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Foster Rush Leading Edge Materials Technology Consulting Recent Developments in the Adoption of Nano- Technology for Electronic Components Brian C. Foster

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Foster RushLeading Edge Materials

Technology Consulting

Recent Developments in the Adoption of Nano-

Technology for Electronic Components

Brian C. Foster

Foster RushLeading Edge Materials

Technology Consulting

Outline

• Market Driving Forces

• Major Product Trends

• Synthesis Approaches

• Enabling Materials and Device Development- Barium titanate for high capacitance MLCC devices

- Metal powders for inks and pastes for multilayer structures

- Nano graphine platelets for supercapacitor electrodes

- Nano oxides for filled polymers for embedded capacitors, antennas, tunable filters and phase shifters

• Conclusions

Foster RushLeading Edge Materials

Technology Consulting

Market Driving Forces

• Smaller footprint, lower mass & reduced cost with increased functionality and improved reliability- Integration of components into modules with higher circuit density,

decrease in component size

• Broad adoption of HDTV

• Increased functionality in portable devices- SMART phones driving consumer interface

- Touchscreen circuitry

- Netbook

- eReader

• Automotive navigation and entertainment systems- Drive by wire

- Telematics

• Hybrid and electric vehicles- Power electronics

• Energy Storage

• Robotics- Consumer oriented

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Major Product Trends

• Higher operating temperature environments (>150 oC)- Down hole, lighting and automotive applications

- Rated operating performance to 350 oC for selected applications

• Noise suppression and tuning at higher operating frequencies- Faster processor speeds and increased bandwidth

• High voltage transient suppression- HDTV, hybrid vehicle

• Smaller footprint, higher volumetric efficiency- High capacitance MLCC X5R

- Lower impedance at higher operating frequencies

- Embedded passives

• Energy Storage- Supercapacitors

• Cost reduction in components for consumer products- Solid state precursors

- Low cost raw materials

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Nano Technology Research Activity

Source: Semiconductor International, 1/21/2010

Ceramic and metal nano technology research has shown steady

growth over the past decade. Graphene research activity is

replacing CNT.

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Nano Powder Synthesis Approaches

• Catalytic Chemical Vapor Deposition: carbon nanotubes (CNTs) such as tangled CNTs, short dispersible CNTs,aligned CNTs, functionalized CNTs. A wide variety of inner diameters, outer diameters, lengths, functionalizations and purities are possible.

• Chemical Precipitation/Coprecipitation: single-metal oxides, multi-metal oxides and rare earth oxides.

• Combustion Chemical Vapor Condenstion: Possible materials include numerous ceramics of one or more cations and certain metals.

• Laser Induced Chemical Vapor Deposition: Si, SiC and oxides, with average particle sizes around 10 nm, 50 nm and 100 nm, free from aggregation.

• Microemulsions: oxides and compounds with precise control of small (5-10 nm) average particle size.

• Sol-Gel: narrow particle size range and aggregated nanopowders.

• Plasma Enhanced Chemical Vapor Deposition: metals (average particle size of 25 nm, 60 nm, 80 nm and 120 nm) and silicon, carbides, borides and nitrides (average particle size of 5 nm, 10 nm, 30 nm, 60 nm, 200 nm, 300 nm and 500 nm), purity of 99% or 99.9%.

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Nano Powder Synthesis Approaches

• Plasma Physical Vapor Deposition: vapor temperature less than 3,000 K, resulting in an average particle size of 90-150nm. Purities of 3N, 4N, 5N or higher. Nanoparticles can be solid elements, metal oxides, carbides, nitrides and more, with a special focus on nanoparticles with superior electronic properties.

• Wet Chemistry: metallic nanopowders (W, Mo, Ta, etc.), oxides and carbides. High-pressure wet chemistry also possible for specific phases.

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MLCC High Capacitance Evolution

Source: Samsung Fine Chemical Co., Ltd.

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Oxalate-Derived Barium Titanate

• Synthesis of barium titanate via the thermal decomposition of barium-titanyl-oxalate- BTO formed from various barium precursors and titanium

oxychloride in the presence of oxalic acid

• Traditional processing results in large agglomerates of BTO in the size range >100 microns- Inhomogeneous formation of barium titanate during

decomposition from the center to the surface of the agglomerated crystals

� Poor particle size and morphology control

� Non-uniform Ba:Ti ratio

� Wide distribution of crystallinity (c/a ratio)

• Mechanical milling to reduce aggregated barium titanate to primary particle size detrimental to electrical properties

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Oxalate-Derived Barium Titanate

• New oxalate synthesis approaches have focused on producing nano-sized BTO without agglomeration- Uniformity of Ba & Ti at the atom scale

- Discrete nano BTO that converts to nano barium titanate particles at lower temperatures with a higher degree of tetragonal crystallinity

Source: S. Wada, Univ. of Yamanashi

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Oxalate-Derived Barium Titanate

Source: Samsung Fine Chemical Co., Ltd.

