# Schottky barriers in carbon nanotube heterojunctions

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## Abstract

Electronic properties of heterojunctions between metallic and semiconducting single-wall carbon nanotubes are investigated. Ineffective screening of the long range Coulomb interaction in one-dimensional nanotube systems drastically modifies the charge transfer phenomena compared to conventional semiconductor heterostructures. The length of depletion region varies over a wide range (from the nanotube radius to the nanotube length) sensitively depending on the doping strength. The Schottky barrier gives rise to an asymmetry of the I-V characteristics of heterojunctions, in agreement with recent experimental results by Yao et al. and Fuhrer et al. Dynamic charge build-up near the junction results in a step-like growth of the current at reverse bias.

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Single-wall carbon nanotubes (SWNTs) are giant linear fullerene molecules which can be studied individually by methods of nanophysics . Depending on the wrapping of a graphene sheet, SWNTs can either be one-dimensional (1D) metals or semiconductors with the energy gap in sub-electronvolt range . While metallic nanotubes can play a role of interconnects in future electronic circuits, their semiconducting counterparts can be used as basic elements of switching devices. An example is the field effect transistor on semiconducting SWNT operating at room temperature .

Of particular interest are all-nanotube devices . The simplest can be fabricated by contacting two SWNTs with different electronic properties. The SWNTs can be seamlessly joined together by introducing topological defects (pentagon-heptagon pairs) into the hexagonal graphene network . The resulting on-tube junction generically has the shape of a kink. Electronic properties of such junctions have been investigated theoretically (see e.g. Refs. ) within the model of non-interacting electrons.

Electron transport in nanotube heterojunctions has been studied in two recent experiments. Yao et al. treated junctions in SWNTs with kinks  whereas Fuhrer et al. explored contacts of crossed nanotubes . Both groups observed non-linear and asymmetric $`IV`$ characteristics resembling that of rectifying diodes. On one hand, the rectifying behavior can be naturally interpreted in terms of Schottky barriers (SBs). On the other hand, formation of a SB might be surprising since one expects no charge transfer in junctions between two SWNTs made of the same material.

A possible reason for the charge transfer might be the doping of the nanotubes forming the heterojunction . The doping can be caused by introduction of dopant atoms into the nanotubes or by charge transfer from metallic electrodes. In the latter case the doping strength can also be controlled by the gate voltage. It is important to mention that screening of the Coulomb interaction is ineffective in one-dimensional nanotubes. For this reason the effect of the doping is long-ranged: the density of the transferred charge decays slowly with the distance from the electrodes and might be appreciable at the heterojunction .

The long-range Coulomb interaction should be properly taken into account when treating the charge transfer in the heterojunction itself. Unfortunately, this was not accomplished in Ref. , where the electric field was assumed to be fully screened in the region of a few atomic layers near the junction. In this Letter we study charge transfer phenomena in nanotube heterojunctions with true long-range Coulomb interaction. We concentrate on the metal-semiconductor SWNT junction and analyze its equilibrium and non-equilibrium properties (SB parameters, I-V characteristics) by solving the Poisson equation self-consistently.

As a model system we consider ”straight” junction  between metallic ($`x<0`$) and semiconducting ($`x>0`$) SWNTs (Fig. 1). We assume that the conducting $`p_z`$ electrons in SWNTs are confined to the surface of a cylinder of radius $`R`$. The nanotubes are surrounded by a coaxial cylindrical gate electrode of radius $`R_sR`$. The Fourier components of the 1D Coulomb interaction are given by

$$U(q)=\frac{2e^2}{\kappa }\left\{I_0(qR)K_0(qR)\frac{I_0^2(qR)K_0(qR_s)}{I_0(qR_s)}\right\},$$
(1)   
with the dielectric constant of the medium $`\kappa `$ and the modified Bessel functions $`I_0`$, $`K_0`$. Equation (1) describes the long-range Coulomb interaction, $`U(x)=1/\kappa x`$, for $`RxR_s`$. The interaction is screened at large distances $`xR_s`$, so that $`U(0)=e^2/C=(2e^2/\kappa )\mathrm{ln}(R_s/R)`$, $`C`$ being the capacitance of SWNT per unit length. The kernel (1) relates the electrostatic potential $`\phi `$ at the surface of SWNTs to 1D charge density $`e\rho `$ ($`e>0`$),

$$e\phi _q=U(q)\rho _q.$$
(2)   
Since experimental values  of the conductance of heterojunctions are small, $`G/(e^2/h)10^2`$, we will assume low transparency $`T1`$ of the barrier between two SWNTs. In this case the electrons in the nanotubes are described by the equilibrium Fermi distribution $`f(E)`$, also when the voltage $`V`$ is applied to the system.

