Shuchen Zhang

Arrays of horizontal carbon nanotubes of controlled chirality grown using designed catalysts

The semiconductor industry is increasingly of the view that Moore’s law—which predicts the biennial doubling of the number of transistors per microprocessor chip—is nearing its end. Consequently, the pursuit of alternative semiconducting materials for nanoelectronic devices, including single-walled carbon nanotubes (SWNTs), continues. Arrays of horizontal nanotubes are particularly appealing for technological applications because they optimize current output. However, the direct growth of horizontal SWNT arrays with controlled chirality, that would enable the arrays to be adapted for a wider range of applications and ensure the uniformity of the fabricated devices, has not yet been achieved. Here we show that horizontal SWNT arrays with predicted chirality can be grown from the surfaces of solid carbide catalysts by controlling the symmetries of the active catalyst surface. We obtained horizontally aligned metallic SWNT arrays with an average density of more than 20 tubes per micrometre in which 90 per cent of the tubes had chiral indices of (12, 6), and semiconducting SWNT arrays with an average density of more than 10 tubes per micrometre in which 80 per cent of the nanotubes had chiral indices of (8, 4). The nanotubes were grown using uniform size Mo2C and WC solid catalysts. Thermodynamically, the SWNT was selectively nucleated by matching its structural symmetry and diameter with those of the catalyst. We grew nanotubes with chiral indices of (2m, m) (where m is a positive integer), the yield of which could be increased by raising the concentration of carbon to maximize the kinetic growth rate in the chemical vapour deposition process. Compared to previously reported methods, such as cloning, seeding and specific-structure-matching growth, our strategy of controlling the thermodynamics and kinetics offers more degrees of freedom, enabling the chirality of as-grown SWNTs in an array to be tuned, and can also be used to predict the growth conditions required to achieve the desired chiralities.

Growth of high-density horizontally aligned SWNT arrays using Trojan catalysts

Single-walled carbon nanotube (SWNT)-based electronics have been regarded as one of the most promising candidate technologies to replace or supplement silicon-based electronics in the future. These applications require high-density horizontally aligned SWNT arrays. During the past decade, significant efforts have been directed towards growth of high-density SWNT arrays. However, obtaining SWNT arrays with suitable density and quality still remains a big challenge. Herein, we develop a rational approach to grow SWNT arrays with ultra-high density using Trojan catalysts. The density can be as high as 130 SWNTs μm(-1). Field-effect transistors fabricated with our SWNT arrays exhibit a record drive current density of -467.09 μA μm(-1) and an on-conductance of 233.55 μS μm(-1). Radio frequency transistors fabricated on these samples exhibit high intrinsic fT and fMAX of 6.94 and 14.01 GHz, respectively. These results confirm our high-density SWNT arrays are strong candidates for applications in electronics.

State of the Art of Single‐Walled Carbon Nanotube Synthesis on Surfaces

Single-walled carbon nanotubes (SWNTs) directly synthesized on surfaces are promising building blocks for nanoelectronics. The structures and the arrangement of the SWNTs on surfaces determine the quality and density of the fabricated nanoelectronics, implying the importance of structure controlled growth of SWNTs on surfaces. This review summarizes the recent research status in controlling the orientation, length, density, diameter, metallicity, and chirality of SWNTs directly synthesized on surfaces by chemical vapor deposition, together with a session presenting the characterization method of the chirality of SWNTs. Finally, the remaining major challenges are discussed and future research directions are proposed.

Diameter-Specific Growth of Semiconducting SWNT Arrays Using Uniform Mo2C Solid Catalyst.

Semiconducting single-walled nanotube (s-SWNT) arrays with specific diameters are urgently demanded in the applications in nanoelectronic devices. Herein, we reported that by using uniform Mo2C solid catalyst, aligned s-SWNT (∼90%) arrays with narrow-diameter distribution (∼85% between 1.0 and 1.3 nm) on quartz substrate can be obtained. Mo2C nanoparticles with monodisperse sizes were prepared by using molybdenum oxide-based giant clusters, (NH4)42[Mo132O372(H3CCOO)30(H2O)72]·10H3CCOONH4·300H2O(Mo132), as the precursor that was carburized by a gas mixture of C2H5OH/H2 during a temperature-programmed reduction. In this approach, the formation of volatile MoO3 was inhibited due to the annealing and reduction at a low temperature. As a result, uniform Mo2C nanoparticles are formed, and their narrow size-dispersion strictly determines the diameter distribution of SWNTs. During the growth process, Mo2C selectively catalyzes the scission of C-O bonds of ethanol molecules, and the resultant absorbed oxygen (Oads) preferentially etches metallic SWNTs (m-SWNTs), leading to the high-yield of s-SWNTs. Raman spectroscopic analysis showed that most of the s-SWNTs can be identified as (14, 4), (13, 6), or (10, 9) tubes. Our findings open up the possibility of the chirality-controlled growth of aligned-SWNTs using uniform carbide nanoparticles as solid catalysts for practical nanoelectronics applications.

