Name: ambient method for the production of an ionically gated carbon nanotube common cathode in tandem organic solar cells
Uploaded: 2014-11-05T15:00:00
Description: Watch this Scientific Journal Video about Ambient Method for the Production of an Ionically Gated Carbon Nanotube Common Cathode in Tandem Organic Solar Cells at JoVE.com

Support for this work was provided by DOE STTR grant DE-SC0003664 on Parallel Tandem Organic Solar Cells with Carbon Nanotube Sheet Interlayers and Welch Foundation grant AT-1617. The authors thank J. Bykova for providing CNT forests and A. R. Howard, K. Meilczarek, and J. Velten for technical assistance and useful discussions.

1. Indium Tin Oxide (ITO) Patterning and Cleaning
NOTE: Use 15&#937;/&#9633; ITO glass, and purchase or cut the ITO glass into sizes suitable for spin coating and photolithography. It is most efficient to perform steps 1.1-1.7 on a piece of glass as large as possible, and then cut it into smaller devices. Also note that steps 1.1-1.7 require the ITO glass to be oriented with the ITO-side up. This can be checked easily with a multimeter&#8217;s resistance setting.
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	<li>Spin coat 1 ml of ...

<ol>
	<li>He, Z., Zhong, C., Su, S., Xu, M., Wu, H., Cao, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enhanced+power-conversion+efficiency+in+polymer+solar+cells+using+an+inverted+device+structure.">Enhanced power-conversion efficiency in polymer solar cells using an inverted device structure.</a> Nature Photonics. 6, 591-595 (2012).</li><li>Yuan, Y., Huang, J., Li, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Intermediate+layers+in+tandem+organic+solar+cells.">Intermediate layers in tandem organic solar cells.</a> Green. 1 (1), 65-80 (2011).</li><li>Kim, J. Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Efficient+tandem+polymer+solar+cells+fabricated+by+all-solution+processing.">Efficient tandem polymer solar cells fabricated by all-solution processing.</a> Science. 317 (5835), 222-225 (2007).</li><li>Yu, B., Zhu, F., Wang, H., Li, G., Yan, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=All-organic+tunnel+junctions+as+connecting+units+in+tandem+organic+solar+cell.">All-organic tunnel junctions as connecting units in tandem organic solar cell.</a> Journal of Applied Physics. 104 (11), (2008).</li><li>Schueppel, R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Controlled+current+matching+in+small+molecule+organic+tandem+solar+cells+using+doped+spacer+layers.">Controlled current matching in small molecule organic tandem solar cells using doped spacer layers.</a> Journal of Applied Physics. 107 (4), (2010).</li><li>Hiramoto, M., Suezaki, M., Yokoyama, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effect+of+thin+gold+interstitial-layer+on+the+photovoltaic+properties+of+tandem+organic+solar+cell.">Effect of thin gold interstitial-layer on the photovoltaic properties of tandem organic solar cell.</a> Chemistry Letters. 19 (3), 327-330 (1990).</li><li>Xue, J., Uchida, S., Rand, B. P., Forrest, S. 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The results highlight a few considerations when designing parallel tandem solar cells. Notably, if one of the sub-cells is performing poorly, tandem performance in negatively affected. The results show that there are two main effects. If one sub-cell is shorted, e.g., shows ohmic behavior, the FFT will be no higher than the FF of the bad sub-cell. JTSC and VTOC will be similarly affected. This is the case when VGate is low and the P3HT sub-cell ha...

