RECENT EFFORTS TO MAKE MONEY FROM CARBON NANOTUBES

1. RECENT EFFORTS TO MAKE MONEY FROM CARBON NANOTUBES H. Kuzmany, Universität Wien, Austria Impressions from a recent visit to Japanese scientific and technological research institutions This visit was supported by the Japanese Society for the Promotion of Science (JSPS) Headquater: Tokyo Institute of Technology National Institute of Advanced Industrial Science and Technology (AIST), 4th Japan-Korean Symposium on Carbon Nanotubes Others: U Tokyo, Shinshu U, Nagoya U, Meijo U; but:

2. A LIST OF COMMERCIAL AND COMMERCIAL ORIENTED CNT PLAYERS World Technology Evaluation Center (WTEC) Report 2007

3. FOR SWCNTs: TWO MAIN CATEGORIES CAN BE DISCRIMINATED GROWTH AND SECONDARY PREPARATION OF TUBES OTHER CATEGORIES Cheap Fast Large amounts Selective Compound materials Electro-optics Field emisson Sensors Small diameter tubes, tube doping, plastic deformation

4. SUMIO IIJIMA Professor at Meijo University, Nagoya Director of Research Center for Advanced Carbon Materials, Tsukuba Head of a research laboratory at NEC Professor at University of Nagoya (from 2008 on) Balzan Prize 2007 Almost untouched Master of the Nanotubes

5. Growth and selection

6. SWCNT SUPERGROWTH K. Hata et al., Science 306 (2004)1362 CVD growth, Ar, He, Alcohol, several catalysts, Si or quartz waver By adding water vapor calalyst life time was extended to 50.000% compared to 300% In HiPco Growth rates best: 0.25 mm/min Diameter 1-3 nm

7. Costs reduction: Metal sheets as substrate Large areas (A4 size) sprayed catalyst Increase of production: Huge CVD furnaces Full automatic controll, 24 h production possible In 2 h 10 mm hight forrests with constant growth rate At the moment 20g/day Scaleable to 1 Kg/h Industrial scale mass production of oriented SWCNT is possible PROGRESS IN SUPERGROWTH Research Center for Advanced Carbon Materials at AIST (Director Iijima, Group leader: K. Hata, both temporary) Intention: masses scale up, costs scale down Already: A Hundreds Time Scale Up from 2004 Declared Goal: $ 500.-/Kg

8. THE MANY WAYS TO GROW SWCNT S. Maruyama, U Tokyo: vertically aligned SWCNT, has 13C tubes for collaboration, polarized optics and Raman S. Lee, Seoul National University: Root growth versus tip growth, uses isotope labelling Y. Homma, Tokyo U of Science: unusual catalysts are possible: Au, Ag, Ge, Si, crystaline structure determines the selection of cap C. J. Lee, Korea U Seoul: Growth of thin MWCNTs (t-MWCNTs) optimized for field emission Y. Achiba, Tokyo Metropolitan U: Models for single chirality growth (with experiments)

9. VISITING KATAURA SAN‘S LABORATORY AT AIST, OCTOBER 2007 Y. Miyata K. Yanagi

10. Semiconductor-Metal separation submitted for publication

11. TOWARDS THE PRODUCTION OF SWCNTs WITH SINGLE CHIRALITY Y. Achiba Laser ablation with Rh/Pd catalyst Controlling the cap growth is important Cooling speed reduces diameter distribution (enhances (6,5)) n - m = 1 family is very much pronounced HiPco New growth model: The final chirality is determined by the growth speed. C2 is added but the success depends on the structure of the dangling bonds (paired DB versus single DB), (7,6) grows fastest N2 Ar Almost single chirality (7,6) S. Suzuki et al., 2007 Distance from center of oven

12. Making money

13. VERTICALLY GROWN CARBON FIBRES (VGCF) Now: VERTICALLY GROWN MULTIWALL CARBON NANOTUBES (VGCNT) A. Oberlin, M. Endo, T. Koyama, 1976 Morinobu Endo Professor at Shinshu University, Nagano

