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 ...

University of Missouri

A fourth-generation (G4) poly(amidoamine) (PAMAM) dendrimer (G4-NH2) has been used as a template to deliver nearly monodispersed catalyst nanoparticles to SiO2/Si, Ti/Si, sapphire, and porous anodic alumina (PAA) substrates. Fe2O3 nanoparticles obtained after calcination of the immobilized Fe3+/G4-NH2 composite served as catalytic "seeds" for the growth of single-wall carbon nanotubes (SWNTs) by microwave plasma-enhanced CVD (PECVD). To surmount the difficulty associated with SWNT growth via PECVD, reaction conditions that promote the stabilization of Fe nanoparticles, resulting in enhanced SWNT selectivity and quality, have been identified. In particular, in situ annealing of Fe catalyst in an N2 atmosphere was found to improve SWNT selectivity and quality. H2 prereduction at 900 degrees C for 5 min was also found to enhance SWNT selectivity and quality for SiO2/Si supported catalyst, albeit of lower quality for sapphire supported catalyst. The application of positive dc bias voltage (+200 V) during SWNT growth was shown to be very effective in removing amorphous carbon impurities while enhancing graphitization, SWNT selectivity, and vertical alignment. The results of this study should promote the use of exposed Fe nanoparticles supported on different substrates for the growth of high-quality SWNTs by PECVD.

Dendrimer-templated Fe nanoparticles for the growth of single-wall carbon nanotubes by plasma-enhanced CVD.

Using a shielded growth approach and N2-annealed, nearly monodispersed Fe2O3 nanoparticles synthesized by interdendritic stabilization of Fe3+ species within fourth-generation poly(amidoamine) dendrimers, carbon nanotubes and nanofibers were successfully grown at low substrate temperatures (200-400 degrees C) by microwave plasma-enhanced chemical vapor deposition.

Dendrimer-assisted low-temperature growth of carbon nanotubes by plasma-enhanced chemical vapor deposition.

We report a metalization technique for electrically addressing templated vertical single-walled carbon nanotubes (SWNTs) using in situ palladium (Pd) nanowires. SWNTs are synthesized from an embedded catalyst in a modified porous anodic alumina (PAA) template. Pd is electrodeposited into the template to form nanowires that grow from an underlying conductive layer beneath the PAA and extend to the initiation sites of the SWNTs within each pore. In this way, individual vertical channels of SWNTs are created, each with a vertical Pd nanowire back contact. Further Pd deposition results in annular Pd nanoclusters that form on portions of SWNTs extending onto the PAA surface. Two-terminal electrical characteristics produce linear I-V relationships, indicating ohmic contact in the devices.

Lithography-free in situ Pd contacts to templated single-walled carbon nanotubes.

The development of assemblies consisting of unencapsulated, sub-10-nm gold particles attached to individual carbon nanotubes (CNTs) with diameters of 2 nm is described. The assemblies are formed on the surface of a porous anodic alumina (PAA) template on which the CNTs (single- or double-walled) are grown by plasma-enhanced chemical vapor deposition. The Au nanoparticles are formed through an indirect evaporation technique using a silicon nitride membrane mask, and diffuse along the PAA surface into the regions containing CNTs. The nanoparticles bind relatively strongly to the CNTs, as indicated by observations of nanoparticles that are suspended over pores or that move along with the CNTs. This approach may provide a new method to functionalize CNTs for chemical or biological sensing and fundamental studies of nanoscale contacts to CNTs.

Assemblies of carbon nanotubes and unencapsulated sub-10-nm gold nanoparticles.

Quantitative nanoindentation of nominally 7.5 and 600 μm tall vertically aligned carbon nanotube (VACNT) arrays is observed in situ within an SEM chamber. The 7.5 μm array consists of highly aligned and weakly interacting CNTs and deflects similarly to classically defined cylindrical columns, with deformation geometry and critical buckling force well estimated using the Euler-Bernoulli theory. The 600 μm array has a highly entangled foam-like morphology and exhibits sequential buckle formation upon loading, with a buckle first forming near the array bottom at approximately 2% strain, followed by accumulating coordinated buckling at the top surface at strains exceeding 5%.

In situ SEM observation of column-like and foam-like CNT array nanoindentation.

The deformation mechanism and mechanical properties of carbon nanotube (CNT) forests conformally coated with alumina using atomic layer deposition (ALD) are investigated using in situ and ex situ micro-indentation. While micro-indentation of a CNT forest coated with a thin discontinuous layer using 20 ALD cycles results in a deformation response similar to the response of uncoated CNT forests, a similar test on a CNT forest coated with a sufficiently thick and continuous layer using 100 ALD cycles causes fracture of both the alumina coatings and the core CNTs. With a 10 nm coating, 4-fold and 14-fold stiffness increases are measured using a flat punch and a Berkovich tip, respectively. Indentation testing with the Berkovich tip also reveals increased recoverability at relatively low strains. The results show that ALD coated CNT forests could be useful for applications that require higher stiffness or recoverability. Also, fracturing of the nanotubes shows that upper limits exist in the loading of conformally coated CNT forests.

Deformation response of conformally coated carbon nanotube forest.

Artificial hair sensors consisting of a piezoresistive carbon-nanotube-coated glass fiber embedded in a microcapillary are assembled and characterized. Individual sensors resemble a hair plug that may be integrated in a wide range of host materials. The sensors demonstrate an air-flow detection threshold of less than 1 m/s with a piezoresistive sensitivity of 1.3% per m/s air-flow change.

Bioinspired carbon nanotube fuzzy fiber hair sensor for air-flow detection.

Small diameter carbon nanotube (CNTs) are synthesized directly from a parent CNT forest using a floating catalyst chemical vapor deposition (CVD) method. To support a new CNT generation from an existing forest, an alumina coating was applied to the CNT forest using atomic layer deposition (ALD). The new generation of small diameter CNTs (8 nm average) surround the first generation, filling the interstitial regions. The hierarchical forests exhibit a 5-10-fold increase in stiffness, and the two generations are electrically addressable in spite of the interfacial alumina layer between them. This work enables the design of complex CNT architectures with hierarchical features that bring tailored properties such as high specific surface area and robust mechanical properties that can benefit a range of applications.

Matthew R. Maschmann

Department of Mechanical & Aerospace Engineering

University of Missouri

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

Matthew R. Maschmann

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Department of Mechanical & Aerospace Engineering

University of Missouri

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

Department of Mechanical & Aerospace Engineering