単層カーボンナノチューブとグラフェンの応用 Application of Single-Walled Carbon Nanotubes and Graphene

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1 Molecular Thermo-Fluid Engineering 2013 単層カーボンナノチューブとグラフェンの応用 Application of Single-Walled Carbon Nanotubes and Graphene 丸山茂夫 Shigeo Maruyama 東京大学大学院工学系研究科機械工学専攻

2 Application of CNTs (1) Sumsong Noritake A.T.Woolley et al(2000) Nanowires C. Dekker, Delft FET Biosensor Field Emission NEC Tips of AFM Endo, JJAP (2006) Li Ion Battery Electrode of Fuel Cell Hydrogen Storage?

3 Application of CNTs (2) Yakobson et al. (1996) (5,5) SWNTs x 1.6 m atoms Composite Material Conductive Plastic Mechanical Strength Maruyama-Shiomi (2006) Thermal Device Super Capacitor Alnair Lab. Mode-locked Pulse laser (Saturable absorbance) Z. Wu et al., Science (2004) Transparent Conductive Film T. Hatanaka et al. ECS Trans. (2006) Electrode of Fuel Cell

4 Electrode of Fuel Cell VA-MWNTs+Pt TOYOTA FCHV BOOK Better O2 access, Better Proton/Electron Transfer, Higher Durability T. Hatanaka et al. ECS Trans. (2006)

5 Transparent Conductive Film Kaili Jiang Fei Wei Shoushan Fan Yan Li Rong Xiang

6 Transparent Conductive Film State of the art : 84 90% Kauppinen Group at Aalto Univ. Nasibulin et al. ACS Nano 5, 3214 (2011)

7 Field Effect Transistor (FET) 電界効果トランジスタ Source CNT Channel Drain SiO 2 Gate Highly Doped Si (a) C. Dekker, Delft (b) (a) Aikawa et al., 2011

8 Vertically Aligned SWNTs on Quartz Substrate Diameter (nm) Intensity (arb. units) Dr. Yoichi Murakami Raman Shift (cm ) 10 m 25 nm Y. Murakami, S. Chiashi, Y. Miyauchi, M. Hu, M. Ogura, T. Okubo, S. Maruyama, Chem. Phys. Lett. 385 (2004) 298

9 Selective Deposition of Catalyst for Facile Localized Growth of SWNTs Dr. Rong Xiang R. Xiang, T. Wu, E. Einarsson, Y. Suzuki, Y. Murakami, J. Shiomi, S. Maruyama, J. Am. Chem. Soc., 131, 10344(2009).

10 Patterned growth of SWNT for FET (a) SEM image (b) Raman spectrum Diameter (nm) SAM removal region (SWNT film) 1 mm Intensity (arb. units) m : 488 nm Raman Shift (cm 1 ) 300 m 50 m

11 Properties of all-swnt FET D V D S S SWNT electrode 0 V GS = 10 [V] G V G S Output characteristics R on : 370 k 10 6 SWNT channe 5 m l Transfer characteristics I D [ A] 8 [V] I D [A] 10 8 I ON /I OFF : [V] [V] 2 [V] 0 [V] 2 [V] Room Temp V DS [V] V DS = 1 [V] Room Temp V GS [V]

12 Flexible all-swnt FET S. Aikawa, E. Einarsson, T. Thurakitseree, S. Chiashi, E. Nishikawa, S. Maruyama, Appl. Phys. Lett., (2012),

13 Thin Film Network FET D-M. Sun et al., Nature Nanotech. 6, 156 (2011) From Esko Kauppinen Seminar at Aalto Univ.

14 Horizontally Aligned Growth on Crystal Quartz Z ST-cut Pristine AT-cut R-cut R ST-cut AT-cut r Z-cut m Y-cut Y r m X-cut X Annealed 13 h R-cut R m r X X Z 20μm S. Chiashi et al., J. Phys. Chem. C, 116 (2012) T. Inoue et al., Carbon, submitted.

15 High Speed FET John A. Rogers Group (University of Illinois), Jie Liu (Duke University), Avouris (IBM) C. Kocabas et al., JPC C, 111(2007) S. J. Kang et al., Nature Nanotech. 2 (2007) 230.

16 Saturable Excitonic Absorption unsaturated low optical intensity saturable absorber high optical intensity saturated n electron hole excited state ground state photon absorption site (ground state) absorption site (excited state) Applications to passively mode-locked fiber lasers Professor Ref: S. S.Y.Set, Yamashita OFC 03, PD44 Group S.Y.Set, CLEO 03, CThPDA9 Dr. Alnair Labs Co.

