This work was supported by the Air Force Office of Scientific Research grant FA9550-16-1-0011 and University of Missouri startup funds. The authors would like to thank the University of Missouri Electron Microscopy Core facility for assistance with SEM imaging and use of patterning equipment and software.

1. Preparation of CNT Forest Sample for Milling
<ol>
	<li>CNT Synthesis
	<ol>
		<li>Deposit 10 nm of aluminum oxide (alumina) on a thermally oxidized silicon wafer using atomic layer deposition13 or other physical vapor deposition methods.</li>
		<li>Deposit 1 nm of iron on the alumina support layer by sputtering14 or other physical vapor deposition method.</li>
		<li>Synthesize CNTs using an established process, such as thermal chemical vapor deposition15.
		<ol>
			<li>Heat a 20 mm diameter tube furnace to 750 &#176;C in 400 standard cubic centimeters (sccm) of flowing helium and 100 sccm hydrogen. Introduce 100 sccm ethylene as a hydrocarbon feedstock gas for a growth rate of approximately 50 &#956;m/min.</li>
		</ol>
		</li>
	</ol>
	</li>
	<li>SEM Preparation
	<ol>
		<li>Apply carbon tape to a standard 1/2&#34; diameter SEM stub. If tilting the stage is required, overlap the region of the CNT forest sample to be milled over the edge of the stub. If software-controlled electron beam rastering will be used in the milling procedure, secure the CNT sample to an electron beam lithography mount in a similar manner.</li>
		<li>If milling the CNT cross section, secure the stub to a 45&#176; stub holder with a set screw.</li>
		<li>Vent the ESEM by selecting the &#34;Vent&#34; icon from the ESEM control software.</li>
		<li>Open the ESEM stage door, and secure the stub to the SEM stage with a set screw.</li>
		<li>Close the SEM chamber and select &#34;High Vacuum&#34; in the ESEM control software.</li>
		<li>While the ESEM chamber is pumping, select the electron beam parameters of 5 kV and spot size of 3.0 using the Beam Control tab within the control software.</li>
		<li>Select the secondary electron detector by selecting Detectors | ETD(SE) in the ESEM control software.</li>
		<li>Select the &#34;Beam On&#34; icon in the control software. The beam can be activated only once the chamber vacuum is less than 10-4 Torr. Use manual SEM focus control knobs to focus the sample.</li>
		<li>Tilt the sample to 45&#176; using manual tilt stage control knob or by inputting 45&#176; in the &#34;Tilt&#34; field in the &#34;Coordinates&#34; tab of the ESEM software. Focus on the highest sample. Link the focal distance to the working distance by selecting Stage | Link Z to FWD in the ESEM software menu. Input 7 mm into the &#34;Z&#34; field in the &#34;Coordinates&#34; tab within the control software.</li>
		<li>Adjust focus, stigmation, brightness and contrast using the manual control knobs to resolve a well-focused image.</li>
	</ol>
	</li>
	<li>Beam Adjustment in High Vacuum Mode
	<ol>
		<li>Locate a region for milling using navigation controls. Double click within the SEM image view or by manually turning the x and y control knobs of the SEM stage control to navigate.</li>
		<li>Navigate to an adjacent location approximately 100 &#956;m away from the milling region.</li>
		<li>Consult Figure 1 to estimate the material removal rate of the CNT forest as a function of pressure, acceleration voltage, dwell time per pixel, and beam current.</li>
		<li>Adjust the acceleration voltage to 30 kV and spot size to 5.0 using the ESEM control software. Adjust image focus, brightness, and contrast using the ESEM control knobs. For nanometer-scale milling of individual or few CNTs, select 5 kV and spot size of 3.0.</li>
		<li>Select a 1 mm aperture by manual aperture adjustment. Adjust focus, stigmation, brightness, and contrast to obtain a well-resolved image, as previously detailed.</li>
		<li>Decrease magnification to &#60;1,000X.</li>
	</ol>
	</li>
	<li>SEM Setup in Low Pressure Water Vapor
	<ol>
		<li>Select a pressure of 11 Pa in the control software dropdown box.</li>
		<li>Select &#34;Low Pressure&#34; mode in the &#34;Vacuum&#34; settings in the ESEM software to introduce water vapor.</li>
		<li>Select &#34;Beam On&#34; in the control software upon pressure stabilization. Select a dwell time of &#60;10 &#956;s and a resolution of 1,024 x 884 in the drop-down boxes of the control software.</li>
		<li>Adjust the image brightness, contrast, focus, and stigmation as previously detailed.</li>
