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Nanowires and Nanotubes Mildred S 1st International Symposium on Nanomanufacturing Overview of Nanowires and Nanotubes Mildred S. Dresselhaus MIT April 25, 2003 Al2O3 Pores Al Barrier Layer Motivation towards Nanotechnology • Device miniaturization, reducing physical sizes • Exploiting enhanced surface effects by increased surface/volume ratio (e.g. catalysts) • Utilization of biological objects in inorganic nanostructures for various sensors and novel functions • Novel phenomena in low-dimensional structures not observed in their bulk counterparts Science Introduction • Nanostructures (< 30 nm) have become an exciting research field – New quantum phenomena occur at this length scale – New structure – property relations are expected – Promising applications are expected in optics, electronics, thermoelectric, magnetic storage, NEMS (nano-electro-mechanical systems) • Low-dimensional systems are realized by creating nanostructures that are quantum confined in one or more directions and exhibit properties different from their 3D counterparts D. O. S. D. O. S. D. O. S. D. O. S. E E E E 3D 2D 1D 0D Bulk Semiconductor Quantum Well Quantum Wire Quantum Dot Nanotechnology R&D Funding in the USA Fiscal year 2000 2001 2002 2003 (all in million $) __________________________________________________________________________________________________________________________________________________________________ National Science Foundation 97 150 199 221 Department of Defense 70 125 180 201 Department of Energy 58 88 91.1 139.3 National Institutes of Health 32 39.6 40.8 43.2 NASA 5 22 46 51 NIST 8 33.4 37.6 43.8 Environmental Protection Agency - 5.8 5 5 Depart. of Transportation/FAA - 2 2 Department of Agriculture - 1.5 1.5 2.5 Department of Justice - 1.4 1.4 1.4 TOTAL 270.0 466.7 604.4 710.2 Other NNI participants are: DOC, DOS, DOTreas, NOAA, NRC, USG M.C. Roco, NSF, 4/30/02 Context – Nanotechnology in the World Government investments 1997-2002 2500 W. Europe Japan 2000 USA Others 1500 Total 1000 millions $ / year 500 0 1997 1998 1999 2000 2001 2002 Note: • U.S. begins FY in October, six month before EU & Japan in March/April • U.S. does not have a commanding lead as it was for other S&T megatrends (such as BIO, IT, space exploration, nuclear) Senate Briefing, May 24, 2001 (M.C. Roco), updated on February 5, 2002 A “Nano Tool-box” To fabricate/probe nanostructures Nanofabrication Top-down Method Bottom-up Method - create nanostructures - self assembly of out of macrostructures atoms or molecules into nanostructures Various Nanostructures can occur in 1D Each have different structure/properties Selectivity is therefore important (a) Bi Nanowire (b) Bi Nanotube (c) Bi Atomic Line Dresselhaus Group Peidong Yang K. Miki (MIT) UC Berkeley ETL,Japan Wiring on Si with ultra-fine Bi lines Structure different from 3D Bismuth Bi nanoline • Features: • over 300 nm long • 1 nm (3 Si dimers) wide • without kink K. Miki et al. Surf. Sci. 421 (1999) 397 • in terrace (not on top layer) Self-Assembled Nanopores in Alumina for growing nanowires/nanotubes Al2O3 Pores SEM image of the surface of an anodic alumina Al template with self-assembled nanopore structure Barrier Layer • Applications – Templates for ordered arrays of nanowires and nanotubes – 2D photonic crystal Nanowire array – High density magnetic storage media – Filters and gas sensors Densities of 1011 nanowires/cm2 Template Dissolution are achieved Free-standing wires Single Crystal Nanowires X-ray diffraction of Bi nanowire arrays with different diameters. 10 nm TEM and electron diffraction of a 40-nm nanowire (Bi0.85Sb0.15) Quantum Confinement Produces New Materials Classes • Bi • Bi nanowire – Group V element – Semimetal-semiconductor – Semimetal in bulk form transition at a wire diameter – The conduction band (L-electron) about 50 nm due to quantum overlaps with the valence band confinement effects (T-hole) by 38 meV Semimetal Semiconductor Decreasing wire diameter Semimetal-Semiconductor Transition We utilize novel properties in applications Why nanostructures are useful for thermoelectrics Difficulties in increasing ZT in bulk materials: Seebeck Coefficient Conductivity Temperature S ? ?? ? ? S 2 ? T ZT ? ? ? ?? S ? and ?? ? Thermal A limit to Z is rapidly obtained in Conductivity ? conventional materials ZT ~ 3 for conventional refrigerators ? So far, best bulk material (Bi0.5Sb1.5Te3) has ZT ~ 1 at 300 K Low dimensions give independent control of variables: ? Enhanced density of states due to quantum confinement effects ? Increases S without reducing ? ? Boundary scattering at interfaces reduces ? more than ? ? Possibility of carrier pocket engineering to further improve ZT Anodic Alumina on Silicon Wafers - Motivation Fabrication of the porous alumina templates on silicon substrates is an