Polymer semiconductors are the leading organic photovoltaic (OPV) materials due to high absorptivity, good transport properties, flexibility, and compatibility with temperature sensitive substrates. OPV device power conversion efficiencies, &#951;, have jumped significantly in the past years, with single cell efficiencies as high as 9.1%1, making them an increasingly viable energy technology.
Despite the improvements in &#951;, the thin optimal active layer thicknesses of the devices limit light absorption and hinder reliable fabrication. Additionally, the spectral width of light absorption of each polymer is limited compared to inorganic materials. Pairing polymers of differing spectral sensitivity bypasses these difficulties, making tandem architectures2 a necessary innovation.
Series tandem devices are the most common tandem architecture. In this design, an electron transport material, an optional metallic recombination layer, and a hole transport layer connect two independent photoactive layers called sub-cells. Linking sub-cells in a series configuration increases the open circuit voltage of the combination device. Some groups have had success with degenerately doped transport layers3&#8211;5, but more groups have used particles of gold or silver to aid recombination of holes and electrons in the interlayer6,7.
In contrast, parallel tandems require a high conductivity electrode, either anode or cathode, joining the two active layers. The interlayer must be highly transparent, which limits series tandem interlayers containing metallic particles, and even more so for the parallel tandem interlayers composed of thin, continuous metal electrodes. Carbon nanotubes (CNT) sheets show higher transparency than metal layers. So the NanoTech Institute, in collaboration with Shimane University, has introduced the concept of using as the interlayer electrode in monolithic, parallel tandem devices8.
Previous efforts featured monolithic, parallel, tandem OPV devices with CNT sheets functioning as interlayer anodes8,9. These methods require special care to avoid shorting of one or both cells or damaging preceding layers when depositing later layers. The new method described in this paper eases fabrication by placing the CNT electrode on top of the polymeric active layers of two single cells, then laminating the two separate devices together as shown in Figure 1. This method is remarkable as the device, including an air-stable CNT cathode, can be fabricated entirely in ambient conditions employing only dry and solution processing.
CNT sheets are not intrinsically good cathodes, as they require n-type doping to decrease the work function in order to collect electrons from the photoactive region of a solar cell10. Electric double layer charging in an electrolyte, such as an ionic liquid, can be used to shift the work function of CNT electrodes11&#8211;14.
As described in a preceding paper15 and depicted in Figure 2, when the gate voltage (VGate) is increases, the work function of the CNT common electrode is decreased, creating electrode asymmetry. This prevents hole collection from the OPV&#8217;s donor in favor of collecting electrons from the OPV&#8217;s acceptor, and the devices turn ON, changing from inefficient photoresistor into photodiode15 behavior. It should also be noted that the energy used to charge the device and the power lost due to gate leakage currents is trivial compared to the power generated by the solar cell15. Ionic gating of CNT electrodes has a large effect on the work function due to the low density of states and the high surface area to volume ratio in CNT electrodes. Similar methods have been used to enhance a Schottky barrier at the interface of CNT with n-Si16.