		<li>Navigate to the desired milling region. Rotate the image orientation by selecting Scan | Scan Rotation in the control software, if required. Select a suitable rotation angle that aligns with the native vertical and horizontal scan orientation of the SEM.</li>
		<li>For milling feature sizes on the order of 1 &#956;m, select a magnification of 40,000X. Select a magnification of 20,000X to mill features with dimensions up to 5 &#956;m.</li>
		<li>Pause the electron beam by selecting the &#39; &#34; &#39; icon . An image of the CNT forest will be displayed and may be used for selecting reduced area milling regions while the beam is paused.</li>
	</ol>
	</li>
</ol>
2. CNT Forest Milling
<ol>
	<li>Instructions for CNT forest milling using a rectangular selected area
	<ol>
		<li>Choose the &#39;Reduced Area&#39; tool in the control software, or select Scan-Reduced Area in the software menu. Extend a reduced area rectangle over the area to be milled.</li>
		<li>Adjust the image resolution to 2,048 x 1,768. Increase the dwell time to 2 ms. If 2 ms is not available, navigate to the Scan |Preferences and select the &#34;Scanning&#34; tab. Select an existing scan time and type &#34;2.0 ms&#34; into the &#34;Dwell Time&#34; field. Click &#34;OK&#34; to close the menu.</li>
		<li>Select the &#39; &#34; &#39; icon in the control software to activate the electron beam.</li>
		<li>Select the &#39; &#34; &#39; icon so that the beam rasters over the selected area one time. Select the icon immediately after step 2.1.3. The scan duration depends on the size of the selected area, resolution and dwell time and may be approximated by multiplying the number of pixels within the scan area and the dwell time per pixel.</li>
		<li>Decrease magnification to &#60;1,000X once the beam has completed rastering the selected area. Revert to the parameters used in step 1.3, including High Vacuum. Select &#34;Beam On&#34; to engage the beam.</li>
	</ol>
	</li>
	<li>Instructions for CNT forest milling along a horizontal line
	<ol>
		<li>Select the line scan feature by navigating to Scan | Line in the control software. The line width is determined by the size of the electron beam itself. Adjust the image resolution to 2,048 x 1,768 from the control software dropdown box. Increase the dwell time to 2 ms as detailed in step 2.1.2.</li>
		<li>Using the still image acquired before pausing the electron beam, place the line over the area to be milled.</li>
		<li>Select the videoscope icon or navigate to the Scan menu and select &#34;Videoscope.&#34; Using the videoscope tool provides feedback relative to when a line scan has fully completed.</li>
		<li>Select the &#39; &#34; &#39; icon to scan electron beam across the width of the line.</li>
		<li>Select the &#39; &#34; &#39; icon to blank the electron beam.</li>
	</ol>
	</li>
	<li>Instructions for CNT Forest milling using software-controlled electron beam rastering
	<ol>
		<li>Pattern Generation
		<ol>
			<li>Design a milling pattern of interest using a CAD software package such as AutoCAD.</li>
			<li>Using &#34;Nanometer Pattern Generation System&#34; (NPGS) software, import the CAD pattern file.</li>
			<li>Convert the shapes to solid features by selected &#34;Filled Polygons&#34; in the NPGS software.</li>
			<li>Save the drawing as a &#39;.dc2&#39; file in a designated project folder of NPGS.</li>
			<li>Using NPGS, navigate to the project folder containing the &#34;.dc2&#34; file. Right select the &#34;.dc2&#34; file and select &#34;Run File Editor&#34; to convert the drawing to NPGS code. Typical parameters used to pattern CNT forests at given conditions are as listed below: 
			Center-to-center distance = 5 nm 
			Line Spacing = 5 nm 
			Magnification = 10,000X 
			Desired Beam Current = 26 
			Line Dose = 100 nC/cm</li>
		</ol>
		</li>
		<li>Electron Beam Milling using NPGS Lithography Software</li>
		<li>Select the &#34;NPGS Mode&#34; in NPGS software button to give control of the SEM to NPGS.</li>
		<li>Highlight the pattern file and select &#34;Process Run File&#34; in NPGS to initiate milling.</li>
		<li>Select &#34;SEM Mode&#34; in the NPGS software when patterning is finished. Select &#34;High Vacuum&#34; in the ESEM control software.</li>
		<li>Select &#34;Beam On&#34; to inspect the milled region. Use conditions detailed in step 1.3.</li>
	</ol>
	</li>
</ol>
3. Sample Removal
<ol>
	<li>Vent the chamber by selecting &#34;Vent&#34; in the ESEM control software.</li>
	<li>Open the ESEM door. Remove the stub by loosening the set screw.</li>
	<li>Close the chamber door. Select &#34;High Vacuum&#34; in the control software.</li>
</ol>

