IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS, VOL. 40, NO.

5, SEPTEMBER/OCTOBER 2004

1215

Electronic Properties of Single-Wall Carbon Nanotubes and Their Dependence on Synthetic Methods
Dan A. Buzatu, Alexandru Sorin Biris, Alexandru Radu Biris, Dan Miron Lupu, Jerry Anthony Darsey, and Malay K. Mazumder

Abstract—Since their discovery in 1991, carbon nanotubes have been intensively studied, and a number of new applications have been identified. Applications range from nanoelectronics to hydrogen absorption for battery electrodes and fuel cells. Because of their high electrical conductivity and strength, high-sensitivity atomic force microscopes already use carbon nanotubes for their tips, and carbon nanostructures are also used as electron beam emitters for medical and scientific equipment. Electron emission is directly correlated with the work function and the ionization potential of carbon nanotubes. Gaussian 98 software was used to perform theoretical quantum calculations on a limited set of HyperChem 5.01 simulated metallic single-wall carbon nanotubes. These initial sets of calculations show that bandgaps and work functions of these small carbon nanostructures are dependent upon the diameter of the tubes, and to a lesser degree so is the ionization potential. In addition, we demonstrate how the manufacturing methods can directly affect the diameter of the nanotubes produced, and therefore directly influence the electrical properties of the nanotubes. Index Terms—Computational, electronic properties, ionization potential, nanotubes, synthesis, work function.

I. INTRODUCTION

S

INCE their discovery, carbon nanotubes have been proposed and used for a number of potential applications ranging from nanoelectronics [1] to field emitters [2] or atomic force microscopes (AFM) tips [3]. This is because of their exceptional mechanical and electrical properties. They possess high mechanical strength and have a wide range of electrical conductivities, ranging from insulating to conducting. Carbon nanotubes can be made in a wide range of diameters and lengths based on the particular preparation method used [4]. If the tubes are formed by only one carbon sheet, they are

called single-wall carbon nanotubes (SW-CNT), while if they are made of a number of concentric coiled carbon sheets, they are called multiwall carbon nanotubes (MWCNT). The electrical and the mechanical properties are different for SWCNT and MWCNT. Furthermore, two SWCNT with different lengths and diameters will not have the same mechanical, optical, and electrical characteristics. The most interesting properties of carbon nanotubes are the bandgap, ionization potential, high current-carrying capacity, hydrogen absorption, and field emission. In order to explore the full potential of carbon nanotubes, a comprehensive understanding of their electronic properties is required. Papers have previously reported trends in nanotube bandgap variations with tube diameter [5], although some of the results are still controversial. Carbon nanotubes have been shown to have extremely high and stable current densities of 10 A/cm [6], whereas other conductors like copper burn at about 10 A/cm . Carbon nanotubes have also been found to be excellent field emitters, which makes them suitable for flat panel display applications [7]. This paper discusses the effects of diameter size on a nanotube’s electronic properties (especially the work function and the ionization potential) as calculated by accurate ab-initio quantum methods. It then demonstrates how different fabrication techniques can be used to produce different diameter nanotubes which maintain the relationships between diameter and electronic character. II. THEORETICAL CALCULATIONS Molecular simulations and orbital calculations represent some of the best techniques to model and investigate the electronic structure of carbon nanostructures. There has been some experimental work done to measure bandgaps and other important electronic properties of carbon nanotubes [8]. In general, it is difficult to accurately monitor the electronic properties of these structures experimentally and obtain reproducible results. This is especially true because current manufacturing methods produce batches of nanotubes in a wide range of diameters and lengths [9]. This is further complicated by the fact that some of the nanotubes can have metallic properties, while others behave , designated like semiconductors. Armchair nanotubes by , where and are coefficients of the chiral , are believed to have metallic conductive properties, vector (where whereas chiral nanotubes designated by ) are believed to have semiconductor-like properties [9].

Paper MSDAD-A-04-08, presented at the 2003 ESA-IEEE/IAS/EPC Joint Conference, Little Rock, AR, June 24–27, and approved for publication in the IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS by the Electrostatic Processes Committee of the IEEE Industry Applications Society. Manuscript submitted for review June 27, 2003 and released for publication June 14, 2004. D. A. Buzatu is with the Division of Chemistry, FDA National Center for Toxicological Research, Jefferson, AR 72079 USA (e-mail: dbuzatu@nctr.fda.gov). A. S. Biris and M. K. Mazumder are with the Applied Science Department, University of Arkansas at Little Rock, Little Rock, AR 72204 USA (e-mail: asbiris@ualr.edu; mkmazumder@ualr.edu). A. R. Biris and D. M. Lupu are with the Special Materials Department, National Institute for Research and Development of Isotopic and Molecular Technologies, R-3400 Cluj-Napoca, Romania. J. A. Darsey is with the Department of Chemistry, University of Arkansas at Little Rock, Little Rock, AR 72204 USA. Digital Object Identifier 10.1109/TIA.2004.834051

