Carbon NanoBuds (CNB) Synthesis, Structure and Thin Film Device - PowerPoint PPT Presentation

Carbon NanoBuds (CNB) – Synthesis, Structure and Thin Film Device Applications Prof. Dr. Esko I. Kauppinen NanoMaterials Group (NMG) Department of Applied Physics Helsinki University of Technology (TKK) Espoo, Finland FINNISH-JAPANESE WORKSHOP on FUNCTONAL MATERIALS Säätytalo 26.5.2009, Helsinki, Finland

Nan anoM oMat ater erial als (Nan anoM oMat at) Gro roup up Department artment of Applied plied Physics ics and Center er for New Material ials Nanobud Hels lsinki inki Univers ersity ty of Technology ology (TKK) http://www.fyslab.hut.fi/nanomat Carbon nanotube 1 ). Synthesis of carbon nanotubes and nanobuds 2). Synthesis of multicomponent nano- and microparticles for drug and gene delivery 3). Structural characterization of nanotubes and nanoparticles by electron microscopy 4). Generation of novel 2-D and 3-d nanotube, nanobud and polymer/protein structures for transparent electronics and energy applications 5). MD and DFT

NanoMaterials Group, Helsinki University of Technology Dept. of Applied Physics & Center for New Materials Dr. Albert G. Nasibulin Dr. Hua Jiang Dr. Janne Raula Mrs. Jing Tian Ms. Marina Zavodchikova Also: Antti Kaskela, Toma Susi Dr. David P. Brown http://www.fyslab.hut.fi/nanomat/ CEO, Canatu Oy Acknowledgement for Funding * Academy of Finland * EU FP6 & FP7 TKK 100th Anniv. Fund NEDO * TEKES FinNano Program

• Personnel – 1 prof. and 5 post-docs – 10 graduate and 7 undergraduate students • Doctoral level expertise – Carbon nanotubes, nanobuds, metal oxide nanowires (Albert G. Nasibulin - phys.chem) – Drug, polymer, peptide and protein chemistry, nanoparticle synthesis and CNT & CNB surface functionalisation (Janne Raula – polymer mat.) – Transmission electron microscopy of nanomaterials (Hua Jiang - physics) – Electrochemistry with carbon nanomaterials – FC&SC (Virginia Ruiz – phys. chem) – Molecular dynamics and DFT (Markus Kaukonen - physics) • External Funding – More than 1 000 k € /year – EU: BNC Tubes – Strep 2007-2010 3 500 k € ; NanoTox – SSA – Academy of Finland (e.g. NanoDuraMEA), TEKES, companies – CNB-E 2008-2012 MIDE/TKK 100 Years Anniversary Research Program

Acknowledgements for Collaboration – Prof. Yutka Phno, Nagoya U. Prof. Florian Banhart, U. Strasbourg Brad Aitchison, Jussi Sarkkinen, Canatu Oy Dr. Peter V. Pikhitsa and Prof. Mansoo Choi National CRI Center for Nano Particle Control, Institute of Advanced Machinery and Design, Seoul National University, Korea Dr. Abdou Hassanien and Dr. Günther Lientschnig AIST, Tsukuba, Japan Dr. Giulio Lolli and Prof. Daniel E. Resasco Chemical Biological and Materials Engineering, University of Oklahoma, USA Dr. Arkady V. Krasheninnikov and Prof. Risto Nieminen Laboratory of Physics, Helsinki University of Technology, Finland Prof. David Tománek Physics and Astronomy Department, Michigan State University, USA

Known forms of Carbon Nanomaterials Carbon Nanotube (SWCNT): Roll of carbon sheet one atomic layer thick = Graphene NanoRibbons (GNR) 1 000 000 times thinner than paper Rolling in different directions makes different kinds of tubes (10,10) armchair tube (10,5) helical (chiral) tube METALLIC SEMICONDUCTING By Prof. Shigeo Maruyama, Tokyo Universssity, Japan

CNTN -Materials for Flexible Electronics CNTN FET Mobility Year According to Prof. G. Gruner, UCLA,USA

Properties of Carbon Nanotubes • Better conductor than copper • Better transistor material than silicon • Conduct heat twice as efficiently as diamond • Field emit 500 times as efficiently as molybdenum • Thermally stable up to 1500 o C while polymers degrade below 150 o C • Half as dense as aluminum • 25 times stronger than steel • Very inert and difficult to integrate into composite materials and to incorporate into electronics manufacturing

Three allotropic modifications of carbon: diamond, graphite, and fullerene structures (fullerenes and CNTs). PEAPOD ? ? Graphene

CNB- Carbon NanoBud TM New Carbon NanoMaterial Nanobud TM combines Carbon Nanotubes and Fullerenes in Single Structure with Covalent Bonding Nasibulin & Kauppinen et al. Nature Nanotechnology, 2(3) 156 March 2007

Content of the Talk • CNB’s (Carbon NanoBuds = C 60 +SWCNT) – floating CVD synthesis, structure and properties • Novel Dry Thin Film Device Manufacturing Method • Field Electron Emission of CNB vs SWCNT films • Transparent flexible electrode and TFT • Preliminary results on nanocarbon PEMFC applications

