused Innovation Strategy
Particle scienceInorganic and organometallic chem.PhotochemistrySurface SciencePolymer ScienceDispersionsCoatingsColor SciencePrecision PatterningOrganic SynthesisFluorochemistryBiomolecular Eng.Materials Sci & Eng.Process innovations
Technology Toolkit
Construction
Security and Protection
Agriculture
Displays
Alternate Energy
Electronics
Automotive
Elect. machinery
Plastics
Markets Served
Surface propertiesOptical propertiesElect. properties Selective barriers Heat resistanceWeight vs. strength FlexibilityBiological activityUV resistanceCost vs.performance
Properties Needed
DisplaysAdvanced CoatingsFuel CellsPhotovoltaic CellsPrecision patterningProtective ApparelAdvanced MembranesEngineering PlasticsElectronic MaterialsBiosensors
Target Applications
Nanoparticlesand dispersions
Metals
Metal oxides
Nanoclays
Carbon nanotubes
Biomolecules
Membranes
ALD / Thin Films- etc- etc
NS&E enriches the Integrated Science toolbox, but doesn’t stand alone
8
• Control nanostructure to tailor fundamental properties – Thermal, magnetic, electrical, optical…
• Exploit enormous surface/volume ratio
– Composite materials, catalysis, membranes, energy storage, drug delivery, ….
• Apply biological methods to develop new materials or devices
– Self assembly of nanostructures.
Options Offered by NS&E
Overall:Fertile technology arena for new products and applications
9
DuPont Semiconductor Materials SalesLithography• ARC Polymer (EP)• Developers• Mask/Pellicle (Teflon®)• Removers (EKC)• Resist Polymers (EP)
Etch & Clean Processes• Remover/Cleaner (EKC, DCSE)• Liquid Etchants• Spec. Gases (Zyron®)
Deposition• ALD• CVD• PVD• Sputtering• Ion Implant• Low k, High k• PI stress buffers/redistribution (HDMS)
Planarization• Cleaners (EKC)• Pads (Teflon® Release Coat)• Slurries (DANM)
Infrastructure• Fluid Handling (Teflon®, Kalrez®, Vespel®)• Wafer Handling (Teflon®, Kalrez®, Vespel®)• Corrosive Fume Exhaust Linings (Teflon®)
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- Fluid Increases The Numerical Aperture - Fluid Decreases Wavelength λ/nIF
physicalIFeff NAnNA ≈
MIT-LL
Immersion FluidA/cm < 0.22
Projection Lens
Photoresist CoatedSilicon Wafer
IFlithoeff nλλ ≈
90
0.40
0.85
193
1
2004
45
0.3
1.3
193i H2O
65
0.31
0.93
193i H2O
38
0.29
1.5
193iGen2
22
0.3
0.3
EUV?
k1
NA
λ nm
hp nm 130
0.39
0.75
248
1.4361.436 >1.6 1index 1
32
0.25
1.5
193iGen2
>1.6
20082006 2009 20131st Year 2001 2011
26
0.24
1.8
193iGen3
>1.8
2012
22
1
2013
Im-print?
32
0.30
1.8
193iGen3
>1.8
2011
Immersion Lithography Roadmap
11
32nm Imaging with Dupont IF131 & IF132 High-n Immersion Fluids (Initial Fluid Screening)
IF131 n=1.642, A/cm=0.17 IF132 n=1.644, A/cm=0.08Similar imaging performance from the two fluids, both very good!
