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1 LENGTH DEPENDENCE OF ULTRAFAST OPTICAL NONLINEARITIES IN VERTICALLY ALIGNED MULTIWALLED CARBON NANOTUBE FILMS Hendry Izaac Elim (Elim Heaven),1#,2 Yanwu Zhu,3 and Chorng-Haur Sow4 1 Nanomaterials for Photonics Nanotechnology Laboratory (Lab. N4PN), Physics Department, Faculty of Mathematics and Natural Sciences, 2 Research Center of Nanotechnology and Innovative Creation (PPNRI-LEMLIT), Pattimura University, Ambon, Indonesia 97233 3 Department of Materials Science and Engineering, University of Science and Technology of China, 96 Jin Zhai Rd., Hefei 230026 4 Department of Physics, National University of Singapore 2 Science Drive 3, Singapore 117542, Republic of Singapore #Email: [email protected]; [email protected] Telp. (+62-81247524158) Abstract Tube-length-dependent optical nonlinearities of vertically aligned multiwalled carbon nanotube (MWNT) films have been investigated by Z-scan and transient absorption measurements with femtosecond laser pulses in the near-IR spectral range from 780 to 1550 nm. Both saturable absorption and optical Kerr nonlinearity are found to be dependent on excitation wavelength and tube length, indicating that band-filling in semiconducting tubes and longitudinal surface plasmon resonance in metallic tubes play an important role, respectively. The 1-ps relaxation time for the nonlinear response of the MWNT films, however, is independent of tube length, as evidence from dissipation of excited energy in the radial direction. Such ultrafast vertically length-dependent in CNT can significantly contribute to fabricate vertically nanochip in various types of integrated nanodevice just like a creation of living 3D fish bone (a kind of cowfish). Keywords: Carbon nanotubes, Nonlinear Optics, Nanochip, Ultrafast Introduction Recently, ultrafast nonlinear-optical (NLO) responses of single-wall carbon nanotubes (SWNTs) in suspensions and films have received increasing attention.1-6 At resonant band (0.8-1.1 eV) of the lowest inter-band transitions of semiconducting SWNTs, a strong transient photo-bleaching has been observed with femtosecond laser 2 pulses. The strongest imaginary part of the third-order NLO susceptibility, (3) has been determined as large as 10-7 to 10-6 esu.5,7 Moreover, at the second lowest inter-band transitions (~1.6 eV) of semiconducting electronic structure in SWNTs, saturable absorption has also been detected using femtosecond laser pulses. In contrast, photoinduced absorption has been measured under off-resonant conditions of SWNTs. The band-filling effects have been identified as the mechanism responsible for the resonant saturable absorption, while the off-resonant photo-induced absorption is attributed to a global red-shift of the -plasmon resonance.3 These investigations have been so far focused on the ultrafast NLO responses of SWNTs. ……………………………………………………………………………………… ……………………………………………………………………………………………… Experimental Method MWNTs studied in our experiment were grown on quartz substrate. The MWNTs were prepared by a method of plasma-enhanced chemical vapor deposition. The details on the preparation were reported elsewhere.10-11 Figures 1(a)-(c) show high magnification scanning electron microscopy (SEM) images of the films with three different lengths of MWNTs. As shown by these images, the nanotubes were grown mainly in the direction perpendicular to the surface of the quartz substrate. As the MWNTs were grown longer, the higher order in alignment could be evident. There was no significant difference in the outer-layer diameter (~20 nm) of nanotubes for the three films. Both linear optical and NLO properties of the MWNT films were examined as the light propagates in the axis perpendicular to the quartz substrate (or normal incidence on the film) at room 3 temperature. In Fig. 1(d), the near-IR spectra of the MWNT films with L = 4 m, 7 m and 12 m show a feature centered at ~1100 nm, which is assigned to the second lowest interband transitions in semiconducting MWNTs. It