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FUNCTIONALIZATION AND APPLICATION OF NANOMATERIALS FOR ELECTRONIC APPLICATIONS

Dr Toby SainsburyMaterials Division

National Physical Laboratory,

London, United Kingdom

[email protected]

NPL Management Ltd - Commercial

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NPL EI Free Technology WebinarsEnvironmental Robustness: Performance Coatings & High Temperature Interconnects

Tuesday 3 September

NPL Cleaning & Contamination Testing – Causes & Cures Webinar

Tuesday 22nd October

Other Group Activity

NPL Cleaning & Contamination Testing Center at Productronica 2013

12-15th November Productronica, Germany

Conformal Coating Application & Testing Center - NEW Electronics Birmingham 2014

8-10th April 2014 NEC Birmingham

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Productronica, GermanyNPL Cleaning & Contamination Testing Center

12-15th November

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OUTLINE

NANOTECHNOLOGY

PROPERTIES OF NANOMATERIALS

2D NANOMATERIALS GRAPHENE

HEXAGONAL BORON NITRIDE

ALTERNATIVE 2D NANOSHEETS

FUNCTIONALIZED NANOMATERIALS

ELECTRONIC APPLICATIONS OF FUNCTIONALIZED NANOMATERIALS CARBON NANOTUBE COMPOSITE SYSTEMS

FUNCTIONALIZED 2D NANOSHEET SYSTEMS

SUMMARY

• Nanotechnology: Technology involving benefits or attributes specifically assigned to the use or inclusion of materials which have one or more of their dimensions less than 100 nm.

– Synthesis of nanomaterials

– Appl ication by assembly, processing, and integration of materials and structures

– Result: Stronger, more conductive, l ighter, brighter, thermally conductive, smaller, faster, cheaper– Bottom l ine. Financial, environmental, medical, societal, and scientific benefits resulting from nanotechnology

• NANOMATERIALS1D NANOMATERIALS

– NANOTUBES: • C , BN, WS2, TiO2

• SnS2, MoS2, Wse

• NbS2– NANOWIRES:

• Si, Ge, CdSe, ZnO, GaN, Au

3D NANOMATERIALS

– NANOPARTICLES

• Au, Ag, Cu, Pd, Pt, SiO2, TiO2, ZnO,

– NANORODS

• CdS, CdSe, PbSe, PbS, Au, Ag

– QUANTUM DOTS

• CdS, CdSe, CdTe, PbS, PbSe, PbTe

– DNA ASSEMBLIES

– TETRAPODS

– PEPTIDE FIBRES

– MX2 ONIONS

• MoS2, WS2– C60

2D NANOMATERIALS

– GRAPHENE………

NANOTECHNOLOGY


• PROPERTIES

1D NANOMATERIALS

• High aspect ratio

• Highly conductive

• Highly insulating

• Semi ‐conductive

• Super conductive

• UV‐lasing

• Thermally conductive

• High strength

3D NANOMATERIALS

• Size tuneable plasmonic• Conductive

• Semi ‐conductive

• Insulating

• Fluorescent

• Cata lytic

• Biocompatible

• Anti ‐oxidative

2D NANOMATERIALS• GRAPHENE………

NANOMATERIALS

2D NANOMATERIALS: GRAPHENE

PROPERTIES

Conductive (mobility:200,000 cm2v‐1s ‐1) Chemically stability (<400 oC)

Young's modulus: ~1 TPa Surface area: 2630 m2g‐1

Low density (2.3 gcm‐3) Non‐polar bonds (= 0)

Thermal conductivity (~5000 Wm‐1K‐1) Planar structure (sp2)

Optical transmittance : 97.7% Crysta l line

ENVISAGED APPLICATIONS

Thermal management metrology standards ()

Compos ite materials Electronic (sub/super)

Batteries/supercapacitors Sensing and Diagnostics

Optoelectronics Cata lysis

CHALLENGES TO UTILIZATION: exfoliation, compatibilization, large‐area synthesis

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Graphene:Theoretical surface areaHigh intrinsic mobilityHigh Youngs modulusThermal conductivity Optical transmittance band gap Colour

SYNTHESIS CVD, epitaxial SiC, exfoliation

ADVANTAGES reasonably low cost, chemically stable yet highly amenable to specific chemistries. Abundant C as source material.

