Daire J. Cott

Measuring the electrical resistivity and contact resistance of vertical carbon nanotube bundles for application as interconnects

Carbon nanotubes (CNT) are known to be materials with potential for manufacturing sub-20 nm high aspect ratio vertical interconnects in future microchips. In order to be successful with respect to contending against established tungsten or copper based interconnects, though, CNT must fulfil their promise of also providing low electrical resistance in integrated structures using scalable integration processes fully compatible with silicon technology. Hence, carefully engineered growth and integration solutions are required before we can fully exploit their potentialities. This work tackles the problem of optimizing a CNT integration process from the electrical perspective. The technique of measuring the CNT resistance as a function of the CNT length is here extended to CNT integrated in vertical contacts. This allows extracting the linear resistivity and the contact resistance of the CNT, two parameters to our knowledge never reported separately for vertical CNT contacts and which are of utmost importance, as they respectively measure the quality of the CNT and that of their metal contacts. The technique proposed allows electrically distinguishing the impact of each processing step individually on the CNT resistivity and the CNT contact resistance. Hence it constitutes a powerful technique for optimizing the process and developing CNT contacts of superior quality. This can be of relevant technological importance not only for interconnects but also for all those applications that rely on the electrical properties of CNT grown with a catalytic chemical vapor deposition method at low temperature.

Growth of vertically-aligned carbon nanotube forests on conductive cobalt disilicide support

We report the thermal chemical vapor deposition of vertically-aligned multiwalled carbon nanotube forests directly onto electrically conductive cobalt disilicide (CoSi2) support using Fe as catalyst. We find that CoSi2 support layer is able to prevent the agglomeration of the catalyst and favor vertically-aligned growth better than a SiO2 support and comparable to an Al2O3 support. This is an unusual behavior for a conductive support. This is because CoSi2 has a lower surface energy than most metals or metallic compounds. This has great benefits in the application of CoSi2 as support for CNTs as horizontal and vertical interconnects.

Atomic layer deposition-based synthesis of photoactive TiO2 nanoparticle chains by using carbon nanotubes as sacrificial templates

Highly ordered and self supported anatase TiO2 nanoparticle chains were fabricated by calcining conformally TiO2 coated multi-walled carbon nanotubes (MWCNTs). During annealing, the thin tubular TiO2 coating that was deposited onto the MWCNTs by atomic layer deposition (ALD) was transformed into chains of TiO2 nanoparticles (∼12 nm diameter) with an ultrahigh surface area (137 cm2 per cm2 of substrate), while at the same time the carbon from the MWCNTs was removed. Photocatalytic tests on the degradation of acetaldehyde proved that these forests of TiO2 nanoparticle chains are highly photoactive under UV light because of their well crystallized anatase phase.

Integration of Vertical Carbon Nanotube Bundles for Interconnects

Carbon nanotubes (CNTs) are considered a promising material for interconnects for future generation microchips. The integration of vertical CNT in a processing environment is evaluated in this work. Extrapolated performances of CNT-based interconnects are compared with existing technologies at different hierarchy levels including the limitations of present deposition methods for copper and tungsten. For practical implementation, CNT bundles were selectively grown into contact holes using physical vapor deposited and electrochemical deposited cobalt or nickel catalysts. A polishing step was used to control the CNT length after embedding the CNT into an oxide matrix. A CNT metal decoration method based on electrodeposition is presented, which can be used to assess the yield of electrically conductive CNT as well as to form top contacts for electrical characterization. Finally, the importance of having suitable and robust structures for evaluating the integration process is highlighted after the electrical characterization of CNT in a nanoprober station.

Nanostructured TiO2/carbon nanosheet hybrid electrode for high-rate thin-film lithium-ion batteries

Heterogeneous nanostructured electrodes using carbon nanosheets (CNS) and TiO2 exhibit high electronic and ionic conductivity. In order to realize the chip level power sources, it is necessary to employ microelectronic compatible techniques for the fabrication and characterization of TiO2-CNS thin-film electrodes. To achieve this, vertically standing CNS grown through a catalytic free approach on a TiN/SiO2/Si substrate by plasma enhanced chemical vapour deposition (PECVD) was used. The substrate-attached CNS is responsible for the sufficient electronic conduction and increased surface-to-volume ratio due to its unique morphology. Atomic layer deposition (ALD) of nanostructured amorphous TiO2 on CNS provides enhanced Li storage capacity, high rate performance and stable cycling. The amount of deposited TiO2 masks the underlying CNS, thereby controlling the accessibility of CNS, which gets reflected in the total electrochemical performance, as revealed by the cyclic voltammetry and charge/discharge measurements. TiO2 thin-films deposited with 300, 400 and 500 ALD cycles on CNS have been studied to understand the kinetics of Li insertion/extraction. A large potential window of operation (3-0.01 V); the excellent cyclic stability, with a capacity retention of 98% of the initial value; and the remarkable rate capability (up to 100 C) are the highlights of TiO2/CNS thin-film anode structures. CNS with an optimum amount of TiO2 coating is proposed as a promising approach for the fabrication of electrodes for chip compatible thin-film Li-ion batteries.