14. 100 100 95 Charge capacity(%) 90 0 10 20 30 40 50 60 Cyclic number VGCF or VGCNT ARE COMMERCIALLY WELL ESTABLISHED Costs: 0.02 $/g Endo tubes in batteries Numerous examples of applications as reinforcement and anti-static materials Batteries, Skis, tennis rackets, golf clubs, car parts, general surface polishing (black), catheters (0.53 mm, MWCNT/nylon) M. Endo, Carbon 2001

15. MARINOBU ENDO SAN‘s DWCNTs Diameter 2 to 3 nm CVD grown DWCNT bundle Bucky paper As grown M. Endo et al., Nature 2005

16. ALNAIR LABORATORIES CORPORATION

17. ULTRA FAST SATURABLE ABSORBER Transmissive SAINT (saturable absorber incorporating nanotubes) • Key Features: • Transmission/Reflection Type • Ultrafast receovery time (<1 ps) • Higly nonlinear • High optical power damage • Applications: • ASE noise suppression • Femtosecond mode-locker • Ultrafast optical switching • Optical signal regeneration • Nonlinear optics applications S. Yamashita (U Tokyo) S.Y. Set (Alnair lab. Corporation) Superior to semiconductor saturablel absorbers (SESAM)

18. Optical communication needs high repetition frequencies (GHz) and thus short resonator lengths .> high Er doping -> high finess -> low loss saturable abs SATURABLE ABSORBERS FOR FIBER LASER PASSIVE MODE LOCKING (Er doped fiber amplifier, EDFA) S. Yamashita et al. Y.-W. Song et al., 2007

19. TRANSFER CHARACTERISTICS FOR SAINT PASSIVE MODE-LOCKED FIBER LASER For 15 m cavity length Best wavelength for optical communication S. Yamashita et al., 2006, 2007 For 0.4 m cavity length

20. FIELD EMISSION FROM DWCNT Needed D.H. Shin et al., 2007 Other suggestions: Ca@BN tubes (calculations) MgO coating thin multiwall NT

22. LABEL-FREE PROTEIN BIOSENSOR USING APTAMER-MODIFIED CNT-FET

23. IgE: immunoglobulin E Found in human serum, enhanced levels indicate immune deficiency

24. Small diameter tubes and tube doping

25. K. Hata K. Suenaga

26. PREDICTING AND DESIGNING NEW NANOTUBE BASED MATERIAL S. Saito From computer simulation (molecular dynamics including DFT) (4,4) tubes can grow under high pressure and high temperatures from (10,10) bundles. There are other possiblel structures which can be grown Boron doped nanotubes may be superconducting

27. FILLING TUBES WITH BORON CONTAINING MOLECULES ortho-carborane C2B10H12 Near atomic resolution for songle organic molecules M. Koshino et al., Science 2007

28. FILLING TUBES WITH BORON CONTAINING MOLECULES ortho.-carborane C2B10H12 Near atomic resolution for single organic molecules M. Koshino et al., Science 2007

29. CAN NITROGEN BE INSERTED INTO THE INNER-SHELL TUBE? 1064 nm, 80 K expected: 0.14% line shift RBM: 0.5 cm-1 2D: 3.5 cm-1 1545 1548 observed: 2D: 3 cm-1 W. Plank, 2007

30. DWCNT FROM PEAPOD PRECURSOR: FILLING FROM SOLUTION VERSUS FILLING FROM GAS PHASE Raman from G‘-line From the observed reduction of the C60 ppm in the solution prepared peapods: May be solvent (toluene) has entered the tubes. F. Simon et al., 2006

31. Up to 13% of inner tube carbon can come from toluene As evaluated from the G‘ line first spectral moment CARBON FROM SOLVENT ENTERS THE WALL OF THE INNER TUBE Outer tube response subtracted F. Simon et al., 2006

32. SUMMARY Still very strong activities in CNT research. Applications and fundamental research oriented towards application are dominating. Tube growth is a major field. Some applications are on the market. Inner-shell tube doping seems to be possible. Semiconductor - metal separation is possible on a large scale but expensive.