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The authors declare that they have no competing financial interests.

The protocol details best practices for milling relatively large (micron-scale) features in CNT forests. In general, the material removal rate may be reduced by reducing the acceleration voltage, spot size, and aperture diameter. To trim a specific CNT within a forest, recommended conditions include 5 kV, a spot size of 3, and an aperture that is 50 &#956;m or less in diameter. Note that the milling technique using reduced area rectangles is detailed such that the electron beam rasters the enclosed region only one time. ...

Carbon nanotubes (CNTs) and graphene are carbon-based nanomaterials that have attracted significant attention because of their superior strength, durability, thermal, and electrical properties. Precision machining of carbon nanomaterials has become an emerging topic of research and offers the potential to engineer and manipulate these materials towards a variety of engineering applications. Machining CNTs and graphene requires nanoscale spatial precision to first locate a nanoscale area of interest and then to selectively remove only the material within the area of interest. As an example, consider the machining of vertically oriented CNT forests (also known as CNT arrays). The cross section of CNT forests may be precisely defined by lithographic patterning of catalyst films. The top surface of the vertically oriented forests, however, are frequently poorly ordered with non-uniform height. For surface-sensitive applications such as thermal interface materials, the irregular surface may impede optimal surface contact and reduce device performance. Precision trimming of the irregular surface to create a uniform flat surface could potentially offer better, more repeatable performance by maximizing the available contact area.
Precision machining techniques for nanomaterials frequently do not resemble conventional macroscale mechanical machining technologies such as drilling, milling, and polishing by means of hardened tooling. To date, techniques using energetic beams have been most successful at site-selective milling of carbon nanomaterials. These techniques include laser, electron beam, and focused ion beam (FIB) irradiation. Of these, laser machining techniques provide the most rapid material removal rate1,2; however, the spot size of laser systems is on the order of many microns and is too large to isolate nanometer-scale entities such as a single carbon nanotube segment within a densely populated forest. By contrast, electron and ion beam systems produce a beam that may be focused to a spot that is several nanometers or less in diameter.
FIB systems are specifically designed for nanoscale milling and deposition of materials. These systems utilize an energetic beam of gaseous metal ions (typically gallium) to sputter material from a selected area. FIB milling of CNTs is achievable, but often with unintended byproducts including gallium and carbon redeposition in surrounding regions of the forest3,4. When the technique is used for CNT forests, the redeposited material masks and/or alters the morphology of selected milling region, altering the native appearance and behavior of the CNT forest. The gallium may also implant within the CNT, providing electronic doping. Such consequences often make FIB-based milling prohibitive for CNT forests.