unambiguously indicates the existence of semiconducting nanotubes in the films, though they are predominated by metallic nanotubes. The feature decreases to a minimum at ~1400 nm, where the appearance of complex transitions is noticeable, reflecting the complex interplay of various chiral indices (n, m) for different sizes and structures of nanotubes. As the wavelength increases further, the absorbance arises due to be resonant with the lowest interband transitions. ……………………………………………………………………………………… ……………………………………………………………………………………………… Results and Discussions Figure 2(a) illustrates a relationship inspiration of a 3D bone of fish called as “poro bibi” fish (a type of cowfish living in east Africa) in Ambon, Indonesia with an interaction of elastically graphene like structure associated with man-made interaction between 3D vertically aligned MWNTs and laser beams with two different beam waists. We thought in our opinion as the aim of such good illustration was that the created 3D structure of living creature had been there in nature before the MWCNT structure was discovered by man (Ijima, ~1991 at NEC company, Japan). Moreover, this illustration is necessary to open the insight of many different physicist or multidisciplinary scientists to elaborate and extend their work in the near future as an integrated research. 4 ……………………………………………………………………………………… ……………………………………………………………………………………………… Conclusion In summary, we have presented, for the first time, the wavelength and tube-length dependence of NLO properties in vertically aligned MWNT films, determined with femtosecond Z-scans and pump-probe measurements. The wavelength and tube-length dependence are attributed to the semiconducting and metallic properties of MWNTs. ……………………………………………………………………………………………… ……………………………………………………………………………………………… Acknowledgement We would like to thank the support of H.I. Elim current research works from a fund granted by “Riset Unggulan Daerah” grant no. 1039/UN13/SK/2015, Pattimura University, Indonesia about superfibers project. ……………………………………………………………………………………………… References (1) Wang, S.; Huang, W.; Yang, H.; Gong, Q.; Shi, Z.; Zhou, X.; Qiang, D.; Gu, Z. Large and Ultrafast Third-order Optical Non-linearity of Single-wall Carbon Nanotubes at 820 nm. Chem. Phys. Lett. 2000, 320, 411-414. (2) Chen, Y.C.; Raravikar, N.R.; Zhao, Y.P.; Schadler, L.S.; Ajayan, P.M.; Lu, T.M.; Wang, G.C.; Zhang, X.C. Ultrafast Optical Switching Properties of Single-wall Carbon Nanotube Polymer Composites at 1.55 μm. Appl. Phys. Lett. 2002, 81, 975-977. 5 (3) Lauret, J-S. ; Voisin, C. ; Cassabois, G. ; Delalande, C. ; Roussignol, Ph.; Jost, O.; Capes, L. Ultrafast Carrier Dynamics in Single-Wall Carbon Nanotubes. Phys. Rev. Lett. 2003, 90, 057404-057407. (4) Han, H.; Vijayalakshmi, S.; Lan, A.; Iqbal, Z.; Grebel, H.; Lalanne, E.; Johnson, A.M. Linear and Nonlinear Optical Properties of Single-walled Carbon Nanotubes Within an Ordered Array of Nanosized Silica Spheres. Appl. Phys. Lett. 2003, 82, 1458-1460. (5) Tatsuura, S.; Furuki, M.; Sato, Y.; Iwasa, I.; Tian, M.; Mitsu, H. Semiconductor Carbon Nanotubes as Ultrafast Switching Materials for Optical Telecommunications. Adv. Mater. 2003, 15, 534-537. (6) Ostojic, G.N.; Zaric, S.; Kono, J.; Strano, M.S.; Moore, V.C.; Huage, R.H.; Smalley, R.E. Interband Recombination Dynamics in Resonantly Excited SingleWalled Carbon Nanotubes. Phys. Rev. Lett. 2004, 92, 117402-117405. ……………………………………………………………………………………………… ………………………………………………………………………………………………. Figure Captions: Fig. 1 (Color online) SEM images of aligned MWNT films with average tube length of (a) 4 m, (b) 7 m, and (c) 12 m. (d) Absorption spectra provided with the whole UV-VIS-NIR spectra. 6 Table Captions and Table Table 1. Types of carbon nanotubes (CNT) and their nonlinear optical properties. Types Nonlinear Ultrafast Behavior Response Single Walled Carbon Nanotubes (SWCNT) …….. …….. Multiwalled Carbon Nanotubes (MWCNT) …….. …….. Hybrid Polymer CNT …….. …….. Hybrid inorganic nanoparticles coated CNT …….. ……..