# Conductance of Distorted Carbon Nanotubes

## Abstract

We have calculated the effects of structural distortions of armchair carbon nanotubes on their electrical transport properties. We found that the bending of the nanotubes decreases their transmission function in certain energy ranges and leads to an increased electrical resistance. Electronic structure calculations show that these energy ranges contain localized states with significant $`\sigma `$-$`\pi `$ hybridization resulting from the increased curvature produced by bending. Our calculations of the contact resistance show that the large contact resistances observed for SWNTs are likely due to the weak coupling of the NT to the metal in side bonded NT-metal configurations.   

Carbon nanotubes (NTs) can be metallic or semiconducting. They have high mechanical strength and good thermal conductivity , properties that make them potential building blocks of a new, carbon-based, nanoelectronic technology . Conduction in defect-free NTs, especially at low temperatures, can be ballistic, thus involving little energy dissipation within the NT . Furthermore, NTs are expected to behave like quasi one-dimensional systems (Q1D) with quantized electrical resistance, which, for metallic armchair nanotubes at low bias should be about 6 k$`\mathrm{\Omega }`$ ($`h/4e^2`$). The experimentally observed behavior is, however, quite different. The contact resistance of single-wall nanotubes (SWNTs) with metal electrodes is generally quite high. Furthermore, at low temperatures a localization of the wavefunction in the nanotube segment contained between the metal electrodes is observed that leads to Coulomb blockade phenomena . The latter observation suggests that a barrier or bad-gap develops along the NT near its contact with the metal. In an effort to understand the origin of these discrepancies we have used Green’s function techniques to calculate the effect of the modification of the NTs by bending on their electronic structure and electric transport properties. We also investigated the effects of the strength of the NT-metal pad interaction on the value of the contact resistance.   

Most discussions on the electronic structure of NTs assume perfect cylindrical symmetry. The introduction of point defects such as vacancies  or disorder  has been shown to lead to significant modification of their electrical properties. Here we focus on the effects of structural (axial) distortions on the transport properties of armchair NTs. AFM experiments  and molecular mechanics simulations  have shown that the van der Waals forces between NTs and the substrate on which they are placed can lead to a significant deformation of their structure. To maximize their adhesion energy the NTs tend to follow the topography of the substrate . Thus, for example, NTs bend to follow the curvature of the metal electrodes on which they are deposited. When the strain due to bending exceeds a certain limit, kinks develop in the nanotube structure . It is important to understand how these NT deformations affect the electrical transport properties of the NTs. Could they be responsible for the low temperature localization observed ?  Early theoretical work on this issue was based on tight-binding model involving only the $`\pi `$-electrons of the NTs and accounted for the electronic structure changes induced by bending through the changes in $`\pi `$-orbital overlap at neighboring sites. This study concluded that bending distortions would have a negligible effect on the electrical properties of the NTs . The applicability of this approach is limited to weak distortions. Experiments, however, show that strong deformations and kink formation are common. Under such conditions, bending-induced $`\sigma `$-$`\pi `$ mixing, which was not considered before, becomes very important in strongly bent NTs . In this work, the NT electronic structure is computed using the extended Hückel method (EHM)  that includes both $`s`$ and $`p`$ valence electrons. We have previously  shown that EHM calculations on an armchair $`(6,6)`$ NT model (96 Å long) reproduce the electronic properties obtained with more sophisticated ab-initio and band structure computations on NTs. The approach we used in the computation of the electrical properties is similar to that of Datta et al. .   

The conductance through a molecule or an NT cannot be easily computed; even if the electronic structure of the free molecule or NT is known, the effect of the contacts on it can be substantial  and needs to be taken into account. Typically, there will be two (or more) leads connected to the NT. We model the measurement system as shown in Figure 1a. The leads are macroscopic gold pads that are coupled to the ends of the NT through matrix elements between the Au surface atoms and the end carbon atoms of the NT. In most experiments to date the NTs are laid on top of the metal pads. As we discussed above, the NTs then tend to bend around the pads. Such bending deformations are modelled in our calculations by introducing a single bend placed at the center of the tube.   

