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

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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.

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1802 1830 1850 1900 1925 1945 1990 2000 2050 2090

Explosives

ChemicalsPolymersFibersEnergy

BIRTH

GROWTH

MATURITY

BIRTH

GROWTH

MATURITY

BIRTH

GROWTH

MATURITY

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ChemistryBiotechnologyMaterials ScienceElectronics Safety & Security

Transforming for Our Third Century

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Plastics and Chemicals: 14%

Motor Vehicle: 26%

Textiles/Home Furnishings: 1%Construction Materials: 14%

Agriculture/Food: 28%

Our MarketsElectronics: 9%

Other: 8%

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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…

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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

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• 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

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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?

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0.30

1.8

193iGen3

>1.8

2011

Immersion Lithography Roadmap

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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)

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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

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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

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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

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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.

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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

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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

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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

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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

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Abrasive Characteristics - TEMTypical raw material particles

Spherical, uniform particles 50 nm mean size with tight size distribution

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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)

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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.

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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

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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

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Printed ElectronicsFlexible, low cost electronics through DuPont competencies in materials development, coatings,precision patterning, and characterization

Thermal Multilayer Printing

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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

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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

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• 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

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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

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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

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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

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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

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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

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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

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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”

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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

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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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