Current Applied Physics 2 (2002) 473477 www.elsevier.

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Substitutional boron-doping of carbon nanotubes q

R. Czerw a, P.-W. Chiu b, Y.-M. Choi c, D.-S. Lee c, D.L. Carroll Y.-W. Park c
a c

a,*

, S. Roth b,

School of Materials Science and Engineering, Clemson University, Clemson, SC 29634, USA b Max-Planck-Institut f ur Festk orperforschung, Stuttgart, Germany Department of Physics and Condensed Matter Research Institute, Seoul National University, Seoul, South Korea Received 8 May 2002; accepted 25 May 2002

The substitutional placement of boron within the lattice of carbon nanotubes yields quite dierent transport properties for single walled nanotubes (SWNTs) as compared to multi-walled nanotubes (MWNTs). Boron doping of the MWNTs results in an acceptor state in the local density of states (LDOS) that lies near the Fermi level and can be directly correlated with features in the thermoelectric power (TEP) of B-doped MWNT mats. Transport measurements of individual B-doped MWNTs exhibit features associated with variable range hopping. In contrast, B-doping of SWNTs results in features in the density of states further from the Fermi level, and transport of the SWNTs shows an unusual variability in rectication not observed in the MWNT case. This suggests that boron has been introduced into the lattice of these two morphologies of nanotubes in very dierent ways. Interest in the electrical transport properties of both single-walled and multi-walled carbon nanotubes stems primarily from potential applications in nanoelectronics [1]. Initially, nanoscale electronic architectures will be similar to those in use today. Thus, one expects metallic conduits along with heterojunctions formed from doped nanomaterials in analogy to bulk Si devices connected with metal interconnect lines. Further, it is clear that the eects of lattice impurities are of fundamental interest in understanding transport phenomena in these unusual topological objects. However, the direct substitutional doping of carbon nanotubes is quite dicult. Their low dimensional structure does not provide an energetically

q Original version presented at QTSM & QFS 02 (Multi-lateral Symposium between the Korean Academy of Science and Technology and the Foreign Academies), Yonsei University, Seoul, Korea, 810 May, 2002. * Corresponding author. E-mail address: dcarrol@clemson.edu (D.L. Carroll).

favorable environment for most impurity atoms. There are two promising candidates, boron [2] and nitrogen [3], both of which seem happy to reside within the carbon lattice. The behavior of boron in SWNTs and in MWNTs, as evidenced through transport and tunneling spectroscopy, appears to be quite dierent. In this work, we describe several important dierences in Bdoped MWNTs and B-doped SWNTs. For these studies arc growth methods were used exclusively. Pure carbon nanotubes were arc grown using methods described in detail elsewhere [4]. Transmission electron microscopy (TEM) showed a diameter distribution to be centered around 20 nm with tubes as small as 3 nm and as large as 40 nm with tube lengths typically 1 lm. The primary impurities were carbonaceous materials and polyhedral particles and an scanning tunneling microscopy (STM) image of a typical MWNT bundle is shown in Fig. 1a. B-doped MWNTs were also grown using arc methods as described in the literature [5]. TEM characterization showed these materials to have typical tube diameters of 20 nm with a range of 540 nm. Selected area diraction conrms that these tubes possess predominantly zig-zag chiralities [6]. Tunneling microscopy and spectroscopy, coupled with electron energy loss spectroscopy (EELS), has been used to demonstrate that the boron is incorporated into the lattice as islands of BC3 [7]. The impurities in the growth materials were found to be polyhedral particles (also seen in Fig. 1b) and small concentrations of carbonaceous material. No catalysts were used in the growth of either of these MWNT, arcproduced materials. Finally, B-doped SWNTs were produced by using the same process of arc growth as outlined in the literature for pure SWNTs. However, in the case of B-doping, pure boron was mixed with Ni/Y catalysts and carbon and packed into the center of the graphite anode rod. The raw growth materials resulting from the boron-rich

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Fig. 1. (a) STM image of undoped MWNT bundle, (b) TEM image showing B-doped MWNTs and polyhedral material and (c) STM image of a B-doped SWNT.

growth plasma are much more tightly packed around the cathode than typical pure SWNT growth. Interestingly, we note that atomic resolution of this material shows the existence of chiral nanotubes. Unlike the atomic scale imaging of the zig-zag B-doped MWNTs, the B-doped SWNTs also show a variety of super-