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			<td height="21" style="height:21px;">Poly(3,4-ethylenedioxythiophene):poly-(styrenesulfonate)</td>
			<td style="width:191px;">Heraeus</td>
			<td colspan="2">Clevios PVP AI 4083</td>
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			<td height="21" style="height:21px;width:312px;">poly(3- hexylthiophene-2,5-diyl)&#160;</td>
			<td style="width:191px;">Rieke Metals&#160; Inc.</td>
			<td style="width:119px;">P3HT:&#160; P200</td>
			<td></td>
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			<td height="25" style="height:25px;">phenyl-C61 -butyric&#160; acid methyl&#160; ester</td>
			<td style="width:191px;">1- Material</td>
			<td style="width:119px;">PC61BM</td>
			<td></td>
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			<td height="21" style="height:21px;">Poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b&#8242;]dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})&#160;</td>
			<td style="width:191px;">1- Material</td>
			<td style="width:119px;">PTB7</td>
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			<td height="21" style="height:21px;">phenyl-C61 -butyric acid methyl&#160; ester</td>
			<td style="width:191px;">Solenne</td>
			<td style="width:119px;">PC71BM</td>
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			<td height="21" style="height:21px;">1,8-Diiodooctane</td>
			<td style="width:191px;">Sigma Aldrich</td>
			<td align="right" style="width:119px;">250295</td>
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			<td height="21" style="height:21px;width:312px;">Chlorobenzene</td>
			<td style="width:191px;">Sigma Aldrich</td>
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			<td height="21" style="height:21px;width:312px;">Indium Tin Oxide Coated Glass 15 Ohm/SQ</td>
			<td style="width:191px;">Lumtec</td>
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			<td height="21" style="height:21px;">S1813</td>
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			<td height="21" style="height:21px;">MF311</td>
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			<td height="21" style="height:21px;">HCl</td>
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			<td height="21" style="height:21px;width:312px;">Acetone</td>
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			<td style="width:119px;">A18-20</td>
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			<td height="21" style="height:21px;width:312px;">Toluene</td>
			<td style="width:191px;">Fisher Scientific</td>
			<td style="width:119px;">T323-20</td>
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			<td height="21" style="height:21px;width:312px;">Methanol</td>
			<td style="width:191px;">BDH</td>
			<td style="width:119px;">BDH1135-19L</td>
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			<td height="21" style="height:21px;width:312px;">Isopropanol</td>
			<td style="width:191px;">Fisher Scientific</td>
			<td style="width:119px;">A416-20</td>
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			<td height="21" style="height:21px;width:312px;">CEE Spincoater</td>
			<td style="width:191px;">Brewer Scientific</td>
			<td style="width:119px;"></td>
			<td>http://www.utdallas.edu/research/cleanroom/tools/CEESpinCoater.htm</td>
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			<td height="21" style="height:21px;width:312px;">Contact Printer</td>
			<td style="width:191px;">Quintel</td>
			<td style="width:119px;">Q4000-6</td>
			<td>http://www.utdallas.edu/research/cleanroom/QuintelPrinter.htm</td>
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		<tr height="21">
			<td height="21" style="height:21px;width:312px;">CPK Spin Processor</td>
			<td style="width:191px;"></td>
			<td style="width:119px;"></td>
			<td>http://www.utdallas.edu/research/cleanroom/tools/CPKsolvent.htm</td>
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		<tr height="42">
			<td height="42" style="height:42px;width:312px;">Spin Coater</td>
			<td style="width:191px;">Laurell</td>
			<td style="width:119px;">WS-400-6NPP/LITE</td>
			<td></td>
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		<tr height="21">
			<td height="21" style="height:21px;width:312px;">Glove Box</td>
			<td style="width:191px;">M-Braun</td>
			<td style="width:119px;">Lab Master 130</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:312px;">Solar Simulator</td>
			<td style="width:191px;">Thermo Oriel/Newport</td>
			<td style="width:119px;"></td>
			<td></td>
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		<tr height="21">
			<td height="21" style="height:21px;width:312px;">Keithley 2400 SMU</td>
			<td style="width:191px;">Keithley/Techtronix</td>
			<td align="right" style="width:119px;">2400</td>
			<td></td>
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			<td height="21" style="height:21px;width:312px;">Keithley 7002 Multiplexer</td>
			<td style="width:191px;">Keithley/Techtronix</td>
			<td align="right" style="width:119px;">7002</td>
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			<td height="21" style="height:21px;width:312px;">Ultrasonic Cleaner</td>
			<td style="width:191px;">Kendal</td>
			<td style="width:119px;">HB-S-49HDT</td>
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			<td height="21" style="height:21px;width:312px;">Micropipette</td>
			<td style="width:191px;">Eppendorf</td>
			<td style="width:119px;">200uL</td>
			<td></td>
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ambient method for the production of an ionically gated carbon nanotube common cathode in tandem organic solar cells

A method of fabricating organic photovoltaic (OPV) tandems that requires no vacuum processing is presented. These devices are comprised of two solution-processed polymeric cells connected in parallel by a transparent carbon nanotubes (CNT) interlayer. This structure includes improvements in fabrication techniques for tandem OPV devices. First the need for ambient-processed cathodes is considered. The CNT anode in the tandem device is tuned via ionic gating to become a common cathode. Ionic gating employs electric double layer charging to lower the work function of the CNT electrode. Secondly, the difficulty of sequentially stacking tandem layers by solution-processing is addressed. The devices are fabricated via solution and dry-lamination in ambient conditions with parallel processing steps. The method of fabricating the individual polymeric cells, the steps needed to laminate them together with a common CNT cathode, and then provide some representative results are described. These results demonstrate ionic gating of the CNT electrode to create a common cathode and addition of current and efficiency as a result of the lamination procedure.