Transmission electron microscopes (TEMs) utilize a finely focused beam of electrons to probe the internal structure of materials. Acceleration voltages for TEM operation typically range from 80-300 kV. Because the knock-on energy of CNTs is 86.4 keV5, the electron energy produced by TEM is sufficient to directly remove atoms from the CNT lattice and induce highly localized milling. The technique mills CNTs with potentially sub-nanometer precision5,6,7; however, the process is very slow &#8211; often requiring minutes to mill a single CNT. Importantly, TEM-based milling approaches require CNTs to first be removed from a growth substrate and dispersed onto a TEM grid for processing. As a result, TEM-based methods are generally not compatible with CNT forest milling in which the CNTs must remain on a rigid substrate.
Milling of CNT forests by scanning electron microscopes (SEMs) has also received attention. In contrast to TEM-based techniques, SEM instruments are typically unable to accelerate electrons with sufficient energy to impart the knock-on energy required to directly remove carbon atoms. Rather, SEM-based techniques utilize an electron beam in the presence of a low-pressure gaseous oxidizer. The electron beam selectively damages the CNT lattice and may dissociate the gaseous ambient into more reactive species such as H2O2 and the hydroxyl radical. Water vapor and oxygen are the most commonly reported gases to achieve selective area etching. Because the SEM-based techniques rely on a multiple-step chemical process, numerous processing variables may influence the milling rate and precision of the process. It has been previously observed that increasing acceleration voltage and beam current directly increase the milling rate because of an increased energy flux, as expected11. The effect of chamber pressure is less obvious. A pressure that is too low suffers from a deficiency of the oxidizing agent, decreasing the milling rate. Further, an over-abundance of gaseous species scatters the electron beam and decreases the electron flux in the milling region, also decreasing the material removal rate.
To estimate the carbon removal rate, an approach similar to that used by Lassiter and Rack12 was employed, whereby electrons interact with precursor molecules near the surface to generate reactive species that etch the substrate surface. From this model, the etch rate is estimated as
<img alt="Equation" src="/files/ftp_upload/55149/55149eq1.jpg" />
where NA is the surface concentration of the etchant species, Z is the surface concentration of available reaction sites, x is a stoichiometry factor relating the volatile etching products generated relative to the reactants, A&#963; represents the probability of generating the desired etching species from an electron-water vapor collision, and &#915;e is the electron flux at the surface. The factors of x and A&#963; are assumed to be unity, while Z is assumed to be nearly constant and significantly larger than NA. Further details may be found in our previous work.11
In this article, a procedure is explored that uses low-pressure water vapor within a SEM to mill regions ranging from individual CNTs to large volume (tens of cubic micrometers) material removal. Here we demonstrate the technique used to mill CNT forests using an ESEM by the use of reduced area rectangles, horizontal line scans, and software-controlled rastering of the electron beam. Additional software and hardware are required for pattern generation, as outlined in the Materials List. Emphasis is placed on removing relatively large (100&#39;s of cubic microns) material volume from a CNT forest, so the following processing conditions are relatively aggressive.
When handling the sample and the sample stub, it is important to wear disposable nitrile gloves. This will prevent oils from being transferred to the stub or sample and consequently deteriorating the effectiveness of the pumps.