In equilibrium, the charge density is related to the energy $`\stackrel{~}{E}_0(x)=E_0(x)E_F(x)`$ of the gapless point (charge neutrality level) of graphite $`E_0`$ counted from the Fermi level $`E_F`$,

$$\rho (x)=𝑑Esign(E)\nu (E)f[(E\stackrel{~}{E}_0(x))sign(E)],$$
(3)   
with the density of electronic states $`\nu `$ . Equation (3) is valid provided that $`\stackrel{~}{E}_0(x)`$ varies slowly on the scale of the Fermi wavelength.

We restrict our consideration to low energies $`|\stackrel{~}{E}_0|<\mathrm{\Delta }^{(1)}`$, $`k_BT\mathrm{\Delta }^{(1)}`$ and neglect the effect of higher 1D subbands ($`\mathrm{\Delta }^{(1)}/(\mathrm{}v_F/R)=1,2/3`$ for metallic/semiconducting SWNT). The densities of states in metallic and semiconducting SWNTs are given by

$$\nu _M=\frac{4}{\pi \mathrm{}v_F},\nu _S=\frac{4}{\pi \mathrm{}v_F}\frac{|E|\mathrm{\Theta }(|E|\mathrm{\Delta })}{\sqrt{E^2\mathrm{\Delta }^2}},$$
(4)   
with the Fermi velocity $`v_F8.1\times 10^5`$ m/s and the energy gap $`2\mathrm{\Delta }=2\mathrm{}v_F/3R`$ in semiconducting SWNT ($`\mathrm{\Delta }0.3`$ eV for generic SWNTs  with $`R=0.50.7`$ nm).

In the limit of zero temperature Eq. (3) may be inverted as,

$$\stackrel{~}{E}_0(\rho )=\{\begin{array}{c}\rho /\nu _M,x<0,\\ \sqrt{\mathrm{\Delta }^2+\left(\rho /\nu _M\right)^2},x>0.\end{array}$$
(5)   
The charge neutrality level $`\stackrel{~}{E}_0(x)`$ is related to the electrostatic potential (2),

$$\stackrel{~}{E}_0(x)+e\phi (x)=\mu +eVsign(x)/2,$$
(6)   
$`\mu eV/2`$ being the electro-chemical potentials for holes in metallic and semiconducting SWNTs. The potential $`\mu =\alpha (\mathrm{\Delta }WeV_g)`$ can be controlled by the gate voltage $`V_g`$ (Fig. 1). It also incorporates the difference $`\mathrm{\Delta }W=W_MW_{NT}`$ of the work functions of the gate electrode and SWNT  (the coefficient $`\alpha `$ characterizes mutual capacitance of the nanotubes to the gate and is equal to unity in our case).

We solve Eqs. (2), (3), (6) self-consistently by numerical minimization of the corresponding energy functional. The Coulomb energy is computed in the Fourier space. Figures 2, 3 display the results for the following parameters: $`R_s/R=75`$ ($`R_s50`$ nm for (10,10) SWNTs) and $`\nu _MU(0)/\mathrm{ln}(R_s/R)=5`$. The latter value corresponds to the dielectric constant $`\kappa 1.4`$ which can be inferred from the experimental data (see Fig. 4 of Ref. ).

The band bending diagrams (Fig. 2) display the charge neutrality level $`\overline{E}_0(x)=\stackrel{~}{E}_0(x)eVsign(x)/2`$ counted from the ”average” Fermi level of metallic and semiconducting SWNTs, as well as the energies $`E_{c,v}=\overline{E}_0\pm \mathrm{\Delta }`$

of the conduction and valence bands in semiconducting SWNT. Let us start from the case of zero bias, $`V=0`$ (Figs. 2(a), 2(b)). At zero electro-chemical potential, $`\mu =0`$, the Fermi level of the nanotubes coincides with the gapless point of graphite and the system is charge neutral (Fig. 2(a)). This situation occurs for isolated nanotubes. The barriers for the electron and hole transport are equal to $`\mathrm{\Delta }`$ (Fig. 3(a)).

To make contact with the experiments  we will concentrate on p-doped SWNTs ($`\mu >0`$). Due to larger number of electronic states $`_0^{\stackrel{~}{E}_0}𝑑E\nu (E)`$ the metallic SWNT acquires more charge and has higher electrostatic potential $`\phi (\mathrm{})`$ (lower charge neutrality level $`\stackrel{~}{E}_0(\mathrm{})`$) compared to semiconducting SWNT kept at the same electrochemical potential, see Eqs. (5), (6). The electric field induced by this charge bends the bands in the semiconducting part downwards so that a SB is formed near the interface (Fig. 2(b)).