A tandem device formed from differing polymers, particularly polymers of significantly differing band gaps, is of practical interest as these devices can absorb the largest spectral range of light. In this device structure, the PTB7 sub-cell is the back cell and P3HT is the front sub-cell. This is intended to absorb the greatest amount of light as the P3HT sub-cell is largely transparent to the longer wavelength light absorbed by the PTB7 sub-cell. For the sake of clarity, the solar cell parameters, VOC, J<sub...

Watch this Scientific Journal Video about Ambient Method for the Production of an Ionically Gated Carbon Nanotube Common Cathode in Tandem Organic Solar Cells at JoVE.com

Ambient Method for the Production of an Ionically Gated Carbon Nanotube Common Cathode in Tandem Organic Solar Cells

A method of fabricating, in ambient conditions, organic photovoltaic tandem devices in a parallel configuration is presented. These devices feature an air-processed, semi-transparent, carbon nanotube common cathode.

A method of fabricating organic photovoltaic (OPV) tandems that requires no vacuum processing is presented. These devices are comprised of two ...

ambient-method-for-production-an-ionically-gated-carbon-nanotube

Research

JoVE Journal

Engineering

Controlling the Size, Shape and Stability of Supramolecular Polymers in Water

For aqueous based supramolecular polymers, the simultaneous control over shape, size and stability is very difficult1. At the same time, the ability to do so is highly important in view of a number of applications in functional soft matter including electronics, biomedical engineering, and sensors. In the past, successful strategies to control the size and shape of supramolecular polymers typically focused on the use of templates2,3, end cappers4 or selective solvent techniques5. 
Here we disclose a strategy based on self-assembling discotic amphiphiles that leads to the control over stack length and shape of ordered, chiral columnar aggregates. By balancing electrostatic repulsive interactions on the hydrophilic rim and attractive non-covalent forces within the hydrophobic core of the polymerizing building block, we manage to create small and discrete spherical objects6,7. Increasing the salt concentration to screen the charges induces a sphere-to-rod transition. Intriguingly, this transition is expressed in an increase of cooperativity in the temperature-dependent self-assembly mechanism, and more stable aggregates are obtained. 
For our study we select a benzene-1,3,5-tricarboxamide (BTA) core connected to a hydrophilic metal chelate via a hydrophobic, fluorinated L-phenylalanine based spacer (Scheme 1). The metal chelate selected is a Gd(III)-DTPA complex that contains two overall remaining charges per complex and necessarily two counter ions. The one-dimensional growth of the aggregate is directed by &pi;-&pi; stacking and intermolecular hydrogen bonding. However, the electrostatic, repulsive forces that arise from the charges on the Gd(III)-DTPA complex start limiting the one-dimensional growth of the BTA-based discotic once a certain size is reached. At millimolar concentrations the formed aggregate has a spherical shape and a diameter of around 5 nm as inferred from 1H-NMR spectroscopy, small angle X-ray scattering, and cryogenic transmission electron microscopy (cryo-TEM). The strength of the electrostatic repulsive interactions between molecules can be reduced by increasing the salt concentration of the buffered solutions. This screening of the charges induces a transition from spherical aggregates into elongated rods with a length &gt; 25 nm. Cryo-TEM allows to visualise the changes in shape and size. In addition, CD spectroscopy permits to derive the mechanistic details of the self-assembly processes before and after the addition of salt. Importantly, the cooperativity -a key feature that dictates the physical properties of the produced supramolecular polymers- increases dramatically upon screening the electrostatic interactions. This increase in cooperativity results in a significant increase in the molecular weight of the formed supramolecular polymers in water.

The goal of this experiment is to determine and control the size, shape and stability of self-assembled discotic amphiphiles in water. For aqueous based supramolecular polymers such level of control is very difficult. We apply a strategy using both repulsive and attractive interactions. The experimental techniques applied to characterize this system are broadly applicable.

For aqueous based supramolecular polymers, the simultaneous control over shape, size and stability is very difficult1. At the same time, the ability to do ...