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>100 mm diameter silicon wafer with 1 micron thermal oxide</td>
			<td>University Wafer</td>
			<td></td>
			<td>Beginning substrate</td>
		</tr>
		<tr>
			<td>Iron sputter target</td>
			<td>Kurt J. Lesker</td>
			<td>EJTFEXX351A2</td>
			<td>Sputter target&#160;</td>
		</tr>
		<tr>
			<td>Savannah 200</td>
			<td>Cambridge</td>
			<td></td>
			<td>For atomic layer deposition of alumina</td>
		</tr>
		<tr>
			<td>Quanta 600F Environmental SEM</td>
			<td>FEI</td>
			<td></td>
			<td>Environmental scanning electron microscope used to support a low-pressure water vapor ambient environment for CNT forest milling</td>
		</tr>
		<tr>
			<td>xT Microscope Control software</td>
			<td>FEI</td>
			<td>4.1.7</td>
			<td>Control software used on Quanta 600F ESEM</td>
		</tr>
		<tr>
			<td>Nanometer Pattern Generation System - Software</td>
			<td>JC Nabity Lithography Systems</td>
			<td>Version 9</td>
			<td>Software used for electron-beam lithography</td>
		</tr>
		<tr>
			<td>Dedicated computer with PCI516 Lithography board</td>
			<td></td>
			<td></td>
			<td>Equipment used for electron-beam lithography</td>
		</tr>
		<tr>
			<td>DesignCAD software</td>
			<td></td>
			<td>V 21.2</td>
			<td>Optional equipment used to generate patterns for electron-beam lithography</td>
		</tr>
		<tr>
			<td>E-beam lithography mount</td>
			<td>Ted Pella</td>
			<td>16405</td>
			<td>Electron beam lithography mount with a Faraday cup and gold nanoparticles on carbon tape</td>
		</tr>
		<tr>
			<td>Picoammeter</td>
			<td>Keithley</td>
			<td>6485</td>
			<td>Used with the Faraday cup to quantify beam current</td>
		</tr>
		<tr>
			<td>12.7 mm diameter SEM stub</td>
			<td>Ted Pella</td>
			<td>16111</td>
			<td>SEM stub</td>
		</tr>
		<tr>
			<td>45 degree pin stub holder</td>
			<td>Ted Pella</td>
			<td>15329</td>
			<td>Optional equipment used to mill the cross section of a CNT forest</td>
		</tr>
	</tbody>
</table>

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.

The ESEM technique was used to mill a CNT forest synthesized using thermal CVD15,16. Selected area removal of a few CNTs from within a forest is shown in Figure 211. For this demonstration, parameters include 5 kV, spot size of 3, 11 Pa, 170,000X magnification, 2 ms dwell time, and an aperture of 30 &#181;m.
To demonstrate a large...

Watch this Scientific Journal Video about Precision Milling of Carbon Nanotube Forests Using Low Pressure Scanning Electron Microscopy at JoVE.com

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

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 ...

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7.4K Views.  University of Missouri. Low pressure scanning electron microscopy in a water vapor ambient is used to machine nanoscale to microscale features in carbon nanotube forests.

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

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 ...

Synthesis and Microdiffraction at Extreme Pressures and Temperatures

High pressure compounds and polymorphs are investigated for a broad range of purposes such as determine structures and processes of deep planetary interiors, design materials with novel properties, understand the mechanical behavior of materials exposed to very high stresses as in explosions or impacts. Synthesis and structural analysis of materials at extreme conditions of pressure and temperature entails remarkable technical challenges. In the laser heated diamond anvil cell (LH-DAC), very high pressure is generated between the tips of two opposing diamond anvils forced against each other; focused infrared laser beams, shined through the diamonds, allow to reach very high temperatures on samples absorbing the laser radiation. When the LH-DAC is installed in a synchrotron beamline that provides extremely brilliant x-ray radiation, the structure of materials under extreme conditions can be probed in situ. LH-DAC samples, although very small, can show highly variable grain size, phase and chemical composition. In order to obtain the high resolution structural analysis and the most comprehensive characterization of a sample, we collect diffraction data in 2D grids and combine powder, single crystal and multigrain diffraction techniques. Representative results obtained in the synthesis of a new iron oxide, Fe4O5 1 will be shown.