For $`|\mu |<\mathrm{\Delta }`$, there are no free charges in the semiconducting SWNT. Our numerical results indicate that the electrostatic potential $`\phi (x)`$ decays logarithmically at $`RxR_s`$ so that the bend bending extends over long distances $`xR_s`$ (the analytical estimate, $`\phi (x)e\nu _M\mu \mathrm{ln}(R_s/x)/\kappa `$, is available in the limit of weak interaction, $`\nu _MU(0)1`$). At $`\mu =\mathrm{\Delta }`$ holes enter the semiconducting SWNT. With increasing the electro-chemical potential the holes come closer to the junction reducing the length $`l`$ and the height $`u`$ of a SB (Fig. 2(b)). In the case of weakly doped semiconducting SWNT, $`\mu =\mathrm{\Delta }(1+\delta )`$, $`\delta 1`$, a rough estimate of the depletion length $`l`$ can be made, $`\mathrm{ln}(l/R_s)\delta \mathrm{ln}(R/R_s)`$, for $`RlR_s`$. Therefore, the depletion length changes rapidly from $`lR_s`$ to $`lR`$ with increasing doping in this regime. The height of a SB can be estimated from the difference of the charge neutrality levels in semiconducting and metallic SWNTs, $`u\stackrel{~}{E}_0(\mathrm{})\stackrel{~}{E}_0(\mathrm{})`$. The latter evaluate at $`\stackrel{~}{E}_0(\mathrm{})=\mu /(1+\nu _MU(0))`$ and $`\stackrel{~}{E}_0(\mathrm{})=\mathrm{\Delta }`$ for $`\delta \nu _MU(0)`$, see Eqs. (2), (5), (6). Since the band bending occurs predominantly in the semiconducrting part (Figs. 2(a), 2(b)) and $`\nu _MU(0)1`$, one expects that $`u`$ $`\mathrm{\Delta }`$ for $`\delta \nu _MU(0)`$. Note that SB persists up to remarkably large values of the electro-chemical potential, $`\mu 14\mathrm{\Delta }`$ (Fig. 3(a)) though it becomes rather short ($`l<R`$) for $`\mu 8\mathrm{\Delta }`$.

Figure 3(a) shows the result for the SB height defined as the minimum energy of electron or hole excitation required to transfer the elementary charge across the junction in the absence of tunneling through the SB. The SB height shows pronounced asymmetry as a function of the bias voltage. Under a forward/backward bias the charge density in metallic SWNT decreases/increases. This reduces/enhances the band bending (Figs. 2(c), 2(d)) in the semiconducting part (the charge density and the band bending change sign for $`V>2\mu `$, cf. Fig. 3(a)). As a result, the SB height decreases faster under a forward bias. This gives rise to the asymmetry $`V_+<|V_{}|`$ of positive $`V_+`$ and negative $`V_{}`$ threshold voltages at which SB vanishes ($`u0`$) and the onset of the conductance occurs. The positive threshold voltage is relatively insensitive to the doping strength, Fig. 3(a). This can be used for a rough estimate of the gap $`\mathrm{\Delta }`$ from experimental data, $`\mathrm{\Delta }eV_+`$, for $`\mu 1`$. Note that we assume weak interband tunneling in semiconducting SWNT so that the electronic states in the conductance band are empty in Fig. 2(d).

We will proceed with the analysis of non-equilibrium electron transport. The current through the heterojunction is given by the Landauer formula,

$$I=\frac{2e}{\pi \mathrm{}}𝑑ET(E)\left\{f(EeV/2)f(E+eV/2)\right\},$$
(7)   
with the energy-dependent transmission coefficient $`T(E)`$ of the junction. It is natural to separate the contribution $`T_i(E)`$ of a barrier at the interface between SWNTs  and the contribution $`T_S(E)`$ of a SB to the total transmission. As a minimal model, we assume that the transparency $`T_i`$ is energy independent whereas the transparency $`T_S(E)`$ increases from zero to unity when the energy $`E`$ crosses the edge of a SB. In this case the total transmission reads $`T(E)=0,(T_i)`$, for the energies in (out of) the SB range $`[E_{\mathrm{min}},E_{\mathrm{max}}]`$. In the case of downward bending (Fig. 2) the SB range is given by $`[E_v(0),E_c(\mathrm{})]`$, in the absence of charge carriers in the conduction band, $`\mu +eV/2>\mathrm{\Delta }`$ (Figs. 2(a-d)), and by $`[E_v(0),E_c(0)]`$, in their presence, $`\mu +eV/2<\mathrm{\Delta }`$ (Fig. 2(e)). The results for the $`IV`$ characteristics at zero temperature are presented in Figs. 2(f), 3(b).

With increasing forward bias the SB (Fig. 2(c)) disappears and the hole transport channel opens at $`V>V_+`$.