0093-9994/04$20.00 © 2004 IEEE

and is 1/2 the magnitude of the bandgap of the nanotube.25 eV was calculated for the 1. and 5.5% Cu) catalyst.2-nm nanotube. NO. Metal/oxide catalysts were prepared using the co-precipitation technique.1216 IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS.14 eV for the 0.5% Ni : 2. Once the catalysts were activated.5% : 2. SEPTEMBER/OCTOBER 2004 Hyperchem 5. and an MOE gap of 1. and a temperature of 425 C. Using the B3PW91 functional and the D95 basis set. The total energies of a neutral nanotube molecule and a 1 charge cation of the same molecule were calculated using the DFT procedure just described. (97.6-nm nanotubes. were prepared by mixing the metal powders. ) : Cu at 600 C and a pressure of 0. SEM images of carbon nanostructures obtained from ethylene: H (4 : 1) on a Ni : Cu (97. The ionization energy was then obtained by subtracting the total energy of the neutral nanotube molecule from the energy of the 1 charge nanotube cation. The ionization potential and work functions of the nanotubes were determined by applying the following procedures. and the D95 [14] basis set.2-nm-diameter nanotube. and reaction temperature. The HOMO and LUMO energies of the simulated nanotubes were obtained from DFT SCF-MO calculations performed on neutral charge nanotube molecules. but it was activated in a hydrogen stream at flow rate of 50 mL/min and a temperature of 415 C. Gaussian 98 [11] was then used to perform Density Functional Theory (DFT) self-consistent field molecular orbital (SCF-MO) single-point energy calculations on the structurally optimized nanotubes. 40. starting from solutions of methane nitrates or metal mixtures (with and without metallic support) mixed in required mole ratios. A number of different CVD methods were tested and the results were previously reported [16]. and 0. After precipitation with sodium carbonate.5% Cu) catalyst. The MOE gap of a molecule is simply the relative difference in energy between the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO). The first method uses an ethylene to hydrogen ration of 4 : 1. filtered. 1.5%) catalyst.73 eV was calculated for the 0.01 [10] molecular modeling software was used to construct metallic carbon single-wall nanotubes (SWNTs) and perform MM+ (Molecular Mechanics) geometry optimization on the systems. The most important parameters are the type of catalyst metal used. The SEM pictures of those nanotubes are shown in Fig. Using these values and the previously reported ionization potentials.5 nm in length. The second method used the same catalyst. the ionization potentials were calculated to be 5. VOL. The third method used a Ni : Cu (97. EXPERIMENTAL GROWTH OF CARBON NANOTUBES The method employed to grow carbon nanotubes was chemical vapor deposition (CVD). The scanning electron microscope (SEM) pictures of the carbon nanostructures growth by this method are shown in Fig. Only Ni : Cu catalysts TABLE I EXTERNAL DIAMETER OF THE CARBON NANOTUBES DIFFERENT METHODS GENERATED BY Fig. These conditions favor the formation of metal particles with diameters in the range of a few dozen nanometers and avoid sintering [15].6-nm nanotube. This catalyst was activated in a gas stream of He with 6% H at a flow rate of 50 ml/min.275 eV was eV was calculated for the 0.5% Ni : 2. the precipitate was washed.3 (3. Bandgap is a term that is used when describing solid-state materials. Calculations were carried out using the Becke 3 parameter hybrid functional [12] with Perdew and Wang’s 1991 nonlocal. 5. The two tubes that were constructed were approximately 0. Because of its high efficiency it provides control over the nature and efficiency of different reaction products formed through varying parameters. Fig.25 bars on an Ni (1.18 eV for the 1. 3 shows the nanotubes created using this method. 2. gradient-corrected correlation expression [13]. Four different experimental methods are discussed in this paper and the diameters of the nanotubes they produce are shown in Table I.2-nm nanotube.8m g). the hydrocarbons or a mixture of hydrocarbons were introduced in the reactor in order to allow catalytic decomposition to occur. where III. The were calculated from work functions of the nanotubes the solid-state semiconductor theory equation (1) is the ionization potential of the nanotube. dried at 105 C and finally calcined at 300 C–400 C. which was obtained by the co-precipitation method. and calculated for the 1. The activation of the catalysts was achieved in situ inside a reactor (made of quartz with a diameter of 30 mm and a length of 80 cm) in a hydrogen stream at a flow of 20 ml/min and a temperature of 400 C. a work function of 4. Since the carbon nanotubes are molecules.6-nm-diameter nanotube. 1. activated in He : 6% H .6 and 1.2 nm in diameter. the term molecular orbital energy (MOE) gap will be used. The catalyst was activated in a gas stream of He with 6% H at a flow rate of 50 mL/min. the feedstock hydrocarbon type. and a temperature of 425 C. An MOE gap of 1. . flow and gas pressure.

