Applied Surface Science 137 1999.

8390

The interaction of C 60 fullerene and carbon nanotube with Ar ion beam

Yongfa Zhu
b

a,)

, Tao Yi b, Bin Zheng a , Lili Cao

a Department of Chemistry, Tsinghua Uniersity, Beijing 100084, China State Key Laboratory of Rare Earth Materials Chemistry and Application, Peking Uniersity, Beijing 100871, China

Received 5 December 1997; accepted 17 July 1998

Abstract The interactions of C 60 fullerene and carbon nanotube with Ar ion beam have been studied using XPS and AES in-situ techniques. The studies have shown that the shake-up peaks of C 1s and the valence band peaks of XPS in a C 60 film disappear after it is irradiated with Ar ion beam. The conjugated p bonds in a C 60 molecule are disrupted, and the ball structure of a C 60 molecule is also destroyed by Ar ion beam. After a C 60 film is irradiated with Ar ion beam, the binding energy of C 1s decreases about 0.3 eV and the kinetic energies of C KLL in XAES and in EAES increase about 1.9 and 1.5 eV, respectively. A new kind of carbon species, which does not contain the conjugated p bonds but keeps still sp 2 hybridization, is formed. The shake-up peak of C 1s in carbon nanotube disappears also after it is bombarded with Ar ion beam. After carbon nanotube is irradiated with Ar ion beam, two characteristic peaks that are related to the dangling bonds in amorphous carbon appear in 9.6 and 22.6 eV. In contrast to the results of C 60 , the binding energy of C 1s increases 0.15 eV and the kinetic energy of C KLL in XAES decreases 1.6 eV after carbon nanotube is bombarded with Ar ion beam. The conjugated p bonds and the tube structure of carbon nanotube are destroyed by Ar ion beam. The carbon nanotube is changed into an amorphous carbon rod. q 1999 Elsevier Science B.V. All rights reserved.
Keywords: C 60 fullerene; Carbon nanotube; Ar ion beam; Irradiation

1. Introduction The discovery of the carbon-cage fullerenes w1x and the development of techniques w2x for producing sizable quantities of them have led to intensify the studies on the structure, the properties and their chemical reaction. Many investigations on C 60 materials have been focused on several topics; the separation, new properties and fullerene derivatives w36x. Recently, the surface chemistry and surface modifiCorresponding author. Tel: q86-10-62783586; Fax: q86-1062770327; E-mail: zhuyf@sam.chem.tsinghua.edu.cn
)

cation of C 60 materials abstracted also many researchers w7,8x. Due to the truncated icosahedron structure and semiconductor properties, C 60 materials possess a good prospect to be applied in lubrication, coating, non-linear optical device and electronic device. Besides, carbon nanotube is also a new kind of nano materials of carbon, which is an excellent electronic conductor and holds special mechanical properties due to its pipe structure w911x. Recently, great deals of studies have been stimulated on carbon nanotube w1215x. Because the irradiation of ion beam is an important method to modify and form new carbon materi-

0169-4332r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved. PII: S 0 1 6 9 - 4 3 3 2 9 8 . 0 0 3 7 2 - 9

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als, it is very important to understand the interaction mechanisms of carbon materials with ion beam. This paper has been focused on the interaction mechanism of carbon nano materials with Ar ion beam and the formation of new carbon species. The in-situ techniques of XPS and AES have been adopted to investigate this interaction. The results show that the conjugated p bonds in C 60 and carbon nanotube can be broken by Ar ion beam. The new carbon species formed by Ar ion beam still consists of sp 2 hybridized carbon and contains dangling bonds. But the sp 2 hybridized carbon does not form conjugated p bonds. The ball structure in C 60 and the tube structure in carbon nanotube have been destroyed by Ar ion beam. In addition, the carbon nanotube is deteriorated into an amorphous carbon by Ar ion beam.

keV and 0.5 mA, respectively. The electron beam is incident at an angle of 608 with respect to the specimen surface. During irradiation of Ar ion beam, the energy and beam current of Ar ion beam is 3.0 keV and 6 mA, respectively. The beam is focused to a spot of 1 = 1 mm and the sputtering rate is about 40.0 nmrmin for a thermally oxidized SiO 2 thin film.