structures across the surface. In fact, these superstructure patterns seem more the rule in imaging these materials with STM. A typical superstructure from a Bdoped SWNT is seen in Fig. 1c. This image was acquired at 50 pA and a bias voltage of 1 V with the samples in ultrahigh vacuum at room temperature. As noted in the above references, the B-doped MWNTs are predominately zig-zag and are heavily doped with boron. Previous studies have shown that an acceptor-like state is introduced into the band structure of these metallic tubes. This state derives from the formation of BC3 islands and its position depends on the distribution of island sizes within the matrix. The average position of the acceptor state in this material was around 25 meV as reported previously. To understand the average doping behavior of the boron in the MWNTs and how the large feature near the Fermi level might eect transport, the TEP was measured [8,9]. Since the TEP is a zero current transport coecient, it can probe the intrinsic properties of the individual nanotubes without inuence of the randomly entangled morphology of the mats in which they are normally produced [10]. Generally, both SWNTs and MWNTs mats show a positive and moderately large TEP over the temperature range of 0 to 300 K, with temperature dependencies that approach zero as T0 ! 0 [11]. Nanotube mats were produced by suspending each (as grown) material into chloroform and then ultrasonically agitating until the nanotubes were well dispersed. The suspended materials were found to be relatively undamaged, after the extended ultrasonication using TEM. Each solution was allowed to settle and then was ltered using 0.4 m Teon lters. The remaining solution was composed of nanotubes with little amorphous materials and no polyhedra. Finally a thick lm was built-up from each of the materials using a Teon lter and a polyimide mold (to insure equal dimensions in each case). This resulted in a random packing of nanotubes in a dense mat. The samples were 3 mm 5 mm 0:025 mm in size. Several mats of each material were made and the measurements performed several times on each to insure reproducibility. To carry out TEP measurements, the mat samples were supported on a Teon substrate and mounted on top of two copper blocks. Silver paste was used for the electrical contacts. Chromelconstantan thermocouples were attached to the back of the copper blocks using GE 7031 varnish. Techniques for the TEP measurement of carbon nanotubes are described with more detail in the literature [12]. Fig. 2 shows the TEP as a function of temperature. Note that for pure carbon nanotubes, the shape of the TEP vs. temperature curve is exactly as expected from previous reports. The B-doped mats also exhibit a large

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Fig. 3. Atomic force microscope images of a nanotube transistor. Fig. 2. TEP of pristine and doped MWNTs.

positive TEP but is much more linear in shape and has a lower overall magnitude. The sign of the TEP for the B-doped materials is not surprising since these nanotubes have strong acceptor states and hole-like conductivity should be expected. Further, dierences between the functional forms of the pure and B-doped TEPs should also be expected. This is because the generally accepted physical picture for TEP in mats is a set of semiconducting and metallic parallel conducting paths each of which is separated by randomly placed contact barriers between the tubes. Unlike the pure MWNT case, in the B-doped materials, there are no semiconducting contributions since the majority of the tubes (if not all) are metallic and exhibit zig-zag chiralities (3) [13]. Therefore, the curve should be more linear (metallic) in nature with features arising from the sharp feature in the Fermi window (seen at around 50 C in Fig. 2) [14,15]. Thus, the B-doped MWNTs are behaving very much like degenerately doped bulk materials in this regard. These materials were then used to fashion typical nanotube-eld eect transistor structures as described in the literature elsewhere. Generally, the nanotubes were deposited on a siliconsilicon dioxide substrate with a back gate. Goldpalladium contacts were added onto the nanotube ends using electron beam lithography. A typical device is shown in the atomic force image of Fig. 3, where the length of tube between the contacts is approximately 900 nm. From height measurements, the tubes are isolated (not bundles) and this particular example is approximately 20 nm. The TEP behavior is clearly conrmed in the single tube transport behavior. Little variation in conductance is seen with applied gate voltage (not shown). Fig. 4a shows the normalized resistivity as a function of temperature. The inset shows the log plot of the conductance t to an exponential function with the exponent being 0.25 corresponding to

Fig. 4. (a) Shows the resistance as a function of temperature. The inset ts the conductance to an exponential function vs. temperature and yields an exponent of 0.25 and (b) shows the conductance at low source-drain biases.

a variable range hopping mechanism. Fig. 4b shows the IV characteristics for small applied voltages across the source drain leads for 300 and 4 K clearly showing metallic behavior in the tubes. The situation with B-doped SWNTs is signicantly dierent. Shown in Fig. 5 is the LDOS as determined by

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Fig. 5. LDOS for B-doped SWNT. Notice the acceptor state at about 0.4 eV.

tunneling spectroscopy. Notice that, unlike the case of B-doped MWNTs, the acceptor features in these nanotubes occur at around 0.4 eV. This corresponds quite well with calculations reported earlier and is an indication that the local environment of the boron is not the BC3 as in the case of the MWNTs. We further note that these nanotubes can have a distinct band gap. The examples shown here exhibit a band gap of 0.5 eV. The semiconducting nature of the tubes can be seen in the IV characteristics as shown in Fig. 6. What is curious about the conductance measurements is that they can have dierent rectication features from run to run suggesting that there may be some mobility to the doping species. Notice that the apparent conductance gap remains approximately the same. In summary, the eects of boron doping in multiwalled carbon nanotubes and SWNTs are signicantly dierent. For the multi-walled case, local bonding environments of the boron results in an acceptor state near the Fermi level that strongly eects overall transport behavior. This is seen in both TEP determinations as well as single tube transport measurements. These nanotubes are clearly metallic in nature and are hole-like conductors. In contrast, B-doping in SWNTs results in features much further up in the band structure on the valence band side (acceptors). While this is in agreement with earlier calculations for isolated defects, transport measurements indicate some added variability in rectication for a given tube. We speculate that this may be a result of materials included inside the nanotube but point out that his does not preclude boron added to the lattice as well. Further, these B-doped SWNTs can occur in a variety of chiralities as indicated by atomic scale images as well as the existence of band gaps in their electronic structure. These ndings suggest that the use of dopants in nanotubes might provide unique and in-

Fig. 6. The IV characteristics of a B-doped SWNT device varies from run to run.

teresting ways to inuence and control their electronic properties.

Acknowledgements The authors gratefully acknowledge support from: KISTEP 98-I-01-04-A-026, MOST (Korea), AFOSR F49620-99-1-0173 (US), DFG (Germany).

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