Recent Developments in the Adoption of Nano-Technology for Electronic Components

Foster RushLeading Edge Materials

Technology Consulting

Recent Developments in the Adoption of Nano-

Technology for Electronic Components

Brian C. Foster



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



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



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



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.



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%.



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.



MLCC High Capacitance Evolution

Source: Samsung Fine Chemical Co., Ltd.



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




• 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




Source: Samsung Fine Chemical Co., Ltd.



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



Microemulsion Synthesis of Barium Titanate

Barium titanate nanoparticles Barium titanate thin film formed

with microemulsion precursor

Source: Murata Manufacturing Co., Ltd.



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



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




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




Sintered film density improvement

with the addition of nano Ag

powderSource: NanoMas Technologies



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



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.



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.




• 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




Nanocomposite thin film coating

on copper foil for printed wiring

board applications

Polymer/ceramic nanocomposite on Pt/Si wafer

Source: nGimat Co.



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

Recent Developments in the Adoption of Nano-Technology for Electronic Components

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