The cusp at the $`IV`$ characteristics (Fig. 2(f)) at somewhat higher voltages corresponds to the onset of the electron channel. Note that at high (forward or reverse) bias both the electron and hole channels are open and the current is given by $`I=(2eT_i/\pi \mathrm{})[eV2\mathrm{\Delta }sign(V)]`$.

The onset of the conductance under reverse bias depends critically on the electro-chemical potential $`\mu `$ (Figs. 2(f), 3(b)). At low doping, $`\mu 1.8\mathrm{\Delta }`$, the current increases abruptly at $`V_{}=V_c`$, $`eV_c=2(\mathrm{\Delta }+\mu )`$. The voltage $`V_c`$ corresponds to the alignment of the Fermi level with the conduction band of semiconducting SWNT. Electrons entering the conduction band cause the charge build-up near the junction. The reconstruction of the band profile (cf. Figs. 2(d) and 2(e)) results in the onset of the electron and hole channels of transport giving rise to a step-like growth of the current. At higher doping, $`\mu 1.8\mathrm{\Delta }`$, the threshold voltage $`V_{}>V_c`$ corresponds to the opening of the hole channel. The current gradually grows under reverse bias $`V_c<V<V_{}`$ until the reconstruction of the band profile occurs at $`V=V_c`$ (see the curve for $`\mu =3`$ in Fig. 2(f)).

We now consider quantum tunneling through the SB. The transparency $`T_S(E)`$ of the SB can be evaluated using WKB method and the effective mass approximation. For a triangular barrier of the length $`l`$ and the height $`u`$ we obtain,

$$T_S\mathrm{exp}\left(\frac{4l}{9R}\sqrt{\frac{2u}{\mathrm{\Delta }}}\right).$$
(8)   
The transparency $`T_S`$ increases considerably near the boundaries of the transport blockade region $`[V_{},V_+]`$ (Fig. 3(a)) due to decreasing $`u`$ and $`l`$. For example, $`T_S2.5\times 10^3`$ for the SB in Fig. 2(b), whereas $`T_S1`$ for the SBs in Figs. 2(c), 2(d). This gives rise to a substantial leakage current in the blockade region.

The asymmetry of the $`IV`$ characteristics and threshold voltages has been discovered in recent experiments . According to the data of Ref. , both the thresholds $`V_+`$, $`V_{}`$ shift upwards with the gate voltage. Moreover, the positive threshold shifts less than the negative one. Such behavior is consistent with our model in the regime of moderate doping, $`0.5<\mu /\mathrm{\Delta }1.8`$ (Fig. 3). However, the blockade region of $`34`$ V detected in the experiment is somewhat wider than the theoretical estimate, $`V_+V_{}6.5\mathrm{\Delta }2`$ eV. The extra voltage drop could be due to potential disorder in semiconducting SWNT  and/or an additional SB at the interface between semiconducting SWNT and metallic electrode.

We now check the model against the experimental data of Ref. . The measured width of the blockade region, $`0.50.7`$ V, agrees with the theoretical estimate. The gap in semiconducting SWNT, $`\mathrm{\Delta }eV_+`$, evaluates at $`\mathrm{\Delta }=0.19`$, $`0.29`$ eV for the two devices studied . These values are in the expected range $`\mathrm{\Delta }0.250.35`$ eV . A smooth onset of the current over the range $`0.10.3`$ eV around threshold voltages is naturally associated with quantum tunneling through a ”leaky” SB (thermal energies are much smaller, $`k_BT5`$ meV). Finally, the step-like feature of the current under reverse bias almost certainly corresponds to the reconstruction of the band profile due to the Fermi level entering the conduction band of semiconducting SWNT. Gradual onset of the differential conductance following the reconstruction might be associated with increasing conductance of disordered semiconducting SWNT under the doping .

To conclude, we have studied the electronic properties of carbon nanotube heterojunctions and provided explanation for the main features of recent experimental data . Due to the long-range Coulomb interaction, the charge transfer phenomena in one-dimensional nanotube systems differ drastically from those in conventional semiconductor heterostructures. This creates new challenges in the design of novel electronic devices. In particular, the long-range electrostatic potential in underdoped junctions might affect other components of a circuit, whereas substantial leakage current in overdoped junctions spoils the rectification. In view of these challenges a new concept of functional devices on molecular level might be needed.

In the process of writing this paper I became aware of the preprint by Léonard and Tersoff  who investigated equilibrium properties of junctions between semiconducting SWNTs and found the long-range charge-transfer phenomena in these systems (see also Ref. ).

The author wishes to thank B.L. Altshuler, G.E.W. Bauer, Yu.V. Nazarov, S. Tarucha, Y. Tokura, Z.Yao, and, especially, C. Dekker and P. McEuen for stimulating discussions. F. Léonard and J. Tersoff are acknowledged for sharing the results of Ref.  before publication. This work was supported by the Royal Dutch Academy of Sciences (KNAW).