No visual effect on resist films without topcoat.Ref. H.Sewell, et.al 32nm node technology development, SPIE 5753-56 conference
32nm Lines (pitch 64nm)
12
Advanced Polymerization Technologies for Improved 193, 193i and Beyond Lithographic Performance
1. Advanced Polymerization Process Control for High Compositional Uniformity (HCU)
2. RAFT Technology for Narrow Molecular Weight Distribution
Combine HCU and RAFT for optimum polymer architectural control
13
Copolymer Produced with Good
Compositional Uniformity
Low Line Edge Roughness
Uniform Dissolution Performance (No Nanodefects)
DuPont’s Closed Loop Process Leads to Improved Control of HCU Leading to Lower LWR and Fewer Nanodefects
Clusters with High Solubility
Copolymer Produced with Poor
Compositional Uniformity During film formation,
similarly polarized groups form areal
clusters
Film Formation
Development
Clusters with Low Solubility
14
Effect of Process Variability on Lithography
Acryl conc. (mol%)
0
100
NbFOH conc. (mol%)100
0
TFE conc. (mol%)100
0
Run 31 Closed Loop Composition
Acryl conc. (mol%)
0
100
NbFOH conc. (mol%)100
0
TFE conc. (mol%)100
0
Run 21 Open Loop Composition
StDev = 1.61Z = 0.49
StDev = 0.17 Z = 7
Open Loop
Closed-Loop (HCU)
In-Situ Liquid Phase Composition Control (193 nm terpolymer example) 193 nm Lithography
Higher defects and LWR
Lower defects and LWR
15
RAFT (Reversible Addition Fragmentation Chain Transfer) -Low Polydispersity Technology for 248 and 193 nm Resins
1) Better line shape and sidewall.
2) Better thermal properties (flow) and thermal stability.
3) Higher film transparency at 248 nm and 193 nm.
4) Increased photospeed
Some of the benefits of materials with lower polydispersity are:
DuPont’s RAFT Low PD technology extends to ALL photoresist polymer platforms for both 248 and 193 materials. This technology is not limited by constraints of older cryogenic, alkyl metal polymerization processes.
16
Copper Cleaning Solutions
CuSolve™ - designed to effectively remove post-etch residue from substrates containing copper
• Suitable for via and trench clean.• Non metal hard mask and oxide/PR mask
integration schemes.
• Successful demos and Process of Records at 130nm, 110nm, 90nm, 65nm - evaluations underway at 45nm.
• Optimised for Single Wafer Toolsets but extendable to batch processing due to high selectivity.
• Small Environmental Footprint• Compatible with a wide range of low-k
dielectrics
17
Single Atomic Cu Layer
SiO2 /barrier layer substrate
DuPont DesignerMolecule
Precursor Introduced Chemi-absorbedMonolayer
Copper Seed Through Atomic Layer Deposition (ALD)
Designer Molecules/ALD
Low deposition temperature processF and O freeHighly volatileStableThin, conformal film with no gaps Reducing Agent Introduced
and Ligands Removed
TEM of copper film
18
DuPont Air Products Nanomaterials Product PortfolioStrong products in Copper and barrier
slurries:
• Copper slurries qualified at 130, 90, 65 and 45 nm technology nodes
• Barrier slurries qualified at 90 and 45 nm technology nodes
Long history of successful Tungsten products:
• W slurries qualified at 180, 130, 110 and 90 nm technology nodes
Successful implementation of AutoStopSTI slurries:
• STI slurries qualified at 110, 90 and 65 nm technology nodes
19
Particle Size Distribution
0
25
50
75
100
125
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69
Particle Size (nm)
Mea
n W
t By
Num
ber
Cumulative PSD
20
Abrasive Characteristics - TEMTypical raw material particles
Spherical, uniform particles 50 nm mean size with tight size distribution
21
Next Generation CMP: Membrane-Mediated Electropolishing
+
_CuSO4 Electrolyte
De-ionized Water
Cathode Half-Cell AssemblyNafion® Membrane
Electrolytic process• No abrasives
• No reagents consumed
• No contamination
• No waste
• High removal rate, low pressure
• No erosion of barrier layer
Wafer (anode)
22
Mean Thickness Loss (nm)
0 100 200 300 400 500 600 700 800 900
Step
Hei
ght (
nm)
-100
0
100
200
300
400
500
600
700MMEP (DuPont)ECP*CMP (EKC/DuPont)
Dishing:
100 µm lines & spaces
Mean Cu Thickness
Step Height
Test Wafer : Dielectric
ECD Copper
Planarization Efficiency
* Y. Tohma, et. al., Ebara Corp., ADMETA, 2004.
