FUNCTIONALIZATION AND APPLICATION OF NANOMATERIALS FOR ELECTRONIC APPLICATIONS Dr Toby Sainsbury Materials Division National Physical Laboratory, London, United Kingdom toby.sainsbury@npl.co.uk Your Delegate Webinar Control Panel Open and close your panel Full screen view Raise hand for Q&A at the end Submit text questions during or at the end NPL Management Ltd -Commercial 2
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Cleaning & Contamination Testing Center A2 429 http://productronica.com/link/en/27159297#27159297 FUNCTIONALIZATION AND APPLICATION OF NANOMATERIALS FOR ELECTRONIC APPLICATIONS Dr Toby Sainsbury Materials Division National Physical Laboratory, London, United Kingdom toby.sainsbury@npl.co.uk
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 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 Application by assembly, processing, and integration of materials and structures Result: Stronger, more conductive, lighter, brighter, thermally conductive, smaller, faster, cheaper Bottom line. Financial, environmental, medical, societal, and scientific benefits resulting from nanotechnology NANOMATERIALS 1D NANOMATERIALS NANOTUBES: C, BN, WS 2, TiO 2 SnS 2, MoS 2, Wse NbS 2 NANOWIRES: Si, Ge, CdSe, ZnO, GaN, Au 3D NANOMATERIALS NANOPARTICLES Au, Ag, Cu, Pd, Pt, SiO 2, TiO 2, ZnO, NANORODS CdS, CdSe, PbSe, PbS, Au, Ag QUANTUM DOTS CdS, CdSe, CdTe, PbS, PbSe, PbTe DNA ASSEMBLIES TETRAPODS PEPTIDE FIBRES MX2 ONIONS MoS 2, WS 2 C 60 2D NANOMATERIALS GRAPHENE
NANOMATERIALS 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 Catalytic Biocompatible Anti oxidative 2D NANOMATERIALS GRAPHENE PROPERTIES 2D NANOMATERIALS: GRAPHENE Conductive (mobility:200,000 cm 2 v 1 s 1 ) Chemically stability (<400 o C) Young's modulus: ~1 TPa Surface area: 2630 m 2 g 1 Low density (2.3 gcm 3 ) Non polar bonds ( = 0) Thermal conductivity (~5000 Wm 1 K 1 ) Planar structure (sp 2 ) Optical transmittance : 97.7% Crystalline ENVISAGED APPLICATIONS Thermal management metrology standards ( ) Composite materials Electronic (sub/super) Batteries/supercapacitors Sensing and Diagnostics Optoelectronics Catalysis CHALLENGES TO UTILIZATION: exfoliation, compatibilization, large area synthesis 10
Graphene: Theoretical surface area High intrinsic mobility High Youngs modulus Thermal conductivity Optical transmittance band gap Colour SYNTHESIS ADVANTAGES DRAWBACKS NEED RISK 2D NANOMATERIALS : GRAPHENE CVD, epitaxial SiC, exfoliation reasonably low cost, chemically stable yet highly amenable to specific chemistries. Abundant C as source material. 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. Quality control assessment and metrology surrounding standard graphene reliable, scalable strategies for chemical integration strategies for production scale electronic integration with suitable substrates and electrodes. 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. PROPERTIES 2D NANOMATERIALS : HEXAGONAL BORON NITRIDE Insulator (Eg ~5.5 ev) Chemically stability (0 850 o C) Mechanically robust (E 2d = 270 Nm 1 ) Large surface area Low density (2.3 gcm 3 ) Heteropolar bonds ( = 1) Thermal conductivity (0.3 W.cm 2. o C 1 ) Planar structure (sp 2 ) Macroscopic colour Crystalline ENVISAGED APPLICATIONS Thermal management Radiation Shielding Composite materials Electronic (sub/super) Storage/ Fuel Cell Sensing and Diagnostics Optoelectronics Catalysis CHALLENGES TO UTILIZATION: exfoliation, compatibilization, large area synthesis 12
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) mobili es2 >60 cm2 V 1 s 1 (MoS2) on off current ra os up to 10 8 (MoS2) Thermoelectric (Bi2Te3) Topol ogical insulator (Bi2Te3) Range of mechanical properties Range of thermal properties APPLICATION OF 2D NANOMATERIALS catalysis Lubricant additives Nanoelectronics Sensors Nanocomposites Batteries Supercapacitors, Hydrogen storage Environmental science Metrology standards Themal management Barriers/membranes Dielectrics KEY FACTORS Synthesis, manipulation, integration Chemical functionalization FUNCTIONALIZED NANOMATERIALS
15 BNNT FUNCTIONALIZATION I TEM CHARACTERIZATION OF BNNTS 16
NANOTUBE FUNCTIONALIZATION NANOTUBE FUNCTIONALIZATION AMINE FUNCTIONALIZED BNNTS: BASE MATERIAL FOR EXTENSIVE LIBRARY OF FUNCTIONALIZED BNNTS 18
SELF ASSEMBLY: HYBRID SYSTEMS 19 SELF ASSEMBLY: HYBRID SYSTEMS BNNT-METAL SYSTEMS: Self-Assembly of Gold Nanoparticles at the Surface of Amine- and Thiol- Functionalized BNNTs 20
