SWCNT semiconducting

Although it is required to refine the above condition I in actuality, this rather simple but impressive prediction seems to have much stimulated the experiments on the electrical-conductivity measurement and the related solid-state properties in spite of technological difficulties in purification of the CNT sample and in direct measurement of its electrical conductivity (see Chap. 10). For instance, for MWCNT, a direct conductivity measurement has proved the existence of metallic sample [7]. The electron spin resonance (ESR) (see Chap. 8) [8] and the C nuclear magnetic resonance (NMR) [9] measurements have also proved that MWCNT can show metallic property based on the Pauli susceptibility and Korringa-like relation, respectively. On the other hand, existence of semiconductive MWCNT sample has also been shown by the ESR measurement [ 10], For SWCNT, a combination of direct electrical conductivity and the ESR measurements has confirmed the metallic property of the sample employed therein [11]. More recently, bandgap values of several SWCNT... 

Electronic structures of SWCNT have been reviewed. It has been shown that armchair-structural tubes (a, a) could probably remain metallic after energetical stabilisation in connection with the metal-insulator transition but that zigzag (3a, 0) and helical-structural tubes (a, b) would change into semiconductive even if the condition 2a + b = 3N s satisfied. There would not be so much difference in the electronic structures between MWCNT and SWCNT and these can be regarded electronically similar at least in the zeroth order approximation. Doping to CNT with either Lewis acid or base would newly cause intriguing electronic properties including superconductivity. 

Fig. 4. Calculated density of states for two zigzag individual SWCNTs with (a) semiconducting (10, 0) and (b) metallic (9, 0) configurations. Tight-binding approximation was used for the calculation [6].

As described above, metallic CNTs are of great interest because they possess molecular orbitals which are highly delocalised. However, metallic CNTs are very difficult to use in actual devices because they require very low temperatures to control their carrier transfer. On the contrary, even at room temperature, the nonlinear /-V jas curve and the effective gate voltage dependence have been presented by using individual semiconducting SWCNTs [29]. 

Fig. 9./-Tbias curve of an individual semiconducting SWCNT with different gale voltages measured at room temperature [29].

The electronic properties of CNTs are of particular importance for hybrid materials and strongly depend on the structure of the CNTs. Theoretical [45-48] and experimental results [49] reveal that SWCNTs are either metallic or semiconducting depending on diameter and chirality, while MWCNTs are generally metallic (due to band alignment upon interlayer interactions). 

Information obtained Chirality of semiconducting SWCNTs (and thus diameter), band gap, bundling. 

As mentioned above, the electronic properties of SWCNTs depend on their chirality and may be semiconducting or metallic. There is still no satisfying way to produce just one sort of SWCNTs, which would require the exact control of catalyst particle size at elevated temperature. Hence, the separation of semiconducting from metallic SWCNTs is of paramount importance for their application in, for example, electric devices, field emission and photovoltaics etc. 

Common separation methods can be divided into chemical and physical routes. Chemical approaches rely on the interaction of the surface of different CNT types with surfactant molecules. Early work has shown that octadecylamine [94] and agarose gel [95] adsorb preferably on semiconducting SWCNTs, while diazonium reagents [96] and DNA [97, 98] show preference with metallic tubes. The assemblies with adsorbed molecular species are considerably larger and heavier than the indi-... 

The physical approach uses alternating current (ac-) dielectrophoresis to separate metallic and semiconducting SWCNTs in a single step without the need for chemical modifications [101]. The difference in dielectric constant between the two types of SWCNTs results in an opposite movement along an electric field gradient between two electrodes. This leads to the deposition of metallic nanotubes on the microelectrode array, while semiconducting CNTs remain in the solution and are flushed out of the system. Drawbacks of this separation technique are the formation of mixed bundles of CNTs due to insufficient dispersion and difficulties in up-scaling the process [102]. 

Fig. 16.7 Energy-band diagrams of DSSCs with incorporated (a) semiconducting (s-) SWCNTs and (b) metallic (m-) SWCNTs. The solid and dashed arrows represent desired charge transport and undesired recombination processes. Adapted from Guai etal. [95].

Fig. 17.7 Current-voltage curves (a) and calculated electron diffusion lengths (b) from three DSSCs with Ti02 nanoparticles only, with 0.2 wt% pure semiconducting SWCNT, and with 0.2 wt% pure metallic SWCNT. L is the film thickness and Ln is the electron diffusion length.

The conductive properties of SWCNTs were predicted to depend on the helicity and the diameter of the nanotube [112, 145]. Nanotubes can behave either as metals or semiconductors depending upon how the tube is rolled up. The armchair nanotubes are metallic whereas the rest of them are semiconductive. The conductance through carbon nanotube junctions is highly dependent on the CNT/metal contact [146]. The first measurement of conductance on CNTs was made on a metallic nanotube connected between two Pt electrodes on top of a Si/Si02 substrate and it was observed that individual metallic SWCNTs behave as quantum wires [147]. A third electrode placed nearby was used as a gate electrode, but the conductance had a minor dependence on the gate voltage for metallic nanotubes at room temperature. The conductance of metallic nanotubes surpasses the best known metals because the... 

Semiconductive SWCNT FET transistors capable of operating at room temperature were constructed several years ago and their operation in the terahertz frequency range was predicted [160]. These early devices had p-type characteristics (hole... 

Attaching chemical functionalities to CNTs can improve their solubility and allow for their manipulation and processability [24]. The chemical functionalization can tailor the interactions of nanotubes with solvents, polymers and biopolymer matrices. Modified tubes may have physical or mechanical properties different from those of the original nanotubes and thus allow tuning of the chemistry and physics of carbon nanotubes. Chemical functionalization can be performed selectively, the metallic SWCNTs reacting faster than semiconducting tubes [25]. 

Here 1 labels the electronic states of the SWCNT with the chiral index (p,0), which are described by a simple two-band k p model based on an effective mass approximation [4], p being equal to 3M + v with integer M and v = 0( 1) for metallic (semiconducting) SWCNTs. The energy bands in Eq.(3) are given by... 

Figure 1. Charge transfer Aq/e from the zigzag SWCNTs (p,0) with p = 5-15 to the F atom adsorbed on their surfaces as a function of the tube radius R. The heavy dots and triangles refer to semiconducting and metallic SWCNTs, respectively. The solid lines are intended as a guide to the eye.

---