The electrical transport properties of a system can be described in terms of the retarded Green’s function . To evaluate the conductance of the NT we need to compute the transmission function, $`T(E)`$, from one contact to the other. This can be done following the Landauer-Büttiker formalism as described in . The key element of this approach lies in the treatment of the infinite leads which are here described by self-energies. We can write the Green’s function in the form of block matrices separating explicitly the molecular Hamiltonian. After some simplification we obtain:

$$G_{NT}=\left[ES_{NT}H_{NT}\mathrm{\Sigma }_1\mathrm{\Sigma }_2\right]^1$$
(1)   
where $`S_{NT}`$ and $`H_{NT}`$ are the overlap and the Hamiltonian matrices, respectively, and $`\mathrm{\Sigma }_{1,2}`$ are self-energy terms that describe the effect of the leads. They have the form $`\tau _i^{}g_i\tau _i`$ with $`g_i`$ the Green’s function of the individual leads  and $`\tau _i`$ is a matrix describing the interaction between the NT and the leads. The Hamiltonian and overlap matrices are determined using EHM for the system Gold-NT-Gold. The transmission function, $`T(E)`$, that is obtained from this Green’s function is given by :

$$T(E)=T_{21}=Tr[\mathrm{\Gamma }_2G_{NT}\mathrm{\Gamma }_1G_{NT}^{}].$$
(2)   
In this formula, the matrices have the form:

$$\mathrm{\Gamma }_{1,2}=i(\mathrm{\Sigma }_{1,2}\mathrm{\Sigma }_{1,2}^{}).$$
(3)   
The summation over all conduction channels in the molecule allows the evaluation of the resistance at the Fermi energy, $`R=h/(2e^2T(E_F))`$. Transport in the presence of an applied potential is also computed. The differential conductance is computed in this case using the approximation :

$$\kappa (V)=\frac{I}{V}\frac{2e^2}{h}[\eta T(\mu _1)+(1\eta )T(\mu _2)]$$
(4)   
with $`\eta [0,1]`$ describing the equilibration of the nanotube energy levels with respect to the reservoirs . As a reference, we use the $`E_F`$ obtained from EHM for individual nanotubes as the zero of energy. The NT model used in our calculations is a $`(6,6)`$ carbon nanotube segment containing 948 carbon atoms. The bond distance between carbon atoms in non-deformed regions of the NT is fixed to that in graphite 1.42 Å, leading to a tube length of 96 Å. The building of deformed NTs using molecular mechanics minimization schemes  has been described in detail elsewhere . The structures of the bent NTs are shown in Figure 1b. The metallic contacts consist each of 22 gold atoms in a (111) crystalline arrangement. The height of the NT over the gold layer is 1.0 Å, where the Au-C bond distances vary from 1.1 to 1.6 Å.

In Figure 2 we present the computed transmission function $`T(E)`$ for the bent tubes (note that $`T(E)`$ represents the sum of the transmission probabilities over all contributing NT conduction channels). The upper-right of Figure 2 shows the raw transmission results obtained for the straight NT. The fast oscillations of $`T(E)`$ are due to the discrete energy levels of the finite segment of the carbon nanotubes used. For clarity, we will use smoothed curves in the description of the results. At $`E_F`$, $`T(E)`$ is about 1.2, leading to a resistance ($``$ 11 k$`\mathrm{\Omega }`$ ) higher than expected for ballistic transport ($``$ 6 k$`\mathrm{\Omega }`$ for $`T(E)`$ = 2.0). This reduction in transmission is due to the contribution from the contact resistance. The increasing $`T(E)`$ at higher binding energies is due to the opening of new conduction channels. The asymmmetry in the transmission T(E) is a function of the NT-pad coupling (C-Au distance). A longer NT-Au distance increases the T(E) above $`E_F`$, while it decreases it below $`E_F`$, and vise versa. Since the NT-pad geometry is kept fixed in all computations, this behavior does not influence the effects induced by NT bending.   