Fig. IV.5%) catalyst obtained by coprecipitation and activated in H . Fig. However.5% : 2. 3. 4 shows the carbon nanostructures produced by this method. Therefore. and are similar to those calculated by Zhao and co-workers for metallic single-walled nanotubes with diameters ranging from 5. SEM images of carbon nanostructures obtained from ethylene: H (4 : 1) on a N i: Cu (97. 2. acknowledged that Kohn Sham energies generally underestimate actual bandgap values. with the conductivity increasing (slightly) with increasing length to a constant value. which show (as our calculations show) that bandgap decreases when a nanotube’s diameter increases. 4. which tends to further deepen the HOMO energy levels through increased electron repulsion forces. CONCLUSION Theoretical calculations were used to demonstrate the relationship between the size (diameter) and electronic properties of metallic SW-CNTs.5% : 2.5%) catalyst obtained by coprecipitation and activated in He : 6% H . who used a local density approximation (LDA) generalized gradient approximation (GGA) technique to calculate Kohn Sham bandgap energies for SW-CNTs [18]. work function. The electronic trends predicted by these simulated tubes are expected to be analogous in much larger tubes. The calculated bandgaps are somewhat higher than those calculated by Ito and co-workers. Important electronic properties such as bandgap.: ELECTRONIC PROPERTIES OF SINGLE-WALL CARBON NANOTUBES AND THEIR DEPENDENCE ON SYNTHETIC METHODS 1217 correlation between the diameter of the nanotubes and their electric and electronic properties. after which it does not further increase no matter how long a nanotube is. is the increase in the nanotube’s molecular orbital energy gap (bandgap).3–4. activated in H . Fig. Our calculations also show that a decrease in the diameter of the simulated SW-CNT caused a substantial decrease in the work function eV eV and nm nm a slight.7 to 16. The increase in the energy gap between the HOMOs and LUMOs (analogous to nonconductive and conductive bands in solid state semiconductors) of the smaller diameter nanotube suggests a disruption in the conductive orbital state. we would not expect changes to the diameters of larger nanotubes to have such a pronounced effect on their work functions and bandgaps because the orbital steric encumbrances introduced by small diameter geometries will not exist in those tubes.5% : 2. the fourth method employed the same catalyst as the third method. almost negligible decrease in its ionization potential ( eV vs. thin metallic multiwalled nanotubes (4. A possible reason for the substantial decrease in the work function of the smaller diameter simulated nanotube. Fig. In a different study that we will later communicate. it is possible to use CVD process of different hydrocarbons and on different catalysts to control the nanotubes diameter and. such as the ones we are currently producing. Finally. The diameter values in Table I were estimated from several experimental measurements including SEM and TEM. SEM images of carbon nanostructures obtained from ethylene: H (4 : 1) on a Ni : Cu (97. Table I illustrates how fabrication methods can be used to control the diameter of carbon nanotubes. their work function and ionization potential values. Ito et al. and ionization potential were investigated. This is most likely due to an orbital steric constriction created by the smaller geometry. but it was activated in a hydrogen stream at flow rate of 50 mL/min and a temperature of 415 C. 2. the length of a synthesized carbon nanotube is not dependent on the Fig.SEM images of carbon nanostructures obtained from ethylene: H (4 : 1) on a Ni : Cu (97. Our calculated bandgap values correlate well with experimental values published in 2003 [17]. given the . However. eV). These calcunm nm lated work function values correlate very well with those measured by Shiraishi and co-workers using ultraviolet photoelectron spectroscopy (UPS) for small. In general. calculations will show there is a direct relationship between the conductivity and length of a metallic SW-CNT.5%) catalyst.BUZATU et al. in comparison to the bigger diameter tube. therefore. It is important to point out that length also has an important effect on a nanotube’s conductivity.8 eV) [8].5 [19].

