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

Foster Rush
Leading 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

Foster Rush

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
Foster Rush

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%.

Foster Rush

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.

Foster Rush

MLCC High Capacitance Evolution

Source: Samsung Fine Chemical Co., Ltd.

Foster Rush

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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• 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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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.

Foster Rush

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

Foster Rush

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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Foster Rush


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

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Sintered film density improvement
with the addition of nano Ag
powder
Source: 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

Foster Rush

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.
Foster Rush

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. Foster Rush

• 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

Foster Rush


Nanocomposite thin film coating Polymer/ceramic nanocomposite on Pt/Si wafer
on copper foil for printed wiring
board applications

Source: nGimat Co.

Foster Rush

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

Foster Rush

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

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