Nanotechnology: Here, There, Everywhere!

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Nanotechnology: Here, There, Everywhere! But, What of These Nanowires? Jan Yarrison-Rice, Physics, Miami University

What is Nano anyway?

The scale of things Q. If your hair were 1 km wide (and recall that is ~100 μm), then how large would 1 nanometer (nm) be? To help with your estimate: 1 Km is about the distance from Rte. 65 to River Falls Golf Course or From Main to 6 th St. www.nsf.gov A. 1 cm!

A Silica NW ~50 nm Diam. The Hair 50-100 microns www.hno.harvard.edu

"Nanotechnology has given us the tools...to play with the ultimate toy box of nature -- atoms and molecules. Everything is made from it...the possibilities to create new things appear limitless..." Horst Stormer, Nobel Laureate Columbia University Lucent Technologies

Building Nanostructures Top Down Construction: making large things smaller Bottom Up Construction: building things from atoms and molecules

Using Atoms and Molecules to Build -- STM Images from Almaden Iron on Copper Xenon on Nickel Iron on Copper http://www.almaden.ibm.com/vis/stm/corral.html

Common Nanostructures our building blocks! Chemically Synthesized Quantum Dots Self-assembled Quantum Dots Carbon Nanotubes Semiconducting Nanowires & Nanosheets Other self-assembled molecules

Lawrence Livermore Lab

Quantum Dots all shapes www.scifi.com/sfw/issue203/ drexler3.jpg and sizes nppp.ipl.nasa.gov/topics/ Top.quant.dot.htm The University of Melbourne Bawendi, MIT

Carbon Nanotubes CNTs: SEM Images www.rdg.ac.uk www.me.mtu.edu CNT Geometry www.lanl.gov

And the ever famous: Nanowires & Nanosheets! All pictures of NWs are from ANU and all Nanosheets from KIST

Nanotechnology Begins to Take Its Place The National Nanotechnology Initiative (NNI) is an extraordinarily important investment in the future strength of America's economy, industrial base, and scientific leadership. Recent scientific and technical advances have made it possible to assemble materials and components atom by atom, or molecule by molecule. We are just beginning to understand how to use nanotechnology to build devices and machines that imitate the elegance and economy of nature. Charles M. Vest President Massachusetts Institute of Technology

Nanotechnology is indeed here, there, and everywhere: In the clothes you wear In the makeup you use In the car you drive And, coming soon to medicines and medical procedures that help to cure you

My particular interest is in: Understanding the physics of NWs Applying this knowledge to make NW-based sensors and devices

Nanowire Growth Vapor Liquid Solid Or VLS Method Solid / Liquid Interface Si (111) substrate Begin with Gold Nanosphere Melt Gold Melted Gold Droplet s Diameter NW Diameter Introduce NW material NW material enters Gold & forms eutectic NW grows below Gold as solid forms beneath

Different Growth Conditions are responsible for different NW GaAs (111)B substrate structures: T g < 390 C Irregular orientation Kinked substrate 1 μm 390 C T g > 410 C Straight, [111]B aligned Tapered substrate 1 μm 450 C

TEM pictures of GaAs NW internal structure Original procedure 450 C 100 nm 400 nm Two-temperature procedure T n = 450 C, T g = 390 C 500 nm 100 nm 100 nm twins Twin defects Facetted sidewalls No planar defects Smooth sidewalls

NWs can also be grown into interesting nanostructures. Core-shell Structure NanoTUBE! Axial Differential Growth Quantum Well in NW!

III-V Nanowires SEM images 1 μm InAs NWs 1 μm GaP NWs 1 μm AlAs NWs 1 μm GaAs NWs 1 μm AlGaAs NWs

II-VI CdS Nanosheets Grown by pulsed laser deposition using vapor-phase transport method with gold catalysts (800 o C; 20min) Dimensions: ~50 nm thick; ~ 4 µm wide & 30-100 µm long SEM images of ensemble and single nanosheets

Slit confocal spectroscopy NW Characterization (some physics!)

A series of spectra in 2 InP NWs as Temperature increases. zincblende wurtzite

InP NW Photoluminescence Spectra over Time 1.35 1.4 1.45 1.5

NOW. Onto NW Devices and BioSensors!!

NW of Different Materials as PhotoEmitters From: H. Jackson, UC

NW LEDs and Lasers From: H. Jackson, UC

Nanowires are also finding use in: Filters air and water a woven filter of NWs can filter out ultra-small particles Stronger materials that are still flexible for police and armed forces protection Latest report: for making electricity on a small scale! And of course, in my area of interest

www.azonano.com Other NW Applications include: NW Solar Cell www.newscientist.com NW Electricity NanoFiber Mop

Nanowires as Biosensors! From: H. Jackson, UC

Nanowire BioSensor Schematic Nanowire Sensor Bowtie Resonator Dressed Bowtie Bowtie with Toxins electrodes nanowire I High sensitivity ~10 4 Enhancement at resonance Ligands added Toxins captured, surface plasmon resonance changed

Bowtie Plasmonic Resonators

First Device Structure: CdS Nanosheet w/ Electrodes Current vs. Voltage

Imagine a biosensor array?! A different chemical species detected on each biosensor!