Growth of Close-Packed Semiconducting Single-Walled Carbon Nanotube Arrays Using Oxygen-Deficient TiO2 Nanoparticles as Catalysts

For the application of single-walled carbon nanotubes (SWNTs) in nanoelectronic devices, techniques to obtain horizontally aligned semiconducting SWNTs (s-SWNTs) with higher densities are still in their infancy. We reported herein a rational approach for the preferential growth of densely packed and well-aligned s-SWNTs arrays using oxygen-deficient TiO2 nanoparticles as catalysts. Using this approach, a suitable concentration of oxygen vacancies in TiO2 nanoparticles could form by optimizing the flow rate of hydrogen and carbon sources during the process of SWNT growth, and then horizontally aligned SWNTs with the density of ∼ 10 tubes/μm and the s-SWNT percentage above 95% were successfully obtained on ST-cut quartz substrates. Theoretical calculations indicated that TiO2 nanoparticles with a certain concentration of oxygen vacancies have a lower formation energy between s-SWNT than metallic SWNT (m-SWNT), thus realizing the preferential growth of s-SWNT arrays. Furthermore, this method can also be extended to other semiconductor oxide nanoparticles (i.e., ZnO, ZrO2 and Cr2O3) for the selective growth of s-SWNTs, showing clear potential to the future applications in nanoelectronics.

Selective Scission of C–O and C–C Bonds in Ethanol Using Bimetal Catalysts for the Preferential Growth of Semiconducting SWNT Arrays

For the application of single-walled carbon nanotubes (SWNTs) to electronic and optoelectronic devices, techniques to obtain semiconducting SWNT (s-SWNT) arrays are still in their infancy. We have developed herein a rational approach for the preferential growth of horizontally aligned s-SWNT arrays on a ST-cut quartz surface through the selective scission of C-O and C-C bonds of ethanol using bimetal catalysts, such as Cu/Ru, Cu/Pd, and Au/Pd. For a common carbon source, ethanol, a reforming reaction occurs on Cu or Au upon C-C bond breakage and produces C(ads) and CO, while a deoxygenating reaction occurs on Ru or Pd through C-O bond breaking resulting in the production of O(ads) and C2H4. The produced C2H4 by Ru or Pd can weaken the oxidative environment through decomposition and the neutralization of O(ads). When the bimetal catalysts with an appropriate ratio were used, the produced C(ads) and C2H4 can be used as carbon source for SWNT growth, and O(ads) promotes a suitable and durable oxidative environment to inhibit the formation of metallic SWNTs (m-SWNTs). Finally, we successfully obtained horizontally aligned SWNTs on a ST-cut quartz surface with a density of 4-8 tubes/μm and an s-SWNT ratio of about 93% using an Au/Pd (1:1) catalyst. The synergistic effects in bimetallic catalysts provide a new mechanism to control the growth of s-SWNTs.

Large-area growth of ultra-high-density single-walled carbon nanotube arrays on sapphire surface

A scalable approach to obtaining high-density, large-area single-walled carbon nanotube (SWNT) arrays is essential for realizing the full potential of SWNTs in practical electronic devices; this is still a great challenge. Here, we report an improved synthetic method for large-area growth of ultra-high-density SWNT arrays on sapphire surfaces by combining Trojan catalysts (released from the substrate, to assure ultra-high density) with Mo nanoparticles (loaded on the surface, to stabilize the released Trojan catalysts) as cooperating catalysts. Dense and perfectly aligned SWNTs covered the entire substrate and the local density was as high as 160 tubes/μm. Field-effect transistors (FETs) built on such arrays gave an output current density of −488 μA/μm at the drain-source voltage (Vds) = the gate-source voltage (Vgs) =–2 V, corresponding to an on-conductance per width of 244 μS/μm. These results confirm the wide range of potential applications of Trojan-Mo catalysts in the structure-controlled growth of SWNTs.

Growth of Horizontal Semiconducting SWNT Arrays with Density Higher than 100 tubes/μm using Ethanol/Methane Chemical Vapor Deposition

Horizontally aligned semiconducting single-walled carbon nanotube (s-SWNT) arrays with a certain density are highly desirable for future electronic devices. However, obtaining s-SWNT arrays with simultaneously high purity and high density is extremely challenging. We report herein a rational approach, using ethanol/methane chemical vapor deposition, to grow SWNT arrays with a s-SWNT ratio over 91% and a density higher than 100 tubes/μm. In this approach, at a certain temperature, ethanol was fully thermally decomposed to feed carbon atoms for Trojan-Mo catalysts growing high density SWNT arrays, while the incomplete pyrolysis of methane provided appropriate active H radicals with the help of catalytic sapphire surface to inhibit metallic SWNT (m-SWNT) growth. The synergistic effect of ethanol/methane mixtures resulted in enriched semiconducting SWNTs and no obvious decrease in nanotube density due to their milder reactivity and higher controllability at suitable growth conditions. This work represents a step forward in large-area synthesis of high density s-SWNT arrays on substrates and demonstrates potential applications in scalable carbon nanotube electronics.

High‐Throughput Determination of Statistical Structure Information for Horizontal Carbon Nanotube Arrays by Optical Imaging

Optical multicolor imaging is used as a high-throughput statistical tool to determine the structure information of horizontally aligned carbon nanotube arrays on various substrates and in diverse environments. This high-throughput ability is achieved through the direct use of optical image information and an over 10-fold enhancement of the optical contrast by polarization manipulation.

A Mixed‐Extractor Strategy for Efficient Sorting of Semiconducting Single‐Walled Carbon Nanotubes

A general strategy for sorting semiconducting single-walled carbon nanotubes (s-SWNTs) with high efficiency using a mixed-extractor is reported. When the two extractors have a sufficient difference in binding energy with s-SWNTs, and skeleton flexibility, the mixture shows enhanced yield for sorting s-SWNTs. The strategy could be effective when applied to increase the sorting yield of other selective dispersion systems.