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Template Directed Synthesis of Plasmonic Gold Nanotubes with Tunable IR Absorbance

Published: April 1st, 2013



1Department of Chemistry, University of Toronto

Solution-suspendable gold nanotubes with controlled dimensions can be synthesized by electrochemical deposition in porous anodic aluminum oxide (AAO) membranes using a hydrophobic polymer core. Gold nanotubes and nanotube arrays hold promise for applications in plasmonic biosensing, surface-enhanced Raman spectroscopy, photo-thermal heating, ionic and molecular transport, microfluidics, catalysis and electrochemical sensing.

A nearly parallel array of pores can be produced by anodizing aluminum foils in acidic environments1, 2. Applications of anodic aluminum oxide (AAO) membranes have been under development since the 1990's and have become a common method to template the synthesis of high aspect ratio nanostructures, mostly by electrochemical growth or pore-wetting. Recently, these membranes have become commercially available in a wide range of pore sizes and densities, leading to an extensive library of functional nanostructures being synthesized from AAO membranes. These include composite nanorods, nanowires and nanotubes made of metals, inorganic materials or polymers 3-10. Nanoporous membranes have been used to synthesize nanoparticle and nanotube arrays that perform well as refractive index sensors, plasmonic biosensors, or surface enhanced Raman spectroscopy (SERS) substrates 11-16, as well as a wide range of other fields such as photo-thermal heating 17, permselective transport 18, 19, catalysis 20, microfluidics 21, and electrochemical sensing 22, 23. Here, we report a novel procedure to prepare gold nanotubes in AAO membranes. Hollow nanostructures have potential application in plasmonic and SERS sensing, and we anticipate these gold nanotubes will allow for high sensitivity and strong plasmon signals, arising from decreased material dampening 15.

When their dimensions approach the penetration depth of light (~50 nm; the nanoscale), noble metals, and most importantly gold, exhibit exquisite size, shape and environment dependent optical properties 24, 25. On this scale, direct illumination causes a coherent oscillation of conduction electrons known as the surface plasmon resonance (SPR). SPR is highly dependent on nanostructure size, shape, and the dielectric properties of the surrounding medium. There is great interest in characterizing SPR properties in new materials, as SPR-based devices are emerging for use in sub-wavelength optics, SERS substrates, and ultra-sensitive optical sensors 11-16, ....

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1. Forming the Silver Working Electrode

  1. Secure the AAO membrane substrate top side up on a glass plate using a 2-sided adhesive. Note: minimize the membrane area in contact with the adhesive, as it will clog the pores.
  2. Install the glass plate into the substrate holder of the metal evaporator, close the chamber, and evacuate to a pressure of below 1.0 μTorr.
  3. Using a resistive source, evaporate silver pellets (>99.99% purity) onto the substrate at a rate of 0.8 Å/sec until a laye.......

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After each step, one can visibly determine whether or not the synthesis is successful by observing the color of the membrane. After copper deposition (step 2.3) the template will appear purple. During nickel deposition (step 2.5) the template will slowly turn black. After the polymer deposition (step 3.3) the template should appear darker purple/black and more glossy (Figure 2). Typical chronoapmerograms of successful polymer and gold are included (Figure 3). During the final etching ste.......

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Template directed synthesis of nanorods in AAO membranes has become increasingly popular, however syntheses of nanorods tend to be very sensitive towards minor changes in material and synthesis conditions. Here, a comprehensive understanding of the advantages and limitations of using AAO membranes is outlined, as well as a general guideline for using AAO membranes for electrochemical synthesis of nanostructures.

When purchasing AAO membranes, there are two general types available: asymmetric a.......

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This work was supported by the University of Toronto, the Natural Sciences and Engineering Research Council of Canada, the Canadian Foundation for Innovation, and the Ontario Research Fund. DSS thanks the Ontario Ministry for an Early Researcher Award.


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Name Company Catalog Number Comments
UniKera Standard Membrane Synkera Technologies Inc. SM-X-Y-13 Anodic aluminum oxide membranes are available from synkera in various pore sizes ranging from 13 - 150 nm, and thicknesses from 50 to 100 μm. We use the 50 μm ones. They are symmetric, meaning the pore size is uniform from top to bottom.
Anopore Inorganic Membranes Whatman 6809-7023 13 mm diameter, 200 nm pore size. These membranes are very fragile. The pore diameters are not uniform throughout, so it is important to always use the bottom of the membrane as the working electrode
Silver Pellets %99.99 Kurt J. Lesker EVMAG40EXE-D
Copper(II) sulfate pentahydrate Sigma-Aldrich 209189
Sulfuric acid ACP S8780 Caution: corrosive liquid
Hydrogen peroxide (30%) ACP H7000 Caution: oxidizing liquid
Nitric Acid ACP N2800 Caution: corrosive fuming liquid
Sodium Hydroxide Fisher Scientific S318-1 Caution: caustic powder
Watts Nickel Pure Technic Inc. 130859 Product is no longer available from Technic inc., however other commercial nickelplating solutions will work.
Techni-Gold 434HS Technic Inc. X6763600 Contains cyanide, do not acidify
Boron trifluoride diethyl etherate Sigma-Aldrich 175501-100ML Must be stored and used under inert atmosphere
3-hexylthiophene Sigma-Aldrich 399051-5G
Deuterium Oxide Sigma-Aldrich 151880-100G
Acetonitrile (anhydrous) Sigma-Aldrich 271004
Ethanol (anhydrous) Caledon Labs 1500-1-05
EC Epsilon potentiostat/galvanostat BASi (Bioanalytical Systems, Inc.) N/A Reference electrodes and platinum wires were included with the potentiostat, and replacements can be purchaes from BASi
Cary 5000 UV-Vis-NIR spectrophotometer Agilent Technologies N/A
Thermomixer R Eppendorf N/A
Branson 2510 Ultrasonic Cleaner Bransonic Z244810 (From Sigma Aldrich)
Covap 2 thermal evaporator Angstrom Engineering N/A
Millipore Synergy water purification system Millipore N/A

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