The laser heated diamond anvil cell combined with synchrotron micro-diffraction techniques allows researchers to explore the nature and properties of new phases of matter at extreme pressure and temperature (PT) conditions. Heterogeneous samples can be characterized in situ under high pressure by 2D mapping and combined powder, single-crystal and multigrain diffraction approaches.

High pressure compounds and polymorphs are investigated for a broad range of purposes such as determine structures and processes of deep planetary ...

Scanning-probe Single-electron Capacitance Spectroscopy

The integration of low-temperature scanning-probe techniques and single-electron capacitance spectroscopy represents a powerful tool to study the electronic quantum structure of small systems - including individual atomic dopants in semiconductors. Here we present a capacitance-based method, known as Subsurface Charge Accumulation (SCA) imaging, which is capable of resolving single-electron charging while achieving sufficient spatial resolution to image individual atomic dopants. The use of a capacitance technique enables observation of subsurface features, such as dopants buried many nanometers beneath the surface of a semiconductor material1,2,3. In principle, this technique can be applied to any system to resolve electron motion below an insulating surface.
As in other electric-field-sensitive scanned-probe techniques4, the lateral spatial resolution of the measurement depends in part on the radius of curvature of the probe tip. Using tips with a small radius of curvature can enable spatial resolution of a few tens of nanometers. This fine spatial resolution allows investigations of small numbers (down to one) of subsurface dopants1,2. The charge resolution depends greatly on the sensitivity of the charge detection circuitry; using high electron mobility transistors (HEMT) in such circuits at cryogenic temperatures enables a sensitivity of approximately 0.01 electrons/Hz&frac12; at 0.3 K 5.

Scanning-probe single-electron capacitance spectroscopy facilitates the study of single-electron motion in localized subsurface regions. A sensitive charge-detection circuit is incorporated into a cryogenic scanning probe microscope to investigate small systems of dopant atoms beneath the surface of semiconductor samples.

The integration of low-temperature scanning-probe techniques and single-electron capacitance spectroscopy represents a powerful tool to study the ...

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 ...

In Depth Analyses of LEDs by a Combination of X-ray Computed Tomography (CT) and Light Microscopy (LM) Correlated with Scanning Electron Microscopy (SEM)

In failure analysis, device characterization and reverse engineering of light emitting diodes (LEDs), and similar electronic components of micro-characterization, plays an important role. Commonly, different techniques like X-ray computed tomography (CT), light microscopy (LM) and scanning electron microscopy (SEM) are used separately. Similarly, the results have to be treated for each technique independently. Here a comprehensive study is shown which demonstrates the potentials leveraged by linking CT, LM and SEM. In depth characterization is performed on a white emitting LED, which can be operated throughout all characterization steps. Major advantages are: planned preparation of defined cross sections, correlation of optical properties to structural and compositional information, as well as reliable identification of different functional regions. This results from the breadth of information available from identical regions of interest (ROIs): polarization contrast, bright and dark-field LM images, as well as optical images of the LED cross section in operation. This is supplemented by SEM imaging techniques and micro-analysis using energy dispersive X-ray spectroscopy.

In Depth Analyses of LEDs by a Combination of X-ray Computed Tomography CT and Light Microscopy LM Correlated with Scanning Electron Microscopy SEM

A workflow for comprehensive micro-characterization of active optical devices is outlined. It contains structural as well as functional investigations by means of CT, LM and SEM. The method is demonstrated for a white LED which can be still be operated during characterization.

In failure analysis, device characterization and reverse engineering of light emitting diodes (LEDs), and similar electronic components of ...