SELF ASSEMBLY: HYBRID SYSTEMS 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. Typical Low resolution TEM images of DMAP-stabilized palladium nanoparticles self-assembled at the surface of different thiol-functionalized BNNTs. 21 ELECTRONIC APPLICATIONS OF FUNCTIONALIZED NANOTUBE SYSTEMS
APPLICATION OF BNNT MATERIALS SENSING AND DIAGNOSTIC CdS QRs BNNTs 23 APPLICATION OF BNNT MATERIALS SENSING AND DIAGNOSTIC Electronic Transport properties of Au-NP/BNNT 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 illustration of typical TEM compatible device structure. Fabrication process: (1) Silicon oxide is grown on a silicon wafer (2) Silicon nitride film is deposited by CVD (3) The silicon is then selectively back-etched with KOH (4) The oxide and nitride layers are exposed to HF to remove silicon oxide. 24
APPLICATION OF BNNT MATERIALS SENSING AND DIAGNOSTIC Current-Voltage characteristic of Gold Nanoparticle-functionalized BNNT structure (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. 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. 25 APPLICATION OF BNNT MATERIALS SENSING AND DIAGNOSTIC Optical Response on the Transport Properties of Gold Nanoparticle Functionalized BNNTs 532 nm, <5mW Resistance ( ) 633 nm, =5mW Resistance ( ) 3.0x 10 6 2.5 2.0 1.5 1.0 0.5 0.0 3.0x10 6 1.4x10-3 1.2 1.0 0.8 0.6 0.4 0.2 0.0 10 1 10 2 10 3 10 4 10 5 10 6 10 7 Frequency (Hz) 1.4x10-3 2.5 1.2 2.0 1.0 1.5 0.8 0.6 1.0 0.4 0.5 0.2 Conductance (S) Im[Z] ( ) Conductance (S) -3.0x10 6-2.5-2.0-1.5-1.0-0.5 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 Dark 532nm 633nm 0.0 10 1 10 2 10 3 10 4 10 5 10 6 10 7 Frequency (Hz) 0.0 0.0 0.0 0.5 1.0 1.5 Re[ Z] ( ) 2.0 2.5 3. 0x10 6 26
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 DISPERSION PERCOLATION HIGHLY CONDUCTIVE THERMAL CONDUCTION POOR MECHANICAL CONDUCTIVE POLYMER ESD MANAGEMENT ELECTRODE STRUCTURES NLO PROPERTIES ELECTRONIC CHARACTERIZATION OF CARBON NANOTUBE EPOXY COMPOSITES CHOICE OF NANOTUBE FIXED WEIGHT PERCENT: 1% SWNT MWNT DWNT F CNT I VARIABLE QUALITY WALL STRUCTURE DEFECTS LENGTH CHEMISTRY CLEAR DEMONSTRATION OF VARIABLE DISPERSION: VARIABLE CONDUCTIVITY COMPOSITES V
VARIABLE LOADING MWNT EPOXY COMPOSITES SINGLE VENDOR NANOTUBES ELECTRONIC CHARACTERIZATION OF CARBON NANOTUBE EPOXY COMPOSITES 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
ELECTRONIC CHARACTERIZATION OF CARBON NANOTUBE EPOXY COMPOSITES HIGH QUALITY DIPSERSION ELECTRICAL ANALYSIS UNIFORM PROPERTIES CORRELATE WITH ALTERNATIVE CHARACTERIZATION ELECTRONIC CHARACTERIZATION OF CARBON NANOTUBE EPOXY COMPOSITES x10-9 MWCNT CT TCT 1% Epoxy Composite 0 to +/ 1000V 10 5 0-1000 -500 0 500 1000-5 -1 0 EXCELLENT DISPERSION MECHANICALLY REINFORCING THERMALLY CONDUCTIVE HIGH TURN ON V DIELECTRIC PROPS BREAKDOWN PROTECTION ESD MANAGEMENT MATERIALS
ELECTRONIC CHARACTERIZATION OF CARBON NANOTUBE EPOXY COMPOSITES ESD AND LIGHTNING STRIKE MANAGEMENT Application of ESD event 0 1000 V Analysis 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 ELECTRONIC CHARACTERIZATION OF CARBON NANOTUBE EPOXY COMPOSITES ESD AND LIGHTNING STRIKE MANAGEMENT Leakage testing pre and post ESD pulse vs CNT loading Pre: 10 10 A Post: 10 4 A Pre: 10 10 A Post: 10 6 A Pre: 10 10 A Post: 10 10 A
ELECTRONIC CHARACTERIZATION OF CARBON NANOTUBE EPOXY COMPOSITES ESD AND LIGHTNING STRIKE MANAGEMENT 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 MANIPULATION SEMI CONDUCTING APPLICATIONS SENSING CHEMICAL DERIVITIZATION COMPOSITES FUNCTIONALIZED MoS2 : COOH, OH, PFO, Au, Pd MECHANICAL REINFORCEMENT, THERMAL CONDUCTIVITY, BARRIER COMPOSITES, BAND GAP MANIPULATION GAS 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 Gold Nanoparticle functionalization of MoS2 nanosheets: Gas sensing Ammonia H 2 S SO 2 Chemically Functionalized MoS 2 nanosheets FUNCTIONALIZATION OF MoS 2 Carboxy functionalized MoS 2 Fluorine functionalized MoS 2 Applications: sensing Composites electronics
SUMMARY NANOMATERIAL SYSTEMS NANOTUBES 2D NANOSHEETS FUNCTIONALIZATION OF NANOMATERIALS ELECTRONIC APPLICATIONS OF NANOMATERIALS SENSORS AND DIAGNOSTIC PLATFORMS COMPOSITES FOR ELECTRONIC APPLICATIONS FUNCTIONALIZATION AND APPLICATION OF NANOMATERIALS FOR ELECTRONIC APPLICATIONS Dr Toby Sainsbury Materials Division National Physical Laboratory, London, United Kingdom toby.sainsbury@npl.co.uk
NPL EI Free Technology Webinars Environmental 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 12-15 th November Productronica, Germany Conformal Coating Application & Testing Center - NEW Electronics Birmingham 2014 8-10 th April 2014 NEC Birmingham www.npl.co.uk/ei