3. Results 3.1. The interaction of C6 0 molecules with Ar ion beam Due to the conjugated p bonds in a C 60 molecule, C 1s spectrum of the C 60 material contains many shake-up peaks, which are the characteristic features of a C 60 molecule and can be used to study the interaction of the C 60 material with Ar ion beam. The C 1s spectra of the C 60 material varied with different irradiation conditions of Ar ion beam are shown in Fig. 1. From this figure, it can be seen that the peak shape of C 1s is very narrow and symmetric. The binding energy and the FWHM of the C 1s peak in the C 60 film is 284.7 and 1.05 eV, respectively, which are in good agreement with the Ref. w5x. After the C 60 film is irradiated with a low

2. Experimental The C 60 materials purified using high pressure liquid chromatography is adopted in this work. The C 60 film is prepared by sublimation powder of C 60 from Mo boats, which is resistively heated to 4508C in ultrahigh vacuum, and deposited on the substrate of Si111.. The thickness of the C 60 film is about 400 nm. The carbon nanotube powder is pressed as a plate on silicon wafer directly. The XPS spectra are measured in a PHI 5300 ESCA system. During XPS analysis, Mg K a X-ray beam is adopted and power is set to 250 W. A hemispherical analyzer and a position sensitive detector with a pass energy of 17.25 eV is adopted. The base vacuum of chamber is maintained at 2 = 10y9 Torr during XPS analysis. During the irradiation of Ar ion beam, the beam energy can be adjusted from 1.0 to 4.0 keV, and the ion beam current can be held at 0.4 mA and 20 mA at a spot of 8 = 8 mm in a low density and a high density Ar ion beam mode, respectively. The sputtering rate is about 0.1 nmrmin and 5.0 nmrmin for a thermally oxidized SiO 2 thin film, respectively. The AES spectra are measured in a PHI 610 SAM system. A coaxial electron gun and a single pass cylindrical mirror analyzer CMA. are used. The energy resolution of the CMA is set to 0.3% to obtain a good energy resolution. For AES analysis, the electron beam energy and the beam current is 3.0

Fig. 1. The C 1s spectra of a C 60 film varied with irradiation beam density of Ar ion beam.

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density Ar ion beam, the binding energy of C 1s decreases from 284.7 to 284.4 eV and the FWHM of C 1s increases from 1.1 to 1.8 eV. After the C 60 film is irradiated with a high-density Ar ion beam, the binding energy of C 1s decreases to 284.3 eV and the FWHM of C 1s increases to 2.0 eV. Although the peak shape of C 1s is broaden by Ar ion beam, it is still very symmetric. From this figure, it can also be found that the shake-up peaks of C 1s which is related to pp ) excitation w5x disappear after the C 60 film is bombarded by Ar ion beam. There are seven peaks in the valence band spectrum of the C 60 material that are derived from the pp , sp , and ss orbits of a C 60 molecule w6x. These characteristic peaks can also be used to investigate the interaction of the C 60 material with Ar ion beam. Fig. 2 shows the valence band spectra of the C 60 film varied with irradiation condition. From this figure, it can also be seen that the line shape of the valence spectrum has been changed greatly after the C 60 film is irradiated with Ar ion beam. When the density of Ar ion beam is low, seven characteristic peaks of the C 60 material disappear and a broaden peak appears. When the density of Ar ion beam is high, the result is quite different. The seven characteristic peaks of the C 60 material also disappear but

Fig. 3. The XAES C KLL spectra of a C 60 film varied with irradiation time of Ar ion beam. A: C 60 film, B: irradiated by low density Arq beam, 3 keV 30 min, C: irradiated by high density Arq beam, 3 keV 30 min.

there appear two new characteristic peaks at 9.6 and 22.6 eV. The interaction between the C 60 film and Ar ion beam has also been studied using line shape techniques of XAES and EAES. The XAES C KLL line shapes with various irradiation conditions are shown

Fig. 2. The valence band spectra of a C 60 film varied with irradiation time of Ar ion beam. A: C 60 film, B: with low density Arq beam, 3 keV 30 min, C: with high density Arq beam, 3 keV 30 min, D: with high density Arq beam, 3 keV 210 min.

Fig. 4. The AES C KLL spectra of a C 60 film before and after irradiated with Ar ion beam.

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Fig. 5. The AES C LVV spectra of a C 60 film before and after irradiated with Ar ion beam.