23
CNTThin film gate conductors Thick film emitter
Glass substrate
Thick filminsulator
ITO coated glass substrate
Color phosphor
Cathode
Anode
1-2 mm
Field Emission Displays
24
Activation Is Critical for Uniform Emission
activated
unactivated
1.00E-11
1.00E-10
1.00E-09
1.00E-08
1.00E-07
1.00E-06
1.00E-05
1.00E-04
1.00E-030 0.5 1 1.5 2 2.5
ELECTRIC FIELD (V/µm)
Cur
rent
Den
sity
(Am
p/cm
2
activated
unactivated
25
Printed ElectronicsFlexible, low cost electronics through DuPont competencies in materials development, coatings,precision patterning, and characterization
Thermal Multilayer Printing
26
Printed Electronics:Functional Nanomaterials in Many Layers ?
Conductors:Carbon nanotubesdispersed in modified polyaniline
High K dielectric: Inorganic nanoparticles dispersed in polymer?
Semiconductor: Inorganic or organic nanomaterialsdispersed in host polymer?:
PET substrate
27
Nano Technology in Ink Jet:Effect of Particle Size on Gloss
Particle Size versus 60o Gloss
0
20
40
60
80
100
120
0 50 100 150 200 250
Average Particle Size in nm
60o G
loss
Smaller particles are needed for high gloss applicationsuch as photo printing
Larger particles scatter light, reduce gloss
28
• The presence of particles greater than 100 nm directly affects the reliability on ink jet pens
• Processes and materials had to be developed to eliminate this as an issue
Relationship of Failures versus Large Particles
0
10
20
30
40
50
0.0 5.0 10.0 15.0
ppm of Particles > 500 nm
Num
ber o
f Fai
lure
s
Large particles settle outClog nozzle
Nozzle area
Nano Technology in Ink Jet:Effect of Particle Size on Reliability
29
DuPont Voltron™ Nanocomposite Wire Enamels Protect High Voltage Equipment Against Corona Discharges
0,4 0,3 *)
> 1000
> 900 *)
297
55 *)
120
54 *)2 1 *)
0,0
100,0
200,0
300,0
400,0
500,0
600,0
700,0
800,0
900,0
1000,0
1100,0
Life
time
[h]
Sta nda rd Voltron™ Coa ting 1 Coa ting 2 Coa ting 3
*) m a gne t w ire w ith 10% pre - stre tching
Voltron™
Dispersed Dispersed NanomaterialsNanomaterials
Frank-Rainer Boehm
Example: Inverter driven motors
30
Dispersed Dispersed NanomaterialsNanomaterials
Voltron™: Modified Wire Enamel Polymer Units
OHHO
O CH2CH2
N A N O – P A R T I C L E
Si O2 -
O
CH2CH2O CO
(THEIC-Polyesterimide)
OH
N A N O M E R
OH
OH
N A N O – P A R T I C L E
(THEIC-Polyesterimide)
O Ti
OR
OR
Si O2-
HO
N
NNO CH 2CH 2O
HOCH2CH2
O
O
CO
(THEIC-Polyesterimide) O
O
O
(THEIC-Polyesterimide)
OR
O
TiRO
Frank-Rainer Boehm
31
DuPont Photonic Components & Modules
Blank Wafer to Diced Chips in 6
Hours
iSELECT™ 4000Form 3:Black box with optical and electrical connectors
Form 2:Packaged chip on PCB with control electronics and firmware
Waveguide Fabrication
Metalization
Form 1:Packaged chip
Dicing, Packaging
32
Optical Polymer Requirements
1. Low absorption loss2. Low wavelength dependent loss (WDL)3. Low polarization dependent loss (PDL)4. Low polarization mode dispersion (PMD)5. Low chromatic dispersion (CD)6. Low birefringence7. Low stress8. Low fiber pigtail loss9. Closeness to refractive index of silica fiber10. Stability of refractive index11. Variable refractive index difference (∆n)12. Variable refractive index profile13. Low refractive index dispersion (dn/dλ)14. Large T/O coefficient (dn/dT)15. Linearity of refractive index with temperature16. Optimal thermal conductivity17. Thermal stability18. No phase transition in operating range19. Stability with humidity20. Hydrophobicity21. Stability with optical power22. Adhesion (to substrates, self, electrodes)23. Compatibility with electrode patterning24. Low reactivity to acids, bases, solvents25. Stability with oxygen