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Microemulsion Synthesis of Barium Titanate

• Formation of barium titanate from barium and titanium precursors in a water-oil emulsion- Stable isotropic dispersion of the aqueous phase in the

continuous oil phase

� Nanosized water droplets

- Precipitation/co-precipitation reaction takes place in the nanosized aqueous domains when droplets containing reactants collide

- Water droplets act as a nanosized reactor for forming nanosized precursor particles

• Low reaction temperature to form crystalline barium titanate (80o C)

• Transparent films can be formed directly from the emulsion

• Ferroelectric behavior below 50 nm grain size

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Microemulsion Synthesis of Barium Titanate

Barium titanate nanoparticles Barium titanate thin film formed

with microemulsion precursor

Source: Murata Manufacturing Co., Ltd.

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Solid State Reaction of Composite Particles

• Low cost alternative to chemical synthesis routes

• Formation of composite particles using chemical coating technique

• Thermally reacted to form single phase material- Lower reaction temperatures, finer particle sizes when

compared to mixtures of nanocrystalline raw materials

- Maximized contact surface between reactants

- Minimization of diffusion distances

Source: Solvay Bario e Derivati

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Nano Metal Powders for Inks and Pastes

• Multiple synthesis approaches to produce particles in the 2-100 nm size range

- Au, Pt, Pd, Ag

- Cu, Ni, Al

• High conductivity and low processing temperatures

- Focus on print electronics, sensors and solar cells

� Compatible with processing on flexible organic films

� Photo curable/sintered

- Wirebond replacement for 3D stacked chip architectures

• Additive to conventional thick film pastes to improve sintered film density

- Lower resistivity films

- Thinner deposition

• Extending the technology to include silicon, dielectric and organic inks for passive and active electronic devices

- Diodes, capacitors, resistors, and transistors

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Nano Metal Powders for Inks and Pastes

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Nano Metal Powders for Inks and Pastes

Ag nano-particles stabilized in suspension by organic ligand shellsSource: NanoMas Technologies

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Nano Metal Powders for Inks and Pastes

Sintered film density improvement

with the addition of nano Ag

powderSource: NanoMas Technologies

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Nano Graphene Platelets for Electrodes

• Alternative to carbon nanotubes and fibers- Cost effective mass production

- Very high surface area, 2600 m2/g

- High conductivity

• Can be functionalized via surface grafting or polymerization

• Aspect ratios of thickness as low as ~ 0.34 nm and length (width) range of ~ 100 nm to 10 mm

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Nano Graphene Platelets for Electrodes

• Meso-porous nanocomposites based on NGP- NGP coated with conducting polymer or surface functional

groups

- NGP bonded by a conductive binder,coating or matrix material such as a polymeric carbon

- Comprised of a sheet(s) of graphite plane with thickness <10 nm and an average length, width or diameter <500 nm

Source: US patent 7,623,340

Angstron Materials Inc.

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Nano Oxides for Filled Polymers

• Atomization and combustion to form single, bi-metal and multi-metal oxides- Vapor and plasma arc synthesis

• Critical processing issues:- Control and modification of composition

- Particle size and distribution, morphology

- Surface control and dispersibility

- Scalability and cost

Combustion Chemical Vapor Condensation

Source: nGimat Co.

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Nano Oxides for Filled Polymers

• Polymer/ceramic nanocomposites for embedded capacitors- Dielectric thickness <500 nm to maximize capacitance

- Reduction of ESR and ESL compared to SMD producing cleaner wave forms and improved performance during microprocessor switching

- Better management of plane resonances to reduce EMI

- Supports substantial reduction in package and board size

• Filled polymers for antennas, tunable filters and phase shifters- High dielectric permittivity, low dielectric loss, high dielectric

strength, and large nonlinear response to electric field for high frequency microwave applications

� Wide operating frequency range

� Compact

� Lower transmitter power, longer battery life, reduced handset size

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Nano Oxides for Filled Polymers

Nanocomposite thin film coating

on copper foil for printed wiring

board applications

Polymer/ceramic nanocomposite on Pt/Si wafer

Source: nGimat Co.

Foster RushLeading Edge Materials

Technology Consulting

Conclusions

• Research and Development activity in nano-technology applicable to electronic components has been steadily increasing

• Reduction to practice in some areas has led to the commercialization of next generation devices

• Scalability and manufacturing cost remain barriers for some synthesis approaches

• Continuous improvement in the functionality of electronic devices and the resulting demands on component miniaturization and integration will drive the next wave of nano technology commercialization