Conclusion "The National Nanotechnology Initiative is a big step in a vitally important direction. It will send a clear signal to the youth of this country that the hard core of physical science (particularly physics and chemistry) and the nanofrontiers of engineering have a rich, rewarding future of great social relevance. The coming high tech of building practical things at the ultimate level of finesse, precise right down to the last atom, has the potential to transform our lives. Physics and chemistry are the principal disciplines that will make this all happen. But they are hard disciplines to master, and far too few have perceived the rewards at the end of the road sufficient to justify the effort. The proposed NNI will help immensely to inspire our youth. Richard E. Smalley Gene and Norman Hackerman Professor of Chemistry and Professor of Physics Rice University Center for Nanoscale Science and Technology

Thanks to my collaborators at Miami: Graduate Students : Neil Smith, Senthil Rajagopal, Siwei Cao, & Erich See Undergraduate Students: Katie Beddow, Jesse Manders, Colin Boyle, & Caroline Scacca Colleagues at University of Cincinnati: Graduate Students Melodie Fickenscher Faculty Leigh Smith T.B. Hoang S. Perenga Howard Jackson Ashu Mishra Thanks to Synthesis Colleagues: Chenupati Jagadish s Group: Australian National University Collegues: KIST (Korean Institute of Science & Technology Thanks to NSF & DOE for their support

JYR 2008 Nano Group Caroline Scacca Jesse Manders Colin Boyle Siwei Cao

Grad Students Erich See Siwei Cao

Colin Boyle Off to Australia Jesse Manders Off to NIST

Uses for QDs Include: InP QD Laser (where QDs grow on surfaces) University of Stutgart

Applications of Nanoscience: Medicine Drug Delivery TEM image of the hexagonallytemplated hollow ZnS on Silica Spheres braungroup.beckman.uiuc.edu/dongyeon.html

Bottom Up Approach Self Assembly Self-assembled monolayers (SAM) chemistry.st-and.ac.uk/staffmember.php?id=mb

Self-Assembly & STM Note: STM means Scanning Tunneling Microscope Molecular NanoMan logo (line thickness 1-3 nm), written with STM into a layer of self assembled molecules. www.nano.geo.uni-muenchen.de/.../molecwrite.html

Spherical QDs with Molecular Tethers form Building Blocks for Sensors

CNTs Uses: Similar to nanowires for nanoscale electronics As a strengthener in polymers and other materials As a probe -- in sensors QuickTime and a TIFF (LZW) decompressor are needed to see this picture. Sensor design to left To right, CNTs grown in sensor gap, then used to detect temperature QuickTime and a TIFF (LZW) decompressor are needed to see this picture. IEEE Trans Nanotech, Jan. 2007

CdS Nanowires SEM Image AFM Images CdS nanowires grown with 50 nm Au catalysts 14 mm long 17 mm long

STM Scanning tunneling microscope http://www.iap.tuwien.ac.at/www/surface/stm_gallery/stm_schematic.html

Other cool sites http://www.almaden.ibm.com/vis/stm (Interesting STM images) http://www.nobel.se/physics/educational/mic roscopes/scanning/ (Interesting STM images)

Atomic Force Microscopy

Wafer & TIP Si or SiN 10 nm at end ~100 atoms Electron micrograph of two 100 µm long V-shaped cantilevers (by Jean-Paul Revel, Caltech; cantilevers from Park Scientific Instruments, Sunnyvale, CA). Three common types of AFM tip. (a) normal tip (3 µm tall); (b) supertip; (c) Ultralever (also 3 µm tall). (b) Electron micrographs by Jean-Paul Revel, Caltech. http://stm2.nrl.navy.mil/how-afm/how-afm.html

Non-Contact Mode Solid Lipid Nanoparticles

Top-Down Approach: Electronbeam or Optical Lithography Exposure and development process to fabricate a nanoscale structure

Incorporating Electrodes into a Device Gold squares are 300 mm and electrodes are in between them! When epoxy is added, then we can add the molecules and the experiment begins.

Electrodes for Single Molecules Step 2: Grown shut for 3 nm gap 1 2a Step 1: Fabricated with lithography 2b

The bottom up approach holds the most promise: Types of nanoscale building blocks: Quantum Dots - QDs Nanowires - NWs Carbon Nanotubes - CNTs Nanosheets - NSs

QDs come in all shapes and sizes! nppp.ipl.nasa.gov/topics/ Top.quant.dot.htm www.scifi.com/sfw/issue203/ drexler3.jpg www.aep.cornell.edu/ gif/qdotspbse.jpg qt.tn.tudelft.nl/news/ NN6fig1b.gif

Looking at & Manipulating Atoms STMs & AFMs