Fig. 6. The C 1s spectra of carbon nanotube varied with radiation time of Ar ion beam.

in Fig. 3. The spectra indicate that the kinetic energy of a pure C 60 film is 265.5 eV and is shifted to 267.4 eV after the C 60 film is irradiated with Ar ion beam. Although the interaction with ion beam results in the increase of the C KLL kinetic energy, the line shape and peak position have not been changed by the beam density. The EAES spectra of the C KLL line shape in differentiation mode are shown in Fig. 4. The figure indicates that the kinetic energy of C KLL has been increased from 270.5 to 272.0 eV and a small threshold peak appears in high kinetic energy side after the C 60 film is bombarded by Ar ion beam. Fig. 5 is the C LVV spectra of the C 60 film before and after bombarded with Ar ion beam. From this figure, it can be seen that the two characteristic peaks of the C 60 film at 14.0 and 19.9 eV disappear after bombarded with Ar ion beam. 3.2. The interaction of carbon nanotube with Ar ion beam The interaction of carbon nanotube with Ar ion beam has also been studied using XPS and AES in situ. Fig. 6 indicates that the binding energy of C 1s in carbon nanotube is 284.60 eV and increases to 284.75 eV after carbon nanotube is bombarded with Ar ion beam. The FWHM of C 1s peaks also increases with irradiation time, but the shape of peaks

is still very symmetric. It can also be seen that the shake-up peak of C 1s, which is the characteristic peak of carbon nanotube, decreases with the irradiation time. These results also indicate that the structure of carbon nanotube has been changed and a new kind of carbon species, which does not contain conjugated p bonds, is formed after carbon nanotube is irradiated with Ar ion beam. The valence band spec-

Fig. 7. The valence spectra of carbon nanotube varied with radiation time of Ar ion beam. A: graphite carbon, B: carbon nanotube, C: spt. 30 min, D: spt. 210 min.

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Fig. 8. The XAES C KLL spectra of carbon nanotube before and after irradiated with Ar ion beam. A: carbon nanotube, B: spt. 30 min, C: spt. 210 min, D: graphite carbon.

tra of carbon nanotube are also shown in Fig. 7. It indicates that the line shape of XPS valence band in carbon nanotube is very similar to that in graphite carbon due to similar layer structure. After carbon

nanotube is irradiated with Ar ion beam, two characteristic peaks at 9.6 and 22.6 eV appear in XPS valence band spectra. This result is similar to that of C 60 . The XAES technique has also been used to study the interaction of carbon nanotube with Ar ion beam. The XAES C KLL spectra are shown in Fig. 8. From this figure, it can be seen that the kinetic energy of carbon nanotube is 267.9 eV and decreases to 266.3 eV after it is irradiated with Ar ion beam. This is different from the results of graphite in which the kinetic energy and the line shape almost remain unchanged with irradiation time of ion beam. It is opposite with the result of the C 60 film in which the XAES kinetic energy is increased from 265.5 to 267.4 eV. The effect of Ar ion beam on the micro-structure of carbon nanotube has been studied using TEM technique. The TEM result is shown in Fig. 9. We can see that every carbon nanotube has a pipe structure and the diameter of the tube is about 10 nm. After carbon nanotube is irradiated with Ar ion beam, the tube structure of carbon nanotube disappears gradually and the carbon nanotube becomes a

Fig. 9. The TEM results of carbon nanotube before and after irradiated with Ar ion beam. A: carbon nanotube, B: irradiated with Ar ion beam.

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nano-rod. In addition, the electron diffraction also indicates that the nano-rod is amorphous carbon.

4. Discussion The binding energy of C 1s in the C 60 film is related to the chemical environment of carbon atoms in a molecule. In a C 60 molecule, every carbon atom is in the same chemical environment due to the formation of delocalization conjugated p bonds. So, there is only a narrow peak in C 1s spectrum of the C 60 film. In order to form the delocalization conjugated p bonds; every carbon atom in a C 60 molecule has to contribute partial electron charges. Comparing with a free carbon atom, each carbon atom in a C 60 molecule has to lose partial electron charge. According to electrostatic theory of XPS, the loss of electron charge in an atom will decrease the binding energy. The binding energy of C 1s decreases from 284.7 to 284.4 eV after the C 60 film is bombarded by Ar ion beam, providing an evidence that the interaction with Ar ion beam let carbon atoms obtain some extra electron charges which come from the delocalization conjugated p bonds in C 60 molecules. The irradiation of Ar ion beam results in the disruption of the conjugated p bonds, which make partial electron charges be transferred into carbon atom from p bonds. From above results, it can be concluded that the conjugated p bonds in C 60 molecules have been broken down after the C 60 film is bombarded with Ar ion beam. In general, the carbon atom can exist in three kinds of hybridization bonds; sp, sp 2 and sp 3 hybridization. In C 60 and carbon nanotube, one carbon atom connects with the other carbon atom with sp 2 hybridization bonds to form the delocalization-conjugated p bonds. The evidences that the binding energy of C 1s is closed to 284.7 and the peak shape of C 1s is still very symmetric imply that the carbon atom still exist in sp 2 hybridization because the binding energy of C 1s in a sp 2 hybridized carbon and a sp 3 hybridized carbon is 284.7 and 285.75 eV, respectively w16x. It can be sure that the decrease of the C 1s binding energy after the C 60 material is irradiated with Ar ion beam is not caused by the formation of sp 3 hybridization but by the disruption of conjugated p