Probing C84-embedded Si Substrate Using Scanning Probe Microscopy and Molecular Dynamics

This paper reports an array-designed C84-embedded Si substrate fabricated using a controlled self-assembly method in an ultra-high vacuum chamber. The characteristics of the C84-embedded Si surface, such as atomic resolution topography, local electronic density of states, band gap energy, field emission properties, nanomechanical stiffness, and surface magnetism, were examined using a variety of surface analysis techniques under ultra, high vacuum (UHV) conditions as well as in an atmospheric system. Experimental results demonstrate the high uniformity of the C84-embedded Si surface fabricated using a controlled self-assembly nanotechnology mechanism, represents an important development in the application of field emission display (FED), optoelectronic device fabrication, MEMS cutting tools, and in efforts to find a suitable replacement for carbide semiconductors. Molecular dynamics (MD) method with semi-empirical potential can be used to study the nanoindentation of C84-embedded Si substrate. A detailed description for performing MD simulation is presented here. Details for a comprehensive study on mechanical analysis of MD simulation such as indentation force, Young&#39;s modulus, surface stiffness, atomic stress, and atomic strain are included. The atomic stress and von-Mises strain distributions of the indentation model can be calculated to monitor deformation mechanism with time evaluation in atomistic level.

Probing C84-embedded Si Substrate Using Scanning Probe Microscopy and Molecular Dynamics

This paper reports the nanomaterial fabrication of a fullerene Si substrate inspected and verified by nanomeasurements and molecular dynamic simulation.

This paper reports an array-designed C84-embedded Si substrate fabricated using a controlled self-assembly method in an ultra-high vacuum chamber. The ...

Studying Dynamic Processes of Nano-sized Objects in Liquid using Scanning Transmission Electron Microscopy

Samples fully embedded in liquid can be studied at a nanoscale spatial resolution with Scanning Transmission Electron Microscopy (STEM) using a microfluidic chamber assembled in the specimen holder for Transmission Electron Microscopy (TEM) and STEM. The microfluidic system consists of two silicon microchips supporting thin Silicon Nitride (SiN) membrane windows. This article describes the basic steps of sample loading and data acquisition. Most important of all is to ensure that the liquid compartment is correctly assembled, thus providing a thin liquid layer and a vacuum seal. This protocol also includes a number of tests necessary to perform during sample loading in order to ensure correct assembly. Once the sample is loaded in the electron microscope, the liquid thickness needs to be measured. Incorrect assembly may result in a too-thick liquid, while a too-thin liquid may indicate the absence of liquid, such as when a bubble is formed. Finally, the protocol explains how images are taken and how dynamic processes can be studied. A sample containing AuNPs is imaged both in pure water and in saline.

This protocol describes the operation of a liquid flow specimen holder for scanning transmission electron microscopy of AuNPs in water, as used for the observation of nanoscale dynamic processes.

Samples fully embedded in liquid can be studied at a nanoscale spatial resolution with Scanning Transmission Electron Microscopy (STEM) using a ...

Measurements of Soil Carbon by Neutron-Gamma Analysis in Static and Scanning Modes

The herein described application of the inelastic neutron scattering (INS) method for soil carbon analysis is based on the registration and analysis of gamma rays created when neutrons interact with soil elements. The main parts of the INS system are a pulsed neutron generator, NaI(Tl) gamma detectors, split electronics to separate gamma spectra due to INS and thermo-neutron capture (TNC) processes, and software for gamma spectra acquisition and data processing. This method has several advantages over other methods in that it is a non-destructive in situ method that measures the average carbon content in large soil volumes, is negligibly impacted by local sharp changes in soil carbon, and can be used in stationary or scanning modes. The result of the INS method is the carbon content from a site with a footprint of ~2.5 - 3 m2 in the stationary regime, or the average carbon content of the traversed area in the scanning regime. The measurement range of the current INS system is &#62;1.5 carbon weight % (standard deviation &#177; 0.3 w%) in the upper 10 cm soil layer for a 1 hmeasurement.

Here, we present the protocol for in situ measurement of soil carbon using the neutron-gamma technique for single point measurements (static mode) or field averages (scanning mode). We also describe system construction and elaborate data treatment procedures.

The herein described application of the inelastic neutron scattering (INS) method for soil carbon analysis is based on the registration and analysis of ...