Fabrication, Densification, and Replica Molding of 3D Carbon Nanotube Microstructures

The introduction of new materials and processes to microfabrication has, in large part, enabled many important advances in microsystems, lab-on-a-chip devices, and their applications. In particular, capabilities for cost-effective fabrication of polymer microstructures were transformed by the advent of soft lithography and other micromolding techniques 1, 2, and this led a revolution in applications of microfabrication to biomedical engineering and biology. Nevertheless, it remains challenging to fabricate microstructures with well-defined nanoscale surface textures, and to fabricate arbitrary 3D shapes at the micro-scale. Robustness of master molds and maintenance of shape integrity is especially important to achieve high fidelity replication of complex structures and preserving their nanoscale surface texture. The combination of hierarchical textures, and heterogeneous shapes, is a profound challenge to existing microfabrication methods that largely rely upon top-down etching using fixed mask templates. On the other hand, the bottom-up synthesis of nanostructures such as nanotubes and nanowires can offer new capabilities to microfabrication, in particular by taking advantage of the collective self-organization of nanostructures, and local control of their growth behavior with respect to microfabricated patterns. 
Our goal is to introduce vertically aligned carbon nanotubes (CNTs), which we refer to as CNT "forests", as a new microfabrication material. We present details of a suite of related methods recently developed by our group: fabrication of CNT forest microstructures by thermal CVD from lithographically patterned catalyst thin films; self-directed elastocapillary densification of CNT microstructures; and replica molding of polymer microstructures using CNT composite master molds. In particular, our work shows that self-directed capillary densification ("capillary forming"), which is performed by condensation of a solvent onto the substrate with CNT microstructures, significantly increases the packing density of CNTs. This process enables directed transformation of vertical CNT microstructures into straight, inclined, and twisted shapes, which have robust mechanical properties exceeding those of typical microfabrication polymers. This in turn enables formation of nanocomposite CNT master molds by capillary-driven infiltration of polymers. The replica structures exhibit the anisotropic nanoscale texture of the aligned CNTs, and can have walls with sub-micron thickness and aspect ratios exceeding 50:1. Integration of CNT microstructures in fabrication offers further opportunity to exploit the electrical and thermal properties of CNTs, and diverse capabilities for chemical and biochemical functionalization 3.

We present methods for fabrication of patterned microstructures of vertically aligned carbon nanotubes (CNTs), and their use as master molds for production of polymer microstructures with organized nanoscale surface texture. The CNT forests are densified by condensation of solvent onto the substrate, which significantly increases their packing density and enables self-directed formation of 3D shapes.

The introduction of new materials and processes to microfabrication has, in large part, enabled many important advances in microsystems, lab-on-a-chip ...

Dry Oxidation and Vacuum Annealing Treatments for Tuning the Wetting Properties of Carbon Nanotube Arrays

In this article, we describe a simple method to reversibly tune the wetting properties of vertically aligned carbon nanotube (CNT) arrays. Here, CNT arrays are defined as densely packed multi-walled carbon nanotubes oriented perpendicular to the growth substrate as a result of a growth process by the standard thermal chemical vapor deposition (CVD) technique.1,2 These CNT arrays are then exposed to vacuum annealing treatment to make them more hydrophobic or to dry oxidation treatment to render them more hydrophilic. The hydrophobic CNT arrays can be turned hydrophilic by exposing them to dry oxidation treatment, while the hydrophilic CNT arrays can be turned hydrophobic by exposing them to vacuum annealing treatment. Using a combination of both treatments, CNT arrays can be repeatedly switched between hydrophilic and hydrophobic.2 Therefore, such combination show a very high potential in many industrial and consumer applications, including drug delivery system and high power density supercapacitors.3-5
The key to vary the wettability of CNT arrays is to control the surface concentration of oxygen adsorbates. Basically oxygen adsorbates can be introduced by exposing the CNT arrays to any oxidation treatment. Here we use dry oxidation treatments, such as oxygen plasma and UV/ozone, to functionalize the surface of CNT with oxygenated functional groups. These oxygenated functional groups allow hydrogen bond between the surface of CNT and water molecules to form, rendering the CNT hydrophilic. To turn them hydrophobic, adsorbed oxygen must be removed from the surface of CNT. Here we employ vacuum annealing treatment to induce oxygen desorption process. CNT arrays with extremely low surface concentration of oxygen adsorbates exhibit a superhydrophobic behavior.