DRAWBACKS Grain boundaries, defects, dislocations, intrinsic tendency to aggregate and stack.incompatible with large proportion of solvents, resins, condensed phase and molecular compounds. Zero band gap. Highly sensitive to environmental contaminants, substrate effects.

NEED Qual ity control assessment and metrology surrounding standard graphenerel iable, scalable strategies for chemical integration s trategies for production‐scale electronic integration with suitable substrates and electrodes.

RISK Drawbacks are pertinent and realistic reasons why graphene may not reach anywhere near the theoretical potential discussed at present. Highlights the need for metrology, manufacturing and processing research to be accelerated and for chemistries to be investigated. Alternative nanosheet materials require immediate attention.

2D NANOMATERIALS :GRAPHENE

PROPERTIES

Insulator (Eg ~5.5 eV) Chemically stability (0‐850 oC)

Mechanically robust (E2d = 270 Nm‐1) Large surface area

Low density (2.3 gcm‐3) Heteropolar bonds (= 1)

Thermal conductivity (0.3 W.cm‐2.oC‐1) Planar structure (sp2)

Macroscopic colour Crysta lline

ENVISAGED APPLICATIONS

Thermal management Radiation Shielding

Compos ite materials Electronic (sub/super)

Storage/ Fuel Cell Sensing and Diagnostics

Optoelectronics Cata lysis

CHALLENGES TO UTILIZATION: exfoliation, compatibilization, large‐area synthesis

2D NANOMATERIALS :HEXAGONAL BORON NITRIDE

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2D NANOMATERIALS :ALTERNATIVE 2D NANOSHEETS• RANGE OF MATERIAL PROPERTIES

– Band gap 0‐6 eV, conductive to insulating

– Range of optical absorption wavelengths

– Luminescence quantum efficiency 1000 X bulk (MoS2)

– mobi li es2 >60 cm2 V−1 s−1 (MoS2)

– on−off current ra os up to 108 (MoS2)

– Thermoelectric (Bi2Te3)

– Topological insulator (Bi2Te3)

– Range of mechanical properties

– Range of thermal properties

• APPLICATION OF 2D NANOMATERIALS

– cata lysis

– Lubricant additives

– Nanoelectronics

– Sensors

– Nanocomposites

– Batteries

– Supercapacitors,

– Hydrogen storage

– Environmental science

– Metrology s tandards

– Themal management

– Barriers/membranes

– Dielectrics

• KEY FACTORS• Synthesis, manipulation, integration

• Chemical functionalization

FUNCTIONALIZED NANOMATERIALS


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BNNT FUNCTIONALIZATION ITEM CHARACTERIZATION OF BNNTS

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NANOTUBE FUNCTIONALIZATION

NANOTUBE FUNCTIONALIZATION

AMINE‐FUNCTIONALIZED BNNTS:BASE MATERIAL FOR EXTENSIVE LIBRARY OF FUNCTIONALIZED BNNTS

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SELF‐ASSEMBLY: HYBRID SYSTEMS

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BNNT-METAL SYSTEMS: Self-Assembly of Gold Nanoparticles at the Surface of Amine- and Thiol-Functionalized BNNTs


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Typical Low resolution TEM images of DMAP-stabilized palladium nanoparticlesself-assembled at the surface of different thiol-functionalized BNNTs.

Preparation of BNNT‐Pd‐nanoparticle Hybrid Structures

Aqueous suspensions of thiol‐functionalized BNNTs and palladium nanoparticles are combined and allowed equilibrate (6h).

Palladium nanoparticles are self‐assembled at the surface of BNNTs in solution.

Interaction is mediated by the thiol‐Pd covalent bond formation.


