Fabrication of nanorod arrays and branched nano/microrods

High Aspect Ratio Nanoparticles

What is a high aspect ratio nanoparticle? Aspect ratio refers to the ratio of a particles length to its width Aspect ratio = length width High aspect ratio nanoparticles have elongated structure Examples: nanotubes, nanowires, nanorods Often have distinctive properties as opposed to the bulk materials or even spherical particles

e.g. Chemical, electrical, magnetic, optical, etc.

Nanowires

Types of High Aspect Ratio Nanoparticles

Synthesis Method Templated electrodeposition Sol-gel Nanocluster-mediated vapor-liquidsolid growth Electrodeposition on graphite surface Aspect ratio Up to 250 250 > 100 > 20

Ni, Au, Pt, Ag, Co, Cu, ZnO TiO2, ZnO, SiO2 Silicon

MnO2, Fe2O3, Cu2O, Pd, Cu, Au, Ag

Nanotubes
Gold Silica Carbon Templated electroless deposition Sol-gel High temperature: laser ablation, arc discharge, others 250 250 > 100

Nanorods
Gold CdSe Cu Se Surfactant/seed mediated synthesis Surfactant/seed mediated synthesis Micellar growth Crystal growth ~20 2-10 1.7-3.7 > 100

Applications of High Aspect Ratio Nanoparticles

Several applications of high aspect ratio nanoparticles have been shown, and many others continue to be unfolded Applications is areas such as: Biology Gene therapy Bioseparations Separations Catalysis Sensing Electronics Optical applications Etc.

 Nanostructures,
-> nanorods, -> nanowires, -> nanotubes, -> nanobelts,

have attracted extraordinary attention for their potential applications in device and
interconnect integration in nanoelectronics and molecular electronics. Controlling the particle size & morphology of nanostructures is of crucial importance from a fundamental and industrial point of view

 The nanorod arrays and branched chemical deposited zinc oxide as gas sensors & solar cells.
The merit of this technology is in simplicity of the process, economy in energy, structures with high efficiency, short duration, energy save, accessible auxiliary materials & nonsophisticated equipment.

Nano-patterning techniques
1. Lithographic Methods: Electron beam, ion beam, X-ray lithography 2. Scanning probe techniques (SPM) 3. Self assembly processes

4. Focused ion beam (FIB)

5. Anodized porous alumina templates

Anodized porous alumina templates

Anodized from high-purity aluminum (Al) foils, porous alumina membranes have highly ordered nano-pore arrays with controllable structural parameters. The attractive advantages of the anodic alumina membranes are nanometersized channels, adjustable pore size and length, and ordered pore arrays. These make the anodic alumina membrane an excellent template in fabricating ordered arrays of one-dimensional nanostructures, i.e. ordered nano-wire and nano-tube arrays. Fig.:Anodic alumina nano-porous Membranes. (a) top view (b) cross sectional view (c) the top view of a Pore-widened membrane (d) configuration diagram of porous alumina membranes.

EXPERIMENTAL SETUP
Apparatus used for the anodization A: Motor-controlled rotator for agitating the electrolyte,

B: Pt mesh working as counter electrode,

C: isolator consisting of an outer styrofoam layer and inner brass layer,

D: electrolyte container made of teflon,

E: screw for fixing the electrolyte container to the brass plate, F: aluminum sheet, G: brass plate working as electric conductor connected with a positive electric source,

H : potentiostat/galvanostat (Keithley), and I: computer to operate the potentiostat/galvanostat and the cooling, J: Peltier cooling element.

BARRIER TYPE
This type of films are formed in insoluble electrolytes like neutral boric acid, ethylene glycol etc.

POROUS TYPE
This type of films are formed in soluble electrolytes like sulfuric acid, oxalic acid etc.

PORE FORMATION MECHANISM

At the beginning of anodization barrier film covers the entire surface.

The entire field is focused on the fluctuations on the surface.