This article describes a simple method to fabricate vertically aligned carbon nanotube arrays by CVD and to subsequently tune their wetting properties by exposing them to vacuum annealing or dry oxidation treatment.

In this article, we describe a simple method to reversibly  tune the wetting properties of vertically aligned carbon nanotube (CNT) arrays.  Here, CNT ...

Synthesis and Functionalization of Nitrogen-doped Carbon Nanotube Cups with Gold Nanoparticles as Cork Stoppers

Nitrogen-doped carbon nanotubes consist of many cup-shaped graphitic compartments termed as nitrogen-doped carbon nanotube cups (NCNCs). These as-synthesized graphitic nanocups from chemical vapor deposition (CVD) method were stacked in a head-to-tail fashion held only through noncovalent interactions. Individual NCNCs can be isolated out of their stacking structure through a series of chemical and physical separation processes. First, as-synthesized NCNCs were oxidized in a mixture of strong acids to introduce oxygen-containing defects on the graphitic walls. The oxidized NCNCs were then processed using high-intensity probe-tip sonication which effectively separated the stacked NCNCs into individual graphitic nanocups. Owing to their abundant oxygen and nitrogen surface functionalities, the resulted individual NCNCs are highly hydrophilic and can be effectively functionalized with gold nanoparticles (GNPs), which preferentially fit in the opening of the cups as cork stoppers. These graphitic nanocups corked with GNPs may find promising applications as nanoscale containers and drug carriers.

We discussed the synthesis of individual graphitic nanocups using a series of techniques including chemical vapor deposition, acid oxidation and probe-tip sonication. By citrate reduction of HAuCl4, the graphitic nanocups were effectively corked with gold nanoparticles due to the chemically reactive edges of the cups.

Nitrogen-doped carbon  nanotubes consist of many cup-shaped graphitic compartments termed as  nitrogen-doped carbon nanotube cups (NCNCs).  These ...

Using Neutron Spin Echo Resolved Grazing Incidence Scattering to Investigate Organic Solar Cell Materials

The spin echo resolved grazing incidence scattering (SERGIS) technique has been used to probe the length-scales associated with irregularly shaped crystallites. Neutrons are passed through two well defined regions of magnetic field; one before and one after the sample. The two magnetic field regions have opposite polarity and are tuned such that neutrons travelling through both regions, without being perturbed, will undergo the same number of precessions in opposing directions. In this case the neutron precession in the second arm is said to &#34;echo&#34; the first, and the original polarization of the beam is preserved. If the neutron interacts with a sample and scatters elastically the path through the second arm is not the same as the first and the original polarization is not recovered. Depolarization of the neutron beam is a highly sensitive probe at very small angles (&#60;50&#160;&#956;rad) but still allows a high intensity, divergent beam to be used. The decrease in polarization of the beam reflected from the sample as compared to that from the reference sample can be directly related to structure within the sample.
In comparison to scattering observed in neutron reflection measurements the SERGIS signals are often weak and are unlikely to be observed if the in-plane structures within the sample under investigation are dilute, disordered, small in size and polydisperse or the neutron scattering contrast is low. Therefore, good results will most likely be obtained using the SERGIS technique if the sample being measured consist of thin films on a flat substrate and contain scattering features that contains a high density of moderately sized features (30 nm to 5 &#181;m) which scatter neutrons strongly or the features are arranged on a lattice. An advantage of the SERGIS technique is that it can probe structures in the plane of the sample.

Progress has been made in utilizing spin echo resolved grazing incidence scattering (SERGIS) as a neutron scattering technique to probe the length-scales in irregular samples. Crystallites of [6,6]-phenyl-C61-butyric acid methyl ester have been probed using the SERGIS technique and the results confirmed by optical and atomic force microscopy.

The spin echo resolved grazing incidence scattering (SERGIS) technique has been used to probe the length-scales associated with irregularly shaped ...