bonds. The new carbon species still connects with sp 2 hybridization bonds. According to Auger theory, the increase of kinetic energy is related to the loss of electron charge. The kinetic energy of XAES C KLL in the C 60 film increases from 265.5 to 267.4 eV and that of EAES C KLL increases from 270.5 to 272.0 eV after the C 60 film is bombarded with Ar ion beam. These results of C KLL also suggest that carbon atom obtains some extra electron charges after the C 60 film is irradiated with Ar ion beam. It is concordance with the conclusion of XPS. According to Ref. w17x, it can be known that the XAES C KLL kinetic energy of sp 2 hybirizated carbon is about 7 eV higher than that of sp 3 hybirizated carbon. Besides, there are two shoulder peaks at 242 and 250 eV for sp 3 hybirizated carbon. Based on above results, the kinetic energy shifts are much lower than 7 eV and there is only one shoulder peak at 242 eV in XAES C KLL spectra. It can be concluded from this evidence that the interaction of Ar ion beam does not change the sp 2 hybridization into sp 3 hybridization of carbon. It is also in good agreement with the conclusion of C 1s. Besides, the change of the C LVV line shape is also indicated that the structure of the C 60 film has been changed after bombarded with Ar ion beam. Otherwise, the shoulder peak, which appears on the high kinetic energy side in EAES CKLL spectrum, also indicates that the interaction of Ar ion beam has caused the formation of dangling bonds w16x. The shake-up peaks of C 1s in the C 60 film are produced by pp ) excitation of the conjugated C5C bonds. These peaks are the characteristic features of delocalization p bonds of the C 60 film. After the C 60 film is interacted with Ar ion beam, the shake-up peaks of C 1s in the C 60 film disappears gradually. This indicates that the conjugated p bonds of a C 60 molecule are disrupted by Ar ion beam. The disappearance of valence band features also indicates that the structure of a C 60 molecule has been changed and formed a new kind of carbon species. The evidence that the line shape of valence band spectrum depends on the density of Ar ion beam means that a low density Ar ion beam only causes the disruption of the conjugated p bonds, but a high density Ar ion beam causes not only the disruption of the conjugated p bonds but also the

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formation of dangling bonds. These results also lead to the same conclusion as that from C 1s and C KLL spectra. Based on the above discussion, the increase of the C 1s binding energy of carbon nanotube results also from the disruption of the conjugated p bonds due to the irradiation of Ar ion beam. The increase of the C 1s binding energy implies that carbon atom in carbon nanotube loses some extra electron charges after carbon nanotube is irradiated with Ar ion beam. This conclusion also has been proved by the results of XAES C KLL spectra. The decrease of the C KLL kinetic energy means also that carbon atom loses some extra electron charges according to Auger theory. After carbon nanotube is bombarded with Ar ion beam, the peak shape of C 1s is still symmetric implies that the carbon atoms still exist in sp 2 hybridization though the conjugated p bonds have been destroyed. The disappearance of the C 1s shake-up peak indicates also the disruption of conjugated p bonds in carbon nanotube. The disruption of conjugated p bonds in carbon nanotube changes also the line shape of the valence band spectrum. The graphite-like peak has been changed and two characteristic peaks appear in valence band spectrum. These two peaks can be attributed to surface dangling bonds of carbon atoms w16x. Because the layer structure of carbon nanotube is dependent on the conjugated p bonds, the disruption of the conjugated p bonds results in the destroying of layer structure after the irradiation with Ar ion beam. TEM result gives obvious evidence that the lattice structure of carbon nanotube also becomes unordered and formed an amorphous structure after irradiated with Ar ion beam. These results also indicate that the carbon nanotube has been disrupted and forms a new carbon species, which consists of unconjugated sp 2 hybridization bonds and dangling bonds. From above discussions, it can be concluded that the interaction mechanism and the carbon species is different though the disruption of conjugated bonds and the formation of un-conjugated sp 2 hybridization carbon is the same after the C 60 film and carbon nanotube are irradiated with Ar ion beam. The disruption of conjugated p bonds let carbon atoms obtain extra electron charge in a C 60 film and lose electron charge in carbon nanotube. The density of

