rot. 43 No.

tl

SCIENCE IN CHINA

(Series

A)

~owml~20o0

PHYSICS Single wall carbon nanotubes and their electrical properties

XUE Zengquan (i~>'~ ~r ' , LIU Weimin (~] r HOU Shimin ( ~ . ~ . ~ ) 1 , SHIZujin ($(~.,~-It.-{~)2, GU Zhennan (E~J~-, r~) 2, LIU Hongwen (Y~] ~r_~)',
ZHAO Xingyu (~2~.Y-~-, b,~) ~, ZHANG Zhaoxiang ( ~ E ~ ) ~ , WU Mianlei ( ~. ~ @) ', PENG Lianmao ( .~ ~$ ~ )' & WU Quande ( .~ )~-~,~ )x
1. Departmentof Electronics, Peking University, Beijing 100871, China; 2. College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China Correspondence should be addressed to Xue Zengquan (email:zexue @263. net) Received July 21, 1999

Abstract Single-wall carbon nanotubes (SWCNTs) were synthesized and purified. A water colloid of SWCNTs was prepared and used to assemble SWCNTs onto a gold film surface. Scanning tunneling microscopy (STM) images showed that short SWCNTs stood on gold film surfaces. Using STM tips made of SWCNTs, a crystal grain image of a gold thin film and an atomic resolution image of highly oriented pyrolytic graphite were successfully obtained. The electrical properties of short SWCNTs, which stood on the surface of gold film, were measured using STM. That SWCNTs stand on gold thin films is a promising technique for studying structures and properties of carbon nanotubes, as well as assembling and fabricating high-intensity coherent electron sources, field emission flat panel display, tips for scanning probe microscopes, new nanoelectronic devices, etc.
Keywords: carbon nanotubes, tips for scanning probe microscopes, field emission pattern, electrical properties parallel to the axis of SWCNTs.

Carbon nanotubes, a new one among isomers of carbon discovered first by Iijima in 1991 Ell , may be the most typical and fundamental nanometer-scale material. A carbon nanotube can be described as graphite sheets rolled into seamless cylindrical tubes. There are muhiwall carbon nanotubes (MWCNTs) and single-wall ones; both of them can be different in diameter and ehirality. Carbon nanotubes have aroused great excitement, and more and more researchers focus their attention on carbon nanotubes. Now, the emphasis are laid on the preparation and purification method E2'33 , structural characteristics ~4'51 , electrical and optoelectric properties [6-9] , mechanical properties ~1~ , etc. Because of their simple and well-defined structure, single-wall earbon nanotubes (SWCNTs) are preferable in the basic research. Smalley, who won the Nobel Prize in 1996 for his discovery of C6o, indicated that carbon nanotubes may be an important material for nanoelectronic devices In] . We have explored new functional materials different from silicon and tried to measure single electron phenomena at room temperature. Scanning probe microscopes (SPMs) are important tools for atomic resolution observation and nano-fabrication. Many methods have been adopted to prepare carbon nanotubes, but usually a mixture of many different structures is obtained and most of them are MWCNTs. Synthesis methods for SWCNTs are also developed by some research groups. The structure and electrical properties of a single SWCNT or MWCNT lying on a substrate have also been studiedN2-143 .

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Preparation of SWCNTs

The SWCNTs were produced by DC are discharge method. The anode was an extremely pure graphite rod with 6 mm diameter, on which a hole 3 mm in diameter was drilled and filled with graphite and YNi2 powder with molar ratio 1 : 1. The cathode, which was a graphite rod 10 mm in diameter, was shaped into a sharp tip so that the evaporation of the cathode could be minimized. The are was generated by a current of 40--100 A in a helium atmosphere at a pressure of 1 x 104pa--7 x 10# Pa. During the discharge process, the distance between the anode and the cathode was kept about 5 mm. The obtained cloth-like soot contained about 40 % SWCNTs. The soot was extracted with CS2 and HC1 of molar ratio 1 : 1, and then it was baked at 100~ to remove fullerenes and catalysts. As measured by the high resolution transmission electron microscopy, the purity of SWCNTs was 90% after MWCNTs were filtrated out. A water colloid of SWCNTs was prepared after SWCNTs was cut short by oxidation. The length of SWCNTs was about 10--40
nln.