2 α N Cat Bundling α N CNT Mechanism of 2 TEMPERATURE HIGH CNB Formation ZONE CO . CO . C CO 2 from CO with Fe CO 2 reaction with amorphous carbon: C + CO 2 = 2CO Cluster Catalyst End of CNT growth 900 °C - CARBON DISPROPRTIONATION IS PROHIBITED ( t > 900 ° C ) H 2 O Steady-state growth of CNT CO . - C INCORPORATION INTO GRAPHENE LAYER . . . . - R EACTIONS OF CARBON RELEASE AND ETCHING: CO H 2 CO H 2 2CO <=> C + CO 2 AND H 2+ CO <=> C + H 2 O CO 2 H O CO HEATING ZONE 2 CNT nucleation - HEPTAGON FORMATION Formation of graphene layer - HEXAGON AND PENTAGON FORMATION CO H O CO H 2 O . CO 2 2 CO CO - REACTIONS ON . . CO . REACTOR WALLS: CO 2 . Particle saturation by C . . 2CO = C + CO 2 . . - REACTIONS: 2CO = C + CO 2 AND H 2 +CO=C+H 2 O . H 2+ CO = C + H 2 O H 2 . - C RELEASE ON SURFACE . H 2 - CO 2 AND H 2 O - C DISSOLUTION . . . . CO RELEASE CO . H 2 H 2 F E particle formation 400 °C . . . . - VAPOUR NUCLEATION . . . . - CONDENSATION . . . . . . . - CLUSTER COAGULATION . . . . Fe(g) . . . . . . . . . . . . . . . . . . . . . CO CO CO H 2 /N 2

Synthesis of NanoBuds (CNB) – add CO 2 or H 2 O HWG method Ferrocene-based method

Lab scale (7) and pilot scale (1) reactors for CNT&CNB synthesis and in-situ thin film-based device manufacturing Flow reactors (3) for nanoparticle synthesis Pilot scale reactor Lab scale reactors

CNB formation mechanisms – Fullerenes nucleate from the graphene at the cluster surface Fullerens attached to graphene at Fe cluster surface

TEM of CNB Fe Catalyst via PVD Carbon from ethanol 10 nm 10 nm 10 nm 10 nm

TEM observation of the sample after washing in toluene and decaline Conclusion: nothing happened with fullerenes, they were not dissolved – stronger than Van der Waals bonding toluene decaline 5 5 n n m m 10 nm 10 nm

Controll of Fullerene density on CNB’s via H 2 O increase H 2 O concentration  1 1 0 0 n n m m 1 1 0 0 n n m m 1 0 n m 1 0 n m 1 0 n m 1 0 n m increase H 2 O concentration  1 1 0 0 n n m m 1 1 0 0 n n m m 1 0 n m 1 1 0 0 n n m m 1 0 n m

Synthesis of Carbon NanoBuds 885 ºC ferrocene cartridge water cooling 100 cm 3 /min circulation 300 cm 3 /min particles CO CO CNTs and fullerenes 0 10 0.2 µm 0.2 µm 945 ºC 20 position in reactor, cm 10 nm 10 nm water 30 40 2 nm dilutor 0 - 20 cm 3 /min 50 CO 2 or N 2 N 2 12 L/min 200 400 600 800 1000 1200 FT-IR/ ESP Temperature, °C Filter 0.2 µm 0.2 µm A.G.Nasibulin & E.I.Kauppinen et al, Chem.Phys.Lett, 446(2007), 109-114 .

NanoBuds TM on FEI Titan TEM at 80kV with image C s -corrector - Movie Individual Fullerene Fullerenes are NOT Cluster removed of by electron Fullerenes beam Image :B.Freitag FEI; samples : Prof. Kauppinen Helsinki, Finnland

Number size distribution of NanoBud TM fullerenes measured from HR-TEM images 0.30 C 60 0.25 C 42 0.20 Frequency 0.15 0.10 C 34 C 86 C 20 0.05 0.00 0.41 0.43 0.45 0.47 0.50 0.52 0.55 0.58 0.60 0.63 0.67 0.70 0.73 0.77 0.81 0.85 0.89 0.93 0.98 1.03 Diameter of fullerenes (nm) 0.39 0.41 0.43 0.45 0.47 0.50 0.52 0.55 0.58 0.60 0.63 0.67 0.70 0.73 0.77 0.81 0.85 0.89 0.93 0.98

Comparison of ultraviolet-visible absorption spectra of CNB’s, C 70 and C 60 standards in hexane: in toluene: Fullerene absortion bands: SWCNT absortion bands: 4.0 C 60 C 60 C 70 C 70 3.5 FFCNTs FFCNTs 3.0 Absorbance (au) 2.5 700 800 900 1000 1100 2.0 1.5 1.0 0.5 0.0 200 300 400 500 600 Wavelength (nm)

Raman spectra of NanoBuds carried out by using red (633 nm), green (514 nm), and blue (488 nm) lasers. 4 2.0x10 Intensity (au) 4 1.5x10 4 1.0x10 3 5.0x10 0.0 200 400 600 800 1000 1200 1400 1600 1800 -1 ) Raman shift (cm

Bonding scenarios of fullerenes on nanotubes based on DFT calculations Calculations By Arkady Krasheninnikov, TKK

Ambient STM LT UHV STM: Chemisorbed Fullerene on Nanotube Lattice Peaks in the LDOS are due to nanobuds, cannot be assigned to physisorbed Nanometer Range fullerenes Controll for DOS ! Nasibulin & Kauppinen et al. Nature Nanotechnology, 2(3) 156 March 2007

Calculations by Arkady Krasheninnikov, TKK Experiment This suggests that chemically attached fullerene via 2+2 cycloaddition is energetically favorable

Dry, direct deposition method for Integrated Component Manufacturing Products Synthesis Deposition Process Process . . CNT Aerosol Control of Material Direct Manufacture