Ar ion beam can affect the deteriorated product of the C 60 film and does not affect that of carbon nanotube. After the C 60 film and carbon nanotube are irradiated with Ar ion beam, the binding energy of C 1s and the kinetic energy of C KLL is also different. This result indicated also the deteriorated products of these two nano carbon materials are different though these products possess the same sp 2 hybridized carbon bonds and dangling bonds. 5. Conclusion 1. After a C 60 film is irradiated with Ar ion beam, the binding energy of C 1s decreases from 284.7 to 284.4 eV and the kinetic energy of XAES C KLL increases from 266.5 to 267.4 eV. In contrast to the C 60 film, the binding energy of C 1s increases and the kinetic energy of C KLL decreases for carbon nanotube. The shake-up peaks of C 1s also disappear gradually with the irradiation time. 2. The interaction of the C 60 film with Ar ion beam results in the disruption of the conjugated p bonds and the damage of molecule structure. Finally, the C 60 molecule is decomposed and formed small carbon species, which does not contain conjugated p bonds but contains the sp 2 hybridization bonds and dangling bonds. 3. The interaction of carbon nanotube with Ar ion beam destroyed the conjugated p bond, the layer and tube structure. The carbon nanotube is deteriorated into a nano-rod that is consisted of amorphous carbon and contains many dangling bonds after irradiated by Ar ion beam. This new carbon species does not contain conjugated p bonds though the carbon atom is sp 2 hybirizated. Acknowledgements This work was partly supported by a 1997 Grantin-Aid for Scientific Fundament Research of Tsinghua University and by State Key Laboratory of Rare Earth Materials Chemistry and Application. References
w1x H.W. Kroto, J.R. Heath, S.C. OBrien et al., Nature 318 1985. 162.

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Y. Zhu et al.r Applied Surface Science 137 (1999) 8390 w10x D.H. Roberston, D.W. Brener, J.W. Mintmire, Phys. Rev. B 45 1992. 12592. w11x H. Dal, E.W. Wong, Y.Z. Lu, S.S. Fan, C.M. Lieber, Nature 375 1995. 769. w12x T.W. Ebbesen, H. Hiura, M.E. Bisher, M.M.J. Treacy, J.L. Shreeve-Keyer, R.C. Haushalter, Adv. Mater. 8 2. 1996. 155. w13x R. Sen, B.C. Satishkumar, G. Raina, R. Gargi, C.N.R. Rao, Fullerene Sci. Technol. 5 3. 1997. 489. w14x B. Wei, J. Zhang, J. Liang, W. Liu, Z. Gao, D. Wu, J. Mater. Sci. Lett. 16 5. 1997. 402. w15x O. Chauvet, L. Forro, L. Zuppiroli, W.A. De Heer, Synth. Met. 86 1997. 2311. w16x S.T. Jackson, R.G. Nuzzo, Appl. Surf. Sci. 90 2. 1995. 195. w17x A.P. Dementjev, M.N. Petukhov, Surf. Interface Anal. 24 1996. 517.

w2x Y. Wang, Nature 356 1991. 385. w3x J.J. Carlisle, C.A. Wijayawardhana, T.A. Evans, P.R. Melaragno, I.B. Ailin-Pyzik, J. Phys. Chem. 100 38. 1996. 15532. w4x K. Kim, H.J. Kim, G.S. Oh, C. Jeon, B.J. Ahn, Anal. Sci. Technol. 8 4. 1995. 675. w5x T.R. Ohno, Y. Chen, S.E. Harvey, G.H. Kroll, P.J. Benning, J.H. Weaver, Phys. Rev. B 47 4. 1993. 2389. w6x J.J. Carlisle, C.A. Wijayyawardhana, T.A. Evans, P.R. Melaragno, I.B. Ailin-Pyzik, J. Phys. Chem. 100 38. 1996. 15532. w7x M.M. Cordero, T.J. Cornish, R.J. Cotter, J. Am. Soc. Spectrom. 7 6. 1996. 590. w8x O.V. Boltalina, V.Y. Markov, A.Y. Lukonin, T.V. Avakjan, D.B. Ponomarev, I.D. Sorokin, L.N. Sidorov, Proc. Electrochem. Soc. 95 10. 1995. 1395. w9x S. Ijima, Nature 354 1991. 56.