26. Isotropy27. Homogeneity28. Low level of impurities29. Optimal molecular weight distribution30. Optimal viscosity31. Low volatility32. Optimal photosensitivity33. Optimal cure speed34. Full curability35. Thermoset material36. High crosslink density37. Low shrinkage38. Optimal free volume39. Contrast in patterning40. Optimal surface energy41. Processability for high film quality42. Process latitude in patterning43. Patternability with low scattering loss44. Machinability (cleaving, dicing, polishing)45. Mechanical robustness46. Flexibility47. Stability of mechanical integrity48. Volume manufacturability49. Manufacturability with repeatable properties50. Long shelf life
The Top 50 List
Not an easy task –After 25 years of molecular nanoengineering,
DuPont optical polymers meet all 50 requirements
33
Hyper-branched FluoropolymersNanoengineered for Communication Applications
Properties:Low Absorption at 800-1600 nm
• FluorinationLow Birefringence and PDL
• Isotropic & homogeneousLow Shrinkage
• High MWFast Curing
• One end pre-fixedHigh Crosslink Density
• One end pre-fixedLow Volatility
• High MWControlled Viscosity
• MW & molecular structureHigh dn/dT for Thermo-optics
• High free volume & low Tg
In addition to molecular nanodesignand synthesis, photopolymers have dispersed nanocomposites that allow to achieve improvements in:
• Mechanical properties• High-temperature properties• Barrier properties• Processing characteristics
34
Integrated PhotodetectorsExcimer ablation of out-of-plane
mirrors & flip-chip bonding of photodiode arrays
Measured<0.3dB Excess Loss
<0.1dB PDL
PhotodiodeArray 45o mirror
PolymerCircuits
InP/InGaAs photodiode arraysflip-chip mounted on top of array of
polymer waveguides with 45°mirrors
45° mirror fabricated by Excimer laser ablation and metalization for waveguide to detector coupling
10 nm rms roughness
35
Nanomaterials Product Stewardship: Key Challenge
“ Engineered nanomaterials… typically possess nanostructure-dependent properties (e.g., chemical, mechanical, electrical, optical, magnetic, biological), which make them desirable for commercial or medical applications. However, these same properties potentially may lead to nanostructure-dependent biological activity that differs from and is not directly predicted by the bulk properties of the constituent chemicals and compounds.”
ILSI Nanomaterial Toxicity Screening Working Group October 6, 2005 Report entitled “Principles for characterizing the potential human health effects from exposure to nanomaterials; elements of a screening strategy”
36
NS&E Stewardship: What DuPont is doing
• Conducting toxicology studies DuPont Haskell Lab widely recognized as a leader
• Cooperating with external industry peers, academia, NGOs, government agencies, and standards development organizations
• Creating new tools and techniques for generating nanoparticle safety data and monitoring safety
• Working with Environmental Defense on a practical framework to identify, manage, and reduce SHE risks
37
Final Observations, Opinions, and Caveats:
Nanoscale Science and Engineering have been practiced (by materials suppliers and others) for many years
• Nanostructure is fundamental to properties of materials
• “Micro-Electronics” is already in the nano-world
Advances in NS&E will emerge in many fields, and at their intersections:• Materials Science, Polymer Science, Electronics, Biology, Medicine, …
• New tools; new windows into the nanoscale world: new ways to engineer nanoscalestructures.
Relevant to several distinct technologies with different paradigms • Generalizations about “Nanotechnology” can be confusing or misleading
Many of the foreseeable applications will be extensions of what we already do
Early attention to Product Stewardship is essential
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