17 Saturable Absorbers: Application to Mode-Locked Fiber Lasers 980nm pump LD 40cm F:EDFA isolator 980/1550 coupler isolator collimator lens collimator coupler 70% 10 m spot size SAINT sample 30% isolator output S. Yamashita, S. Maruyama, Y. Murakami, Y. Inoue, H. Yaguchi, M. Jablonski, S. Y. Set, Optics Letters, 29 (2004) 1581.

18 All Fiber Passive Mode-Lockers VA-SWNT Film Isolator LP 01 -Y (Full Interaction w/ CNTs) kz EDFA LP 01 -X (Non-interaction w/ CNTs) VA-CNT Film-Coated D-Shaped Fiber (Passive Mode-Locker) PC Core 5/95 Coupler Isolator Laser Output Conceptual Description of Aligned Individual CNTs Commercial Mode-Lock Fiber Laser with SWNTs by Alnair Labs Y.-W. Song, E. Einarsson, S. Yamashita, S. Maruyama, Optics Letters, 32 (2007) Y.-W. Song, S. Yamashita, S. Maruyama, Appl. Phys. Lett., 92 (2008) (a) Output (dbm) (b) Output (a.u.) FWHM: 0.5 nm Wavelength (nm) 174 ns Time (ns)

19 NanoFluid (1) Maxwell s model When K p >> K f J.A. Eastman, S.U.S. Choi, W. Yu, L.J. Thompson, Appl. Phys. Lett. 78, 718, P. Keblinski, J.A.Eastman, D. Cahill, Materials Today,36, Thermal Conductivity Ratio ( k eff /k f ) Water + SWCNT EG + SWCNT Nanotube Loading (wt %) S.Harish, K. Ishikawa, E. Einarsson, S. Aikawa, S. Chiashi, J. Shiomi, S. Maruyama, Int. J. Heat Mass Transf, 55(13-14), 3885, 2012.

20 NanoFluid (2) Phase Change Material Contrast Ratio Present experiments Zheng et al [9] (b) 1.5 R.Zheng, J. Gao, J. Wang, G. Chen, Nature Comm. 2,289, Thermal Conductivity (W m 1 K 1 ) Solid state Nanomaterial Loading (wt %) n Octadecane (OD) OD wt % SWCNT OD wt % SWCNT OD wt % SWCNT OD wt % SWCNT Liquid state Temperature (K) S. Harish et al. to be submitted.

21 Bulk SWNT materials for thermal applications Moore s law SWNT films for ITM High thermal conductivity Mechanical flexibility Chip Heat Spreader Heat Sink 10 m Source: Pat Gelsinger ISSCC 2001 <<Individual SWNT T-reflectance (O-assisted) Laser flash (Super growth) 3-omega (ACCVD) Futaba etal, ACS Nano (2008), Panzer etal, J. Heat Trans. (2008) Akoshima etal, JJAP (2009) Ishikawa etal. (2008)

22 Dye-sensitized solar cell Photo electrode TiO 2 paste Squeeze on FTO ethanol 10ml N719Dye 3.5mg min sintering 24 hour Counter electrode 100 [mw/cm 2 ] AM1.5G Pt sputtered on FTO SWNT measurment [1]M. Gratzel, et al., J. Electrochem. Soc., 144(1997)876. [2]B. Li, et al., Sol. Mater., 90(2006)549. [3] K. Schwartburgell, et al., J. Phys. Chem. B, 103(1999)5743. FTO (a) (b) (c) (d)

23 Dye-sensitized solar cell (VA-SWNTs) 15 Curent Density [ma/cm 2 ] 10 5 Pt Air brush SWNT VASWNT Z"[Ω] kHz Pt Air brush SWNT VA SWNT 10Hz Voltage [V] 0 0.1MHz 0.1Hz Z'[Ω]

24 CNT-Si Heterojunction Solar Cell Three-dimensional view SWNT-Si Cell 20 5mm random honeycomb quasi- honeycomb Cross-sectional view J (ma/cm 2 ) Bias (V)

25 CNT-Si Heterojunction Solar Cell J V Plot of Micro Honeycomb SWNT/Si Heterojunction J (ma/cm 2 ) 0 10 Dark AM1.5 3 hours after 21 days after acid doping 20 Acid Doping HNO3 (10%) PCE = % FF = 73 % Bias (V)