Lupsa. B. U. Lupu. Cluj Napoca. M. J. M. He has been involved in nanotechnology since 1998. M. Saito. “Purification and size-selection of carbon nanotubes. M. Misan. J. B. W. C. M. Rev. M. and P. pp. [14] T. 40. degree.” Adv. D. J. from the University of Cluj Napoca. S. Stefanov.. A.” Nanotechnol. [5] J. Canada. M. 827. Peng. and N. “AFM manipulation of carbon nanotubes: realization of ultra-fine electrodes. C. vol. He was a Research Scientist at the National Center for Isotopic and Molecular Technologies. 3. Duschl.” Scientif. P. G. U. W. 65. G. A. work function. M. who is currently developing and testing spectral-based methods for rapid detection of biological pathogens and hoax materials. [17] C. C.-M. pp. A. 1. Andres. K. and M. L. ON. Hay. in 1997. 69. degree in materials science/applied engineering from the University of Arkansas. Nanayakkara. I. Scuseria. Pomelli. He is an FDA Staff Research Chemist at the FDA National Center for Toxicological Research (NCTR). and P. Pittsburgh. T. Little Rock. J. vol. B. Malick. T. he started a research program for the synthesis of carbon nanostructures and their interaction with hydrogen. J. R. Replogle. L. Johnson. pp. J. 2000. vol. J. 1976. LA. pp. V. M.” J. J. 3. Challacombe. vol.. Rev. [13] J. Legagneux. C. E. He is the author of numerous articles and several book chapters on computational nanoscale molecular electronics. H. Hoboken. Turpin. and has been involved extensively in predictive computational work on carbon nanotubes and nanostructures since 2000. [10] “HyperChem 5. pp. R. R. degree in physics and the M. O. Wang. D. A. 9. B. A. B. Alexandru Radu Biris received the B. Ito. Inc. Particulate Sci. since 1974. Pribat. Morokuma. pp. 5648. we strongly believe the calculations demonstrate an extremely useful and important predictive power in nanoscale electronics. “Density-functional thermochemistry. I.S. Cluj Napoca. Phys. 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Dr. Darsey has organized numerous sessions at national and international meetings.D. Little Rock. Several years ago. degree in instrumental sciences from the University of Arkansas. the influence of substitutions on thermodynamic and kinetic properties of hydrogen absorbing inter-metallics. and Informatics. as a faculty member in 1971. FL. U. 1st ed. including the 6th World Multiconference on Systemics. and novel alloys for use as hydride electrodes in Ni/MH batteries. Switzerland. Malay K. His work has been cited in six books. He is currently a Professor in the Department of Chemistry. . He is the author of more than 50 journal manuscripts and gave the 1992 invited lecture at the International Symposium of Hydrogen in Metals. Jerry Anthony Darsey received the Ph. and served as the Director of the Graduate Institute of Technology until 1988. Mazumder serves as a Chief Co-Editor of Particulate Science and Technology: An International Journal. patent of the E-SPART Analyzer.: ELECTRONIC PROPERTIES OF SINGLE-WALL CARBON NANOTUBES AND THEIR DEPENDENCE ON SYNTHETIC METHODS 1219 Dan Miron Lupu received the degree from the Department of Chemistry. Romania.). He also gave the Outstanding Research Presentation at the 17th Southwest Theoretical Chemistry Conference. He joined the Department of Electronics and Instrumentation (now known as the Applied Science Department) in the Graduate Institute of Technology. Cybernetics. in which he organized the session on recent developments in nanotechnology. medical aerosols. degree in physical chemistry from Louisiana State University. and international meetings. May 2001. he was the Chairman of the Department of Electronics and Instrumentation from 1981 to July 1990. His research accomplishments include the development and resulting U. working on hydrogen storage alloys. and electrostatic engineering. He was selected to be included in 2000 Eminent Scientist of Today (Cambridge. a laser-based research instrument unique in the field of aerosol science and powder technology. in June 2000. Romania. Additionally. CA. held in Uppsala. Prof. College Station. He was Chairman of the 1st Symposium on the Applications of Artificial Neural Networks and Other Artificial Intelligence Procedures to Chemical Systems at the national meeting of the American Physical Society. He is a Senior Distinguished Researcher and Head of the Department of Materials at the Romanian National Institute for R&D of Isotopic and Molecular Technologies. This work resulted in the first ever demonstration in the literature (2004) of a chemical vapor deposition/inductive heating technique being used for the synthesis of various carbon nanostructures. He is the author or coauthor of more than 90 publications. he also participated as a research guest at the Institute of Physics-University of Fribourg. Cluj-Napoca. in 1982. he was promoted to the rank of University Professor. Sweden. Mazumder received the Ph. He is the author of over 100 publications in the field of molecular modeling and has presented over 300 talks at regional.K. national. he and his co-workers started working on the synthesis of carbon nanostructures and determining their potential for hydrogen uptake. held in Orlando. Dr. Texas A&M University.S. He was promoted to the rank of Professor in 1981. University Babes-Bolyai. Lupu served as a Reviewer for the International Journal of Hydrogen Energy from 1980 to 2004. Cluj-Napoca. University of Arkansas. He has devoted most of his career of more than 30 years to hydrogen storage. He is also currently serving as the Commissioner of the Arkansas Martin Luther King Commission. He received the University of Arkansas at Little Rock’s 1988 R&D Award. His research interests include particle and powder technology. San Jose. University of Arkansas at Little Rock.BUZATU et al.D. In 1991.: International Biographical Centre.