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ELECTRONIC APPLICATIONS OF FUNCTIONALIZED NANOTUBE SYSTEMS


CdS QRsBNNTs

APPLICATION OF BNNT MATERIALSSENSING AND DIAGNOSTIC

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TEM compatible devices: Standard TEM architectures do not allow electron transmission. Silicon nitride (Si3N4) membranes have been used as electron transparent supports for TEM imaging.

Schematic i llustration of typical TEM compatible device structure.

Fabrication process: (1) Silicon oxide is grown on a sil icon wafer(2) Silicon nitride fi lm is deposited by CVD(3) The sil icon is then selectively back-etched with KOH(4) The oxide and nitride layers are exposed to HF to remove

sil icon oxide.

Electronic Transport properties of Au-NP/BNNT


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The charging energy and the energy between step levels are estimated to be 1 eV and 0.25 eV, respectively. The capacitance of the device is approximately 0.16 aF.

(a) Current-voltage (I-V) property of gold nanoparticle-functionalized BNNT on the membrane device, which is measured at room temperature, and (b) a magnified I-V property of (a) and differential conductance plotted versus bias voltage. A series of

current steps is observed.

Current-Voltage characteristic of Gold Nanoparticle-functionalized BNNT structure


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3.0x106

2.5

2.0

1.5

1.0

0.5

0.0

Re

sist

anc

e (

)

101

102

103

104

105

106

107

Frequency (Hz)

1.4x10-3

1.2

1.0

0.8

0.6

0.4

0.2

0.0

Co

ndu

ctanc

e (S)

3.0x106

2.5

2.0

1.5

1.0

0.5

0.0

Re

sist

anc

e (

)

101

102

103

104

105

106

107

Frequency (Hz)

1.4x10-3

1.2

1.0

0.8

0.6

0.4

0.2

0.0

Co

ndu

ctan

ce (S

)

532 nm, <5mW

633 nm, =5mW

Optical Response on the Transport Properties of Gold Nanoparticle Functionalized BNNTs

-3.0x106

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

Im[Z

] (

)

3. 0x106

2 .52.01.51.00.50.0Re[ Z] ()

Dark 532nm 633nm

R (M) C (pF)

Dark 2.8 9.2

532 nm 2.6 10.2

632 nm 2.1 13.6

Nyquist plots: Optical Response of DPAP-Au-BNNT device


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CARBON NANOTUBE COMPOSITE SYSTEMS

CARBON NANOTUBE POLYMER COMPOSITES

CNT‐Polymer composites Conductive Shielding materials Protective materials High strength composites Thermal management materials

Properties highly dependent on nanotube type and dispersion.


ELECTRONIC CHARACTERIZATION OF CARBON NANOTUBE EPOXY COMPOSITES

KEY ROLE OF DISPERSION

NANOTUBE STRUCTURE

POOR DISPERSIONPERCOLATIONHIGHLY CONDUCTIVETHERMAL CONDUCTIONPOOR MECHANICAL

CONDUCTIVE POLYMER• ESD MANAGEMENT

• ELECTRODE STRUCTURES

• NLO PROPERTIES

I

V

CHOICE OF NANOTUBE• FIXED WEIGHT PERCENT: 1%

• SWNT• MWNT• DWNT• F‐CNT

• VARIABLE QUALITY• WALL STRUCTURE• DEFECTS• LENGTH• CHEMISTRY

• CLEAR DEMONSTRATION OF VARIABLE DISPERSION: VARIABLE CONDUCTIVITY COMPOSITES



VARIABLE LOADING MWNT‐EPOXY COMPOSITESSINGLE VENDOR NANOTUBES


CHEMICAL FUNCTIONALIZATION OF CARBON NANOTUBES Manipulates surface energy of CNTs Introduces chemical functional groups Facilitates compatibility and specific chemical integration via bonding RESULTING DISPERSION DICTATES ELECTRICAL, THERMAL AND