SWCNTs assembled perpendicularly on the surface of crystal Au thin film

We studied the behavior of SWCNTs on a gold thin film. The gold thin film was deposited on a freshly cleaved mica substrate retained at 300 ~ in a chamber of a vacuum system under a pressure of 10 -4 Pa. The deposition rate of gold was about 1 n m ' s -1 . The gold thin film was about 500 nm thick. Atomic resolution images of Au thin films were obtained with TEM and scanning tunneling microscopy (STM). A water colloid of SWCNTs described above was dropped onto the gold thin film after it was taken out from the vacuum chamber. This sample was observed by STM after the water evaporated. The STM was P47 SPM made by the NT-MDT Company of Russia. A mechanically formed tip was made of an 80 ~m diameter platinum wire welded on a 0.3 mm diameter tungsten wire. STM was operated at a constant current mode with a bias voltage of 0.94 V and a setpoint current of 1.10 nA. The section analysis showed that the apparent height of SWCNTs was about 10 nm and the diameter was about 1.4 nm (fig. 1 ). Fig. 2 gives an STM current image of SWCNTs on the gold thin film. The STM worked at the condition of a constant bias voltage, with the tunneling current as the image signal. Known from the section analysis, the diameter of the electron emission area was about 1.4 nm, and the current of an SWCNT could reach about 30 hA. These results indicated that SWCNTs all stood discretely on the gold thin film surface, and that SWCNTs were able to transport electrons better than that of the gold thin film. The field emission properties of SWCNTs, which stood discretely on the surface of Au thin film, could be studied using field emission microscopy ( F E M ) . Short SWCNTs were assembled on a W tip and the whole tip was installed in an ultrahigh vacuum system, with the base vacuum above 3 x 10- 7 Pa. The distance between the tip and the phosphor screen was 5 cm. Field emission patterns could be observed when a 3 000V voltage was applied on the screen (the tip was grounded). Fig. 3(a) gives a field emission pattern of a single SWCNT, and fig. 3 ( b ) was a theoretically calculated electron cloud distribution on the open end of a ( 9 , 9 ) "armchair" SWCNT; they were consistent with each other. Fig. 3 ( a ) was a nearly atomic resolution pattern, which was astonishing because it was theoretically impossible to get an atomic resolution image using FEM with metal tips. These results indicated that these SWCNTs with open ends were metallic and the measure field emission current could reach I.LA. The electron beam emitted from SWCNTs was very thin and coherent probably, which nearly could be used as a coherent electron

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SCIENCE IN CHINA (Series A)

Vol. 43

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Fig. 1 STM topography image of SWCNTs standing on the surface of gold thin film. (a) Two-dimension image; (b) three-dimension image ; (c) section analysis. nA 30 3O

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SINGLE WALL CARBON NANOTUBES & THEIR ELECTRICAL PROPERTIES

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source with high luminance. Details of the field emission properties of SWCNTs will be published elsewhere.

(hi
Fig. 3. Field emission properties of SWCNTs. (a) Field emission pattern; (b) theoretically calculated electron cloud distribution on the open end of a ( 9 , 9 ) "armchair" SWCNT.

SWCNTs used as tips for STM

The properties of SWCNTs standing on the surface of gold thin film can be exploited in numerous areas. One interesting example is the use of SWCNTs as tips for SPMs. First tips for STM were successfully made of SWCNTs. To make sure whether the SWCNT did play an important role, we made a 1.0 mm diameter small ball at an end of a gold wire and assembled an SWCNT on the top of the gold ball as an STM tip, the schematic diagram was shown in fig. 4 ( a ) . The quality of such tips was examined by measuring the I ( z ) function, where I was the tunneling current and z was the distance between the tip and the sample. A typical I-z curve was shown in fig. 4 ( b ) . Usually a tip is good if the current is dropped to half of the start value in 10 angstroms; a tip is excellent enough to reach atomic resolution if the current is dropped to half of

(b)

Fig. 4.

(a) Schematic diagram of an STM tip made of SWCNT on the top of a gold ball; (b) l-z curve.

