The Bio-Nano Nano-ECRIS project: a new ECR ion source at Toyo University to produce endohedral fullerenes ECRIS 2008 