MECHANICAL PROPERTIESS



• HIGH QUALITY DIPSERSION

• ELECTRICAL ANALYSIS

• UNIFORM PROPERTIES

• CORRELATE WITH ALTERNATIVE CHARACTERIZATION

10

5

0

-5

-10

x10

-9

-1000 -500 0 500 1000

MWCNT –CT‐TCT‐1% Epoxy Composite 0 to +/‐1000V

EXCELLENT DISPERSION MECHANICALLY REINFORCING THERMALLY CONDUCTIVE HIGH TURN ON V DIELECTRIC PROPS BREAKDOWN PROTECTION ESD MANAGEMENT MATERIALS




ESD AND LIGHTNING STRIKE MANAGEMENT

Application of ESD event 0‐1000 VAnalysis of V vs T

FORMULATION MANIPULATION:

1. High pulse : 1000 V Clamping at 1000 V: conductor

2. Lowering of Vc – clamp voltage

3. CNT loading manipulated Vc

4. Vc controlled: 1000 V clamping at 50 V

V

V

V

T

T

T



Leakage testing pre and post ESD pulse vs CNT loading

Pre: 10‐10 APost: 10‐4 A

Pre: 10‐10 APost: 10‐6 A

Pre: 10‐10 APost: 10‐10 A




V

T (mS)

FUNCTIONALIZED 2D NANOSHEET SYSTEMS


FUNCTIONALIZED NANOSHEET SYSTEMS

FUNCTIONALIZED H‐BN :OH, COOH, BROMINE

MECHANICAL REINFORCEMENT , THERMAL CONDUCTIVITY, BARRIER COMPOSITES, DI‐ELECTRIC COATINGS, BAND GAP MANIPULATION

FUNCTIONALIZED GRAPHENE: BROMINE, CHLORINE, IODINE

BAND GAP MANIPULATIONSEMI‐CONDUCTING APPLICATIONSSENSING CHEMICAL DERIVITIZATIONCOMPOSITES

FUNCTIONALIZED MoS2 :COOH, OH, PFO, Au, Pd

MECHANICAL REINFORCEMENT , THERMAL CONDUCTIVITY, BARRIER COMPOSITES, BAND GAP MANIPULATIONGAS SENSING

FUNCTIONALIZATION OF BNNSs

Chemical functionalization of h‐BN nanosheets:

Mechanical reinforcement of polymer systems

Indicates chemical compatibilization

Chemical bonding

Utilization of h‐BN intrinsic properties

Implications towards, thermal, barrier, chemical protection,

Dielectric applications


FUNCTIONALIZATION OF GRAPHENE

Chemical functionalization of Graphene

Distortion of delocalized electron system

Chemical doping

Chemical functionality

Band gap manipulation

Application: Sensing Electronics Composites catalysis

FUNCTIONALIZATION OF MoS2Gold Nanoparticle functionalization of MoS2 nanosheets:

Gas sensing Ammonia H2S SO2

Chemically Functionalized MoS2nanosheets

Carboxy functionalized MoS2Fluorine functionalized MoS2

Applications: sensingCompositeselectronics


SUMMARY

NANOMATERIAL SYSTEMS

NANOTUBES

2D NANOSHEETS

FUNCTIONALIZATION OF NANOMATERIALS

ELECTRONIC APPLICATIONS OF NANOMATERIALS

SENSORS AND DIAGNOSTIC PLATFORMS

COMPOSITES FOR ELECTRONIC APPLICATIONS





[email protected]


NPL EI Free Technology WebinarsEnvironmental Robustness: Performance Coatings & High Temperature Interconnects

Tuesday 3 September

NPL Cleaning & Contamination Testing – Causes & Cures Webinar

Tuesday 22nd October

Other Group Activity

NPL Cleaning & Contamination Testing Center at Productronica 2013

12-15th November Productronica, Germany

Conformal Coating Application & Testing Center - NEW Electronics Birmingham 2014

8-10th April 2014 NEC Birmingham

www.npl.co.uk/ei

Documents

Your Delegate Webinar Control · PDF fileHEXAGONAL BORON NITRIDE ... Thermal conductivity (~5000 Wm‐1K‐1) ... nanosheet materials require immediate attention