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SCIENCE IN CHINA (Series A)

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the start value in 3. This is a characteristic of our P47 SPM. The tip of an SWCNT was very good known (fig. 4 ( b ) ) . Fig. 5 ( a ) was an STM image of a gold thin film containing many crystal grains and had a very good depth of field on the topography, which demonstrated that the SWCNT tip could reach into deep trenches. STM was operated with a bias voltage of 0 . 9 4 V and current setpoint of 1 . 0 8 nA. An atomic resolution image of highly oriented pyrolytic graphite (HOPG) is shown in fig. 4 ( b ) , the bias voltage was 49 mV and the current setpoint was 0 . 5 5 nA. Such tips were very stable and reliable. The end of an SWCNT is open or has a hemisphere cap; its atomic structure and electronic states can be determined by calculations or experimental measurements. It is more convenient to do deconvolutions and thus the performance of STM can be improved when such tips are used to study samples.
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Fig. 5. STM image obtained with an STM tip made of SWCNT. (a) A crystal grain image of gold film; (b) an atomic resolution image of HOPG.

Electrical properties of short SWCNTs

The most promising application direction of carbon nanotubes is the exploration of nanoelectronics. Carbon nanotubes can be functional materials for nanoelectronic devices. They can also serve as conducting nanometer-scale wires. At present, most measurements on carbon nanotubes lying on silicon substrates were carried out at liquid helium or even lower temperatures due to very large environmental parameter effects El3'lSl . The electrical properties of SWCNTs, which stood on the surface of gold thin film, could be measured at high temperature because environmental effects were minimized drastically. After an STM image of SWCNTs was obtained, the tip was positioned on an SWCNT. When the tip touched the SWCNT, the feedback of the amplifier circuit was switched off and current versus voltage ( I - V ) curves of the junction between the Pt tip and the SWCNT were measured at room temperature in air. When I-V curves were reproducible several times, the last data was recorded. If the Pt tip did not touch an SWCNT, the scanning tunneling microscopy curves were different and unsymmetrical. Four typical I-V data were selected. Shown in fig. 6 ( a ) was an I-V curve. Fig. 6 ( b ) was its differential conductance versus voltage (dI/d V-V) curve. The normalized differential conductance is a measure of the density of states. There was a portion of every I-V curve in which the current was zero, corresponding to the smallest conductance in the dI/dV-V curve. According to the theoretical calculations and the experimental results of SWCNTs lying on the Si substrate Es'14] , SWCNTs can be metallic or semiconducting. The gap for the semiconducting SWCNTs is in the range between 0 . 5 eV to 0 . 7 eV. The lowest conductance width for the metallic SWCNTs ranges from 1.7 to 1.9 eV. Most of our

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SINGLE WALL CARBON NANOTUBES & THEIR ELECTRICAL PROPERTIES

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results were in this range, with only few exceptions. E s denotes the lowest conductance width. Four results were shown in table 1. The difference between our experimental results and those of other groups were large, for which the exact reason was not clear yet. The diameter of SWCNTs standing on the surface of gold thin film was 1.4 nm, and the length was about 10--15 nm. The difference in length could not result in so large a difference among the electrical properties. Especially, peaks appeared on the d I / d V - V curves of figs. 6 ( b ) and 6 ( c ) between which the distance was nearly the same. According to the tight binding calculations by Carrol et al. ~53, there existed resonant states in the valence band of the cap of SWCNTs, so peaks appeared in the density of states, which was the electron state distribution perpendicular to the axis of SWCNTs. But the electrical properties measured in our experiments were parallel to the axis of SWCNTs. There must be more resonant states if there were resonant states in the valence band, and the symmetry may be better under some conditions. Further studies on the electrical properties are in progress.
Table 1 Eg of SWCNTs measured parallelly to the axis of SWCNTs

No.
Es/eV

(a)
0.40

(b)
1.25

(c)
1.80

(d)
3.80

Conclusion

SWCNTs were synthesized by DC arc discharge method, a water colloid of short SWCNTs was prepared after SWCNTs were segregated, purified and cut short by oxidation. The water colloid of SWCNTs was used to assemble SWCNTs onto a gold film surface. Using STM tips made of SWCNTs, a crystal grain image of a gold thin film and an atomic resolution image of highly oriented pyrolytic graphite were successfully obtained. That SWCNTs stand on gold thin films is a promising technique for assembling and fabricating high-intensity coherent electron sources, field emission flat panel display, tips for scanning probe microscopes, new nanoelectronic devices, etc.

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Acknowledgements 69890221, 69701001).

This work is partially supported by the National Natural Science Foundation of China (Grant Nos.

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