appealing improvement over the conventional fabrication process for the following reasons: • Elimination of unfavorable fabrication steps. • Rigid substrate, affords extended crack-free films. • Low surface roughness. • Solution to the barrier layer problem for electrical connects. • Incorporation into electronic, optical devices on the wafer. • Combined nano-scale and micro-scale patterning. Alumina Templates on Silicon Wafers thermal evaporation Al Si (100) Si (100) patterned conducting layer patterned conducting layer electrochemical Al anodization polishing Si (100) patterned conducting layer Si (100) porous alumina selective etch patterning deposition Si (100) Si (100) nanowires Advantages of the New Process ? The high-quality porous alumina films prepared on silicon substrates are rigid and easy to handle. ? This method affords very large area films (70 cm2) with a very flat interface. ? Films were grown on conducting (Ti) and insulating (SiO2) substrates. ? Both adhesion to and separation from the substrate are possible. ? Pores are accessible from both ends. ? Growth of nanowires in the templates was demonstrated by two different methods. ? The porous films were patterned using lithography techniques. Towards Multi-Component Nanowire Arrays By means of lithography, a design allowing deposition of both p-type and n-type components on the same support could be achieved. deposit p-type nanowires cold-end junction deposited and patterned Si(100) Si(100) POTENTIOSTAT deposit n-type nanowires patterned titanium Si(100) back electrodes and Si(100) hot-end junction POTENTIOSTAT Structural Features Oblique View Cross Section Al Ti Si For Comparison The new Al2O3/Si structure conserves the dense uniform porous morphology with long channels, but consists of a thinner barrier layer. Characterization of Nanowires Arrays 2-Point Resistance Setup Seebeck Coefficient Measurement V V V Al Si (100) Si (100) Pt/Ti Heater Pt/Ti Filled alumina template Filled alumina template Silver paint contacts Gold film Thermocouple Growth of Semiconductor Nanowires by Vapor Liquid Solid (VLS) method 50 n m 5 ? m Laser ablation overcomes thermodynamic equilibrium constraints, and enables liquid nanocluster formation. a) FESEM image of GaP nanowires. The inset is a TEM image of the end of one of these wires. b) TEM image of a GaP wire. The [111] lattice planes 10 nm are resolved, showing that wire growth occurs along this axis. Peidong Yang et al. ZnO Nanowires on Sapphire by VLS method *SEM images of ZnO nanowire arrays grown on a sapphire substrate, where (a) shows patterned growth, (b) shows a higher resolution image of the parallel alignment of the nanowires, and (c) shows the faceted side-walls and the hexagonal cross-section of the nanowires. For nanowire growth, the sapphire substrates were coated with a 1.0 to 3.5nm thick patterned layer of Au as the catalyst, using a TEM grid as the shadow mask. These nanowires have been used for nanowire laser applications (Huang et al., 2001a). *Patterned growth can be arranged. *Proper selection of nanowires and substrate materials can led to facets, useful for nanowire lasers. Nano-Lasers using ZnO Nanowires Nanowire UV Nanolaser UV Laser Output ZnO nanowires grown by VLS method. Excitation Intensity (a.u.) 370 380 390 400 Wavelength (nm) Emission spectrum from ZnO nanowires. Peidong Yang et al Tunable Bandgap in Nanowires InP nanowire diameter ? energy ? ? light emission can occur at a p-n junction from the same material M. S. Gudiksen et al., J. Phys. Chem B 106, 4036 (2002) Unique Properties of Carbon Nanotubes Roll up Graphene sheet SWNT • Size: Nanostructures with dimensions of ~1 nm diameter (~20 atoms around the cylinder) • Electronic Properties: Can be either metallic or semiconducting depending on the diameter or orientation of the hexagons • Mechanical: Very high strength and modulus. Good properties on compression and extension • Heat pipe and electromagnetic pipe • Single nanotube spectroscopy yields structure • Many applications are being attempted worldwide Field Emitter Applications for Nanotubes Scanning tips and Electronics • STM/AFM tips Transistor • Direct Analysis of DNA • Semiconductor devices • Field Emitters New Materials S.J. Tans et al. Nature, 393, 49 (1998) Imaging biological molecules AFM image of Immunoglobulin G Fullerene C60 inside nanotubes resolved by nanotube tips Rolling up graphene layer Nanotubes armchair ? ??30 zigzag ? ??0 chiral 0?? ??30 (4,2) ? La d??n22??nmm ? ?? ? t ?? Ch ?na12??ma(nm,) ? 3m (n-m) = 3q metallic ?? ? tan? 1 ? (n-m) = 3q ?1 semiconducting ? 2nm? Synthesis S. Iijima, Nature 354 56 (1991) Arc Method: Y. Saito • Laser Ablation • Arc Discharge 5-20mm diameter carbon rod Nd-Yb-Al-garnet Laser, 1200? 500torr He 50-120A DC A. Thess et al. Science Y. Saito et
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