Fabrication of Low Temperature Carbon Nanotube Vertical Interconnects Compatible with Semiconductor Technology

We demonstrate a method for the low temperature growth (350 &#176;C) of vertically-aligned carbon nanotubes (CNT) bundles on electrically conductive thin-films. Due to the low growth temperature, the process allows integration with modern low-&#954; dielectrics and some flexible substrates. The process is compatible with standard semiconductor fabrication, and a method for the fabrication of electrical 4-point probe test structures for vertical interconnect test structures is presented. Using scanning electron microscopy the morphology of the CNT bundles is investigated, which demonstrates vertical alignment of the CNT and can be used to tune the CNT growth time. With Raman spectroscopy the crystallinity of the CNT is investigated. It was found that the CNT have many defects, due to the low growth temperature. The electrical current-voltage measurements of the test vertical interconnects displays a linear response, indicating good ohmic contact was achieved between the CNT bundle and the top and bottom metal electrodes. The obtained resistivities of the CNT bundle are among the average values in the literature, while a record-low CNT growth temperature was used.

A method for the growth of low temperature vertically-aligned carbon nanotubes, and the subsequent fabrication of vertical interconnect electrical test structures using semiconductor fabrication is presented.

We demonstrate a method for the low temperature growth (350 &#176;C) of vertically-aligned carbon nanotubes (CNT) bundles on electrically conductive ...

Quantification of Hydrogen Concentrations in Surface and Interface Layers and Bulk Materials through Depth Profiling with Nuclear Reaction Analysis

Nuclear reaction analysis (NRA) via the resonant 1H(15N,&#945;&#947;)12C reaction is a highly effective method of depth profiling that quantitatively and non-destructively reveals the hydrogen density distribution at surfaces, at interfaces, and in the volume of solid materials with high depth resolution. The technique applies a 15N ion beam of 6.385 MeV provided by an electrostatic accelerator and specifically detects the 1H isotope in depths up to about 2 &#956;m from the target surface. Surface H coverages are measured with a sensitivity in the order of ~1013 cm-2 (~1% of a typical atomic monolayer density) and H volume concentrations with a detection limit of ~1018 cm-3 (~100 at. ppm). The near-surface depth resolution is 2-5 nm for surface-normal 15N ion incidence onto the target and can be enhanced to values below 1 nm for very flat targets by adopting a surface-grazing incidence geometry. The method is versatile and readily applied to any high vacuum compatible homogeneous material with a smooth surface (no pores). Electrically conductive targets usually tolerate the ion beam irradiation with negligible degradation. Hydrogen quantitation and correct depth analysis require knowledge of the elementary composition (besides hydrogen) and mass density of the target material. Especially in combination with ultra-high vacuum methods for in-situ target preparation and characterization, 1H(15N,&#945;&#947;)12C NRA is ideally suited for hydrogen analysis at atomically controlled surfaces and nanostructured interfaces. We exemplarily demonstrate here the application of 15N NRA at the MALT Tandem accelerator facility of the University of Tokyo to (1) quantitatively measure the surface coverage and the bulk concentration of hydrogen in the near-surface region of a H2 exposed Pd(110) single crystal, and (2) to determine the depth location and layer density of hydrogen near the interfaces of thin SiO2 films on Si(100).

We illustrate the application of 1H(15N,&#945;&#947;)12C resonant nuclear reaction analysis (NRA) to quantitatively evaluate the density of hydrogen atoms on the surface, in the volume, and at an interfacial layer of solid materials. The near-surface hydrogen depth profiling of a Pd(110) single crystal and of SiO2/Si(100) stacks is described.

Nuclear reaction analysis (NRA) via the resonant 1H(15N,&#945;&#947;)12C reaction is a highly effective method of depth profiling that quantitatively and ...