Optimization of multi-walled carbon nanotube–metal contacts by electrical stressing

We present experimental data on the contact resistances of three different metal probes, tungsten, palladium and indium, with chemical vapour deposited (CVD) multi-wall carbon nanotubes (MWCNTs). We demonstrate that there is an irreversible modification of the contacts following electrical stressing whereby the circuit resistance converges towards its optimal value prior to current-induced tube failure. Once the probe-MWCNT contact is broken, subsequent recontact experiments reveal that the circuit resistance returns to its initial high level, demonstrating that the modification occurs at the probe contact location and not elsewhere in the circuit. Contact studies with the different metals reveal that Pd metal provides the lowest resistance contact to the MWCNT in our sample.

Porous nanostructured metal oxides synthesized through atomic layer deposition on a carbonaceous template followed by calcination

Porous metal oxides with nano-sized features attracted intensive interest in recent decades due to their high surface area which is essential for many applications, e.g. Li ion batteries, photocatalysts, fuel cells and dye-sensitized solar cells. Various approaches have so far been investigated to synthesize porous nanostructured metal oxides, including self-assembly and template-assisted synthesis. For the latter approach, forests of carbon nanotubes are considered as particularly promising templates, with respect to their one-dimensional nature and the resulting high surface area. In this work, we systematically investigate the formation of porous metal oxides (Al2O3, TiO2, V2O5 and ZnO) with different morphologies using atomic layer deposition on multi-walled carbon nanotubes followed by post-deposition calcination. X-ray diffraction, scanning electron microscopy accompanied by X-ray energy dispersive spectroscopy and transmission electron microscopy were used for the investigation of morphological and structural transitions at the micro- and nano-scale during the calcination process. The crystallization temperature and the surface coverage of the metal oxides and the oxidation temperature of the carbon nanotubes were found to produce significant influence on the final morphology.

Growth and characterization of horizontally suspended CNTs across TiN electrode gaps

A technique is proposed to grow horizontal carbon nanotubes (CNTs) bridging metal electrodes and to assess their electrical properties. A test structure was utilized that allows for selective electrochemical sidewall catalyst placement. The selectivity of the technique is based on the connection of the desired metal electrodes to the silicon substrate where the potential for electrochemical deposition was applied. Control over the Ni catalyst size (15-30 nm) and density (up to 3 x 10(11) particles cm(-2)) is demonstrated. Horizontal CNTs with controlled diameter and density were obtained by CVD growth perpendicular to the sidewalls of patterned TiN electrode structures. Electrode gaps with spacings from 200 nm up to 5 microm could be bridged by both direct CNT-electrode contact and CNT-CNT entanglement. The TiN-CNT-TiN and TiN-CNT-CNT-TiN bridges were electrically characterized without any further post-growth contacting. Resistance values as low as 40 Omega were measured for the smallest gap spacing and depended mainly on the number and configuration of the CNT bridges. The proposed method could be implemented for CNT-based horizontal interconnections and be a route to make different nanoelectronic devices such as chemical and electromechanical sensors.

Electrochemical Tailoring of Catalyst Nanoparticles for CNT Spatial-Dimension Control

Electrodeposition is an excellent method for a site-selective and direct fabrication of catalyst nanoparticles for subsequent carbon nanotube (CNT) growth. Nickel nanoparticles with densities as high as 10 11 cm -2 and diameters down to 15 ± 4 nm are deposited on blanket and patterned TiN wafers. Ni nanoparticles are selectively placed at the bottom of submicrometer vias by through-mask electrodeposition. The spherical nanoparticles all produce aligned multiwalled CNTs. The CNT diameter is directly determined by the diameter of the as-deposited nanoparticles, which is tailored by the electrodeposition conditions. Such control of CNT size, density, and location represents an important step toward the implementation of CNTs in device fabrication.

Electrical improvement of CNT contacts with Cu damascene top metallization

We discuss the improvement in the electrical characterization and the performance of 150 nm diameter contacts filled with carbon nanotubes (CNT) and a Cu damascene top metal on 200mm wafers. The excellent agreement between the yield curves for the parallel and single contacts shows that a reliable electrical characterization is obtained. We demonstrate that integration changes improved the resistivity of the CNT contact significantly by reducing it from 11.8·10³ μΩ·cm down to 5.1·10³ μΩ·cm. Finally, a length scaling of the CNT contacts was used to find the individual contributors to the lowering of the single CNT contact resistance.