Name: ultrahigh density array of vertically aligned small-molecular organic nanowires on arbitrary substrates
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This work has been financially supported by NSERC, CSEE, nanoBridge and TRLabs.

As mentioned above, the two key steps in the AAO-based fabrication process are (a) synthesis of the empty AAO template on arbitrary (primarily conductive and/or transparent) substrates (schematic description in Figure 1) and (b) growth of small molecular organic nanowires within the nanopores of the AAO template (Figure 2). In this section we provide a detailed description of these processes.
1. Growth of Anodic Aluminum Oxide (AAO) Templates on Conductive Alumi...

     

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Physical Picture for Nanowire Growth
It is first important to fully understand the growth method of the organic nanowires. Once we know exactly how they grow and form themselves in the pores we can use this deposition method to engineer nanostructures, devices and materials. In the past, polymer nanowires have been fabricated using the template wetting procedure without the assistance of a centrifuge, but for some materials such as organic small molecules, we have found this to be ineffective. D...

A template-assisted method is commonly used for the fabrication of vertically oriented nanowire arrays 1-3. This method allows straightforward fabrication of complex nanowire geometries such as an axially 4-6 or radially 7 heterostructured nanowire superlattice, which are often desirable in various electronic and optical applications. In addition, this is a low-cost, bottom-up nanosynthesis method with high throughput and versatility. As a result, template-directed methods have gained immense popularity among researchers worldwide 2,3.
The basic idea of the "template-directed method" is as follows. First a template is fabricated, which contains an array of vertically oriented cylindrical nanopores. Next, the desired material is deposited within the nanopores until the pores are filled. As a result the desired material adopts the pore morphology and forms a nanowire array hosted within the template. Finally, depending on the target application, the host template may be removed. However, this also destroys the vertical order. The geometry and dimensions of the final nanostructures mimic the pore morphology and hence synthesis of the host template is a critical part of the fabrication process.
Various types of nanoporous templates have been reported in literature 8. The most commonly used templates include (a) polymer track-etched membranes, (b) block copolymers and (c) anodic aluminum oxide (AAO) templates. To create the polymer track etched membranes a polymer foil is irradiated with high-energy ions, which completely penetrate the foil and leave latent ion tracks within the bulk foil 9. The tracks are then selectively etched to create nanosized channels within the polymer foil 9. The nanosized channels can be further widened by a suitable etching step. Key problems with this method are the non-uniformity of the nanochannels, lack of control of location, non-uniform relative distance between the channels, low density (number of channels per unit area ~108/cm2), and poorly ordered porous structure 1. In the block copolymer method a similar cylindrical nanoporous template is first created, followed by the growth of desired material within the pores 8.
In the past, methods (a) and (b) mentioned above have been used to fabricate polymer nanowires 8. However, these methods may not be suitable for synthesizing nanowires of any arbitrary organic material due to the potential absence of selective etching during post-processing steps. Post-processing typically involves removal of the host template, which for the above-mentioned templates would require organic solvents. Such solvents may have deleterious effect on the structural and physical properties of the organic nanowires. However, these templates work as ideal hosts for inorganic nanowires such as cobalt 10, nickel, copper and metallic multilayers 11, which remain unaffected in the etching process that removes the polymer host. Another potential challenge for the above-mentioned methods is the poor thermal stability of the host matrix at higher temperatures. High temperature annealing is often required to improve crystallinity of the organic nanowires, which indicates the necessity of good thermal stability of the host matrix.
Controlled electrochemical oxidation of aluminum (also known as "anodization" of aluminum) is a well-known industrial process and is commonly used in the automobile, cookware, aerospace and other industries to protect aluminum surface from corrosion 12. The nature of the oxidized aluminum (or "anodic alumina") depends critically on the pH of the electrolyte used for anodization. For corrosion-resistance applications, anodization is generally performed with weak acids (pH ~5-7), which create a compact, non-porous, "barrier-type" alumina film 12. However, if the electrolyte is strongly acidic (pH &lt; 4), the oxide becomes "porous" due to local dissolution of the oxide by the H+ ions. The local electric field across the oxide determines the local concentration of the H+ ions and hence surface pre-patterning prior to anodization offers some control over the final porous structure. The pores are cylindrical, with small diameter (~10-200 nm) and hence such nanoporous anodic alumina films have been used extensively in recent years for synthesizing nanowires of various materials 2,3.
Nanoporous anodic alumina templates offer better thermal stability, high pore density, long-range pore order, and excellent tunability of pore diameter, length, inter-pore separation and pore density via judicious choice of anodization parameters such as pH of the electrolyte and anodization voltage 2,3. Due to these reasons we choose AAO templates as the host matrix for the organic nanowire growth. Further, inorganic oxides such as alumina have high surface energy, thus facilitating uniform spreading of the organic solution (low surface energy) on the alumina surface 13. In addition, our goal is to grow these nanowire arrays directly on a conductive and/or transparent substrate. As a result, the pore is closed at the bottom end, which needs additional consideration as we describe below. Growth of nanowires within a through-pore template and subsequent transfer to the desired substrate is often undesirable due to poor interface quality and this method is not even feasible for short-length nanowires (or thin templates) due to poor mechanical stability of the thin templates.
&pi;-conjugated organic materials can be broadly classified into two categories: (a) long-chain conjugated polymers and (b) small molecular weight organic semiconductors. Many groups have reported synthesis of long chain polymer nanowires within the cylindrical nanopores of an AAO template in the past. Comprehensive review on this topic is available in refs 8,14. However, synthesis of nanowires of commercially important small molecular organics (such as rubrene, tris-8-hydroxyquinoline aluminum (Alq3), and PCBM) in AAO is extremely rare. Physical vapor deposition of rubrene and Alq3 within the nanopores of AAO template has been reported by several groups 4,15-17. However, only a thin layer (~30 nm) of organics can be deposited within the pores (~50 nm diameter) and prolonged deposition tends to block the pore entrance 4,16,17. Complete pore filling can be achieved in this method if the pore diameter is sufficiently large (~200 nm) 15. Thus it is important to find an alternative method that is applicable for pore diameters in the sub 100 nm range.
Another approach that has been used for some other small-molecular organics is a so-called "template wetting" method 8,14. However, in most reports thick commercial templates (~50 &mu;m) with both side open pores and large diameter (~200 nm) have been used. Such method has not produced nanowires in one-side closed pores as mentioned before, presumably due to the presence of trapped air pockets within the pores, which prevents infiltration of the solution within the pores. We have previously reported a novel method that overcomes these challenges and allows growth of small molecular organic nanowire arrays with arbitrary dimensions on any desired substrate. In what follows, we will describe the detailed protocol, potential limitations and future modifications.