Digital Printing of Titanium Dioxide for Dye Sensitized Solar Cells

Silicon solar cell manufacturing is an expensive and high energy consuming process. In contrast, dye sensitized solar cell production is less environmentally damaging with lower processing temperatures presenting a viable and low cost alternative to conventional production. This paper further enhances these environmental credentials by evaluating the digital printing and therefore additive production route for these cells. This is achieved here by investigating the formation and performance of a metal oxide photoelectrode using nanoparticle sized titanium dioxide. An ink-jettable material was formulated, characterized and printed with a piezoelectric inkjet head to produce a 2.6 &#181;m thick layer. The resultant printed layer was fabricated into a functioning cell with an active area of 0.25 cm2 and a power conversion efficiency of 3.5%. The binder-free formulation resulted in a reduced processing temperature of 250 &#176;C, compatible with flexible polyamide substrates which are stable up to temperatures of 350 &#730;C. The authors are continuing to develop this process route by investigating inkjet printing of other layers within dye sensitized solar cells.

This paper investigates the suitability of inkjet printing for the manufacturing of dye-sensitized solar cells. A binder-free TiO2 nanoparticle ink was formulated and printed onto a FTO glass substrate. The printed layer was fabricated into a cell with an active area of 0.25 cm2 and an efficiency of 3.5%.

Silicon solar cell manufacturing is an expensive and high energy consuming process. In contrast, dye sensitized solar cell production is less ...

Morphology Control for Fully Printable Organic&#8211;Inorganic Bulk-heterojunction Solar Cells Based on a Ti-alkoxide and Semiconducting Polymer

The photoactive layer of a typical organic thin-film bulk-heterojunction (BHJ) solar cell commonly uses fullerene derivatives as the electron-accepting material. However, fullerene derivatives are air-sensitive; therefore, air-stable material is needed as an alternative. In the present study, we propose and describe the properties of Ti-alkoxide as an alternative electron-accepting material to fullerene derivatives to create highly air-stable BHJ solar cells. It is well-known that controlling the morphology in the photoactive layer, which is constructed with fullerene derivatives as the electron acceptor, is important for obtaining a high overall efficiency through the solvent method. The conventional solvent method is useful for high-solubility materials, such as fullerene derivatives. However, for Ti-alkoxides, the conventional solvent method is insufficient, because they only dissolve in specific solvents. Here, we demonstrate a new approach to morphology control that uses the molecular bulkiness of Ti-alkoxides without the conventional solvent method. That is, this method is one approach to obtain highly efficient, air-stable, organic-inorganic bulk-heterojunction solar cells.

Morphology Control for Fully Printable Organic&amp;#8211;Inorganic Bulk-heterojunction Solar Cells Based on a Ti-alkoxide and Semiconducting Polymer

A method for fully printable, fullerene-free, highly air-stable, bulk-heterojunction solar cells based on Ti alkoxides as the electron acceptor and the electron-donating polymer fabrication is described here. Moreover, a method for controlling the morphology of the photoactive layer through the molecular bulkiness of the Ti-alkoxide units is reported.

The photoactive layer of a typical organic thin-film bulk-heterojunction (BHJ) solar cell commonly uses fullerene derivatives as the electron-accepting ...

Precision Milling of Carbon Nanotube Forests Using Low Pressure Scanning Electron Microscopy

A nanoscale fabrication technique appropriate for milling carbon nanotube (CNT) forests is described. The technique utilizes an environmental scanning electron microscope (ESEM) operating with a low pressure water vapor ambient. In this technique, a portion of the electron beam interacts with the water vapor in the vicinity of the CNT sample, dissociating the water molecules into hydroxyl radicals and other species by radiolysis. The remainder of the electron beam interacts with the CNT forest sample, making it susceptible to oxidation from the chemical products of radiolysis. This technique may be used to trim a selected region of an individual CNT, or it may be used to remove hundreds of cubic microns of material by adjusting ESEM parameters. The machining resolution is similar to the imaging resolution of the ESEM itself. The technique produces only small quantities of carbon residue along the boundaries of the cutting zone, with minimal effect on the native structural morphology of the CNT forest.

Low pressure scanning electron microscopy in a water vapor ambient is used to machine nanoscale to microscale features in carbon nanotube forests.

A nanoscale fabrication technique appropriate for milling carbon nanotube (CNT) forests is described. The technique utilizes an environmental scanning ...