 This leads to the dissolution in the formed oxide and thus to the growth of pores.

Some pores begin to stop growing in size due to competition among the pores.
When the process comes to a steady state uniform array of pores will be appeared.

Ultra-thin alumina membranes

The ultra-thin alumina mask (UTAM), as a special type of the anodic alumina membranes, is a through hole porous membrane with small thickness of about several hundred nanometers. The pores of the UTAMs are short nano-channels with a small aspect ratio. UTAMS can be used as deposition or etching masks in fabricating ordered nano-particle or nano-hole arrays on almost any smooth substrate. This non-lithographic surface nano-patterning approach provides an efficient and low-cost alternative in fabricating large-scale ordered arrays of surface nanostructures.

Schematic outline of the

general fabrication processes of nano-particles.

Schematic outline of the general fabrication processes of nano-holes.

Highly ordered arrays of parallel carbon nanotubes grown by pyrolysis of acetylene on cobalt within a hexagonal close-packed Nanochannel alumina template at 650o C. (a) Schematic of fabrication process (b) SEM image of the resulting hexagonally ordered array of carbon nanotubes.

AFM images of (a) Anodized alumina membrane (b) ZnO nanodots deposited at 600o C by the PLD technique.

ZnO is a key functional material exhibiting : near-ultraviolet emission , transparent conductivity semiconducting, magnetic, and piezoelectric properties. It has a : wide direct band gap (3.37 eV), & large exciton binding energy (60 meV) excellent chemical, mechanical, and thermal stability

Zinc oxide has extensive commercial use during the past 100 years in: optoelectronics nano/microelectronics sensors, transducers, hydrogen storage material and biomedicine. ZnO is a phosphor materials with ability to retain a high efficiency, even at low-voltage excitation.

Aligned Growth of ZnO Nanorods

Basic Properties: band gap 3.4eV, direct exciton binding energy 60 meV piezoelectricity 12.4 pm/V Nanostructures: nanobelts, nanowires, nanorods, nanosprings, nanorings, nanosaws, nanocombs, etc. Potential Applications: cantilevers, field-effect transistors, gas sensors, photonic crystal, etc.

Aligned Growth Nanorods by

Thermal Evaporation
One of the simplest and most popular synthesis methods. Very successful and versatile in fabricating nanobelts and nanowires with various characteristics. Process: sublimation of source material deposition of vapor at a certain temperature region. Processes: w/ carbon catalyst ZnO(s) + C(s) Zn(v) + CO(v) w/o carbon catalyst 1. 2ZnO(s) 2Zn(v) + O2(v) 2. ZnO(s) ZnO(v)

Tube Furnace

Substrate

Source Materials

Tube Furnace
Pump Cooling Water Carrying Cooling Gas Water

Growth Mechanisms
Vapor-Solid Vapor-Liquid-Solid (VLS)

Data & Results

Sample Data:
Source Materials: ZnO - 0.6g C - 0.6g Substrate: AlGaN:Mg catalyst, sputter 30 Au 25cm from the end Low temperature furnace: Small valve: 0.1 mbar Big valve: 4.0 x 10^-2 mbar Heat rate: 50C/min Keep at 950C for 30 minutes Gas: Ar 49.0 sccm O2 1.0 sccm Keep pressure at 30 mbar

Gold & Ag Nanoparticles with Increasing Aspect Ratio

Increasing aspect ratio

Au

18

Increasing aspect ratio

1
Ag

10

Silver Nanoparticles with Increasing Aspect Ratio

Increasing aspect ratio

10

Murphy, C. J.; Jana, N. R. Adv. Mater. 2002, 14, 80

Nanowire Synthesis by Electrodeposition

Sputter copper on bottom Nanoporous alumina membrane Place membrane in aqueous solution of metal salt

M+
Apply potential

e-

M+(aq) + eRemove copper with CuCl/HCl solution Dissolve alumina in warm .5 M KOH

M(s)