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			<td>Reagents</td>
		 </tr>
		 <tr>
			<td>Toluene</td>
			<td>Fisher Scientific</td>
			<td>T324-4</td>
			<td></td>
		 </tr>
		 <tr>
			<td>68% Nitric Acid</td>
			<td>Fisher Scientific</td>
			<td>A200-212</td>
			<td></td>
		 </tr>
		 <tr>
			<td>85% Phosphoric Acid</td>
			<td>Fisher Scientific</td>
			<td>A242-4</td>
			<td></td>
		 </tr>
		 <tr>
			<td>10% Chromic Acid</td>
			<td>RICCA Chemical Company</td>
			<td>2077-32</td>
			<td></td>
		 </tr>
		 <tr>
			<td>10% Oxalic Acid</td>
			<td>Alfa Aesar</td>
			<td>FW.90.04</td>
			<td></td>
		 </tr>
		 <tr>
			<td>Chloroform</td>
			<td>Fisher Scientific</td>
			<td>C607-4</td>
			<td></td>
		 </tr>
		 <tr>
			<td>Aluminum Sheets</td>
			<td>Alfa Aesar</td>
			<td>7429-90-5</td>
			<td></td>
		 </tr>
		 <tr>
			<td>PCBM</td>
			<td>Nano-C</td>
			<td>Nano-CPCBM-BF</td>
			<td></td>
		 </tr>
		 <tr>
			<td>Alq3</td>
			<td>Sigma Aldrich</td>
			<td>444561-5G</td>
			<td></td>
		 </tr>
		 <tr>
			<td>Rubrene</td>
			<td>Sigma Aldrich</td>
			<td>551112-1G</td>
			<td></td>
		 </tr>
		 <tr>
			<td></td>
			<td></td>
			<td></td>
			<td>Equipment</td>
		 </tr>
		 <tr>
			<td>FlexAL Atomic Layer Deposition (ALD)</td>
			<td>Oxford Instruments</td>
			<td></td>
			<td>For deposition of TiO2</td>
		 </tr>
		 <tr>
			<td>PVD Sputter System</td>
			<td>Kurt J. Lesker</td>
			<td></td>
			<td>For deposition of Au &amp; Al</td>
		 </tr>
		 <tr>
			<td>Flat Cell</td>
			<td>Princeton Applied Research</td>
			<td>K0235</td>
			<td>For anodization of Al</td>
		 </tr>
		 <tr>
			<td>Centrifuge</td>
			<td>HERMLE Labnet</td>
			<td>Z206 A</td>
			<td>For deposition of organic nanowires</td>
		 </tr>
	 </tbody>
 </table>

ultrahigh density array of vertically aligned small-molecular organic nanowires on arbitrary substrates

In recent years &pi;-conjugated organic semiconductors have emerged as the active material in a number of diverse applications including large-area, low-cost displays, photovoltaics, printable and flexible electronics and organic spin valves. Organics allow (a) low-cost, low-temperature processing and (b) molecular-level design of electronic, optical and spin transport characteristics. Such features are not readily available for mainstream inorganic semiconductors, which have enabled organics to carve a niche in the silicon-dominated electronics market. The first generation of organic-based devices has focused on thin film geometries, grown by physical vapor deposition or solution processing. However, it has been realized that organic nanostructures can be used to enhance performance of above-mentioned applications and significant effort has been invested in exploring methods for organic nanostructure fabrication.	
A particularly interesting class of organic nanostructures is the one in which vertically oriented organic nanowires, nanorods or nanotubes are organized in a well-regimented, high-density array. Such structures are highly versatile and are ideal morphological architectures for various applications such as chemical sensors, split-dipole nanoantennas, photovoltaic devices with radially heterostructured "core-shell" nanowires, and memory devices with a cross-point geometry. Such architecture is generally realized by a template-directed approach. In the past this method has been used to grow metal and inorganic semiconductor nanowire arrays. More recently &pi;-conjugated polymer nanowires have been grown within nanoporous templates. However, these approaches have had limited success in growing nanowires of technologically important &pi;-conjugated small molecular weight organics, such as tris-8-hydroxyquinoline aluminum (Alq3), rubrene and methanofullerenes, which are commonly used in diverse areas including organic displays, photovoltaics, thin film transistors and spintronics.	
Recently we have been able to address the above-mentioned issue by employing a novel "centrifugation-assisted" approach. This method therefore broadens the spectrum of organic materials that can be patterned in a vertically ordered nanowire array. Due to the technological importance of Alq3, rubrene and methanofullerenes, our method can be used to explore how the nanostructuring of these materials affects the performance of aforementioned organic devices. The purpose of this article is to describe the technical details of the above-mentioned protocol, demonstrate how this process can be extended to grow small-molecular organic nanowires on arbitrary substrates and finally, to discuss the critical steps, limitations, possible modifications, trouble-shooting and future applications.

As evidenced by the figures shown below (Figures 5 and 6), this centrifuge assisted drop casting method produces continuous nanowires. The nanowires, fabricated inside the pores of the AAO template, are vertically aligned, uniform, and electrically isolated from one another with capped bottoms. The diameter of the nanowires is determined by the diameter of pores in the template. They can be successfully fabricated on several different substrates, which lead to the potential application o...

Watch this Scientific Journal Video about Ultrahigh Density Array of Vertically Aligned Small-molecular Organic Nanowires on Arbitrary Substrates at JoVE.com

Ultrahigh Density Array of Vertically Aligned Small-molecular Organic Nanowires on Arbitrary Substrates

We report a simple method for fabricating an ultrahigh density array of vertically ordered small-molecular organic nanowires. This method allows for synthesis of complex heterostructured hybrid nanowire geometries, which can be inexpensively grown on arbitrary substrates. These structures have potential applications in organic electronics, optoelectronics, chemical sensing, photovoltaics and spintronics.

In  recent years &pi;-conjugated  organic semiconductors have emerged as the active material in a number of  diverse applications including large-area, ...

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