According to our calculation the contact resistance at $`E_F`$ is only about 5 k$`\mathrm{\Omega }`$, much smaller than the $``$ 1 M$`\mathrm{\Omega }`$ resistance typically observed in experiments on single-wall NTs . The dependence of $`T(E)`$ and contact resistance at $`E_F`$ on the Au-NT distance is shown in the upper-left of Figure 2. We see that $`T(E_F)`$ remains nearly constant between 1-2 Å, then decreases exponentially. For distances appropriate for van der Waals bonding ($`3`$ Å) the contact resistance is already in the M$`\mathrm{\Omega }`$ range. The above findings suggest that the high NT contact resistance observed experimentally may, in addition to experimental factors such as the presence of asperities at the metal-NT interface, be due to the topology of the contact. In most experiments, the NT is laid on top of the metal pad. The NT is at nearly the van der Waals distance away from the metal surface, and given that transport in the NT involves high $`k`$-states which decay rapidly perpendicular to the tube axis, the coupling between NT and metal is expected to be weak . Direct chemical bonding between metal and the NT, or interaction of the metal with the NT cap states  should lead to stronger coupling. In this respect, it has been found  that high energy electron irradiation of the contacts leads to a drastic reduction of the resistance. Since the irradiation is capable of breaking NT C-C bonds it may be that the resulting dangling bonds lead to a stronger metal-NT coupling.

The strongest modification of $`T(E)`$ as a result of bending is observed at around $`E`$=-0.6 eV where a transmission dip appears. This dip is strongest in the $`60^{}`$ bent NT. Furthermore, its transmission function at higher binding energies (BE) is lower than those of the 0-45 bent NTs, indicating that the transmission of higher conduction channels is also decreased. The nature of the dip at about -0.6 eV can be understood by examining the local density-of-states (LDOS) of bent tubes shown in Figure 3 . A change (increase) in the LDOS is seen in the same energy region (0.5-0.8 eV below $`E_F`$) as the transmission dip. This change is essentially localized in the vicinity of the deformed region. The new states result from the mixing of $`\sigma `$ and $`\pi `$ levels, have a more localized character than pure $`\pi `$ states leading to a reduction of $`T(E)`$. As Figure 3 shows, the change in transmission with bending angle is not gradual; the transmission of the 30 and 45 models is only slightly different from that of the straight tube. Apparently, large changes in DOS and $`T(E)`$ require the formation of a kink in the NT structure, as is the case in the 60 and 90 bent NTs.

Once the transmission function is computed, the determination of the differential conductance and resistance is straigtforward. Figure 4 shows the results for two extreme cases of equilibration of the Fermi levels. The first is when $`\eta =0`$ (Figure 4a), and the symmetric case $`\eta =0.5`$ (Figure 4b). When $`\eta `$=0.0, the Fermi level of the NT follows exactly the applied voltage on one gold pad and the conductance spectrum is directly proportional to $`T(E)`$. As expected, there is no large difference between the 0, 30 and 45 models, while the 60 and 90 models show the dip structure at around 0.6 V. The non-linear resistance (NLR) spectra show clearly a sharp increase by almost an order of magnitude at 0.6 V. These features are also observed when $`\eta `$=0.5, where the Fermi level of the NT is floating at half the voltage applied between the two gold pads. The dip at around 1.2 V in the conductance spectra is now broader, and the NLR of the 60 bent tube increases by about a factor of 4 from the computed resistance of the straight tube. These results suggest that there exists a critical bending angle (between 45 and 60) above which the conduction in armchair carbon nanotubes is drastically altered .

In conclusion, we have calculated the effects of structural distortions of armchair carbon nanotubes on their electrical transport properties. We found that bending of the nanotubes decreases their transmission function and leads to an increased electrical resistance. The effect is particularly strong at bending angles higher than 45 degrees when the strain is strong enough to lead to kinks in the nanotube structure. The electronic structure calculations show that the reduction in $`T(E)`$ is correlated with the presence at the same energy of localized states with significant $`\sigma `$-$`\pi `$ hybridization due to the increased curvature produced by bending. Resistance peaks near $`E_F`$ are the likely cause for the experimentally observed low temperature localization in carbon NTs bent over metal electrodes . Our calculations of the resistance (including the contact resistance) of a perfect NT give a value close to $`h/2.4e^2`$ instead of $`h/4e^2`$. This increase in resistance is solely due to the finite transmission of the contacts. The much larger contact resistances observed in many experiments on SWNTs are likely due to the weaker coupling of the NT to the metal when the NT is simply placed on top of the metal electrodes. We predict that NTs end-bonded to metal pads will have contact resistances of only a few k$`\mathrm{\Omega }`$. Such low contact resistances will greatly improve the performance of NT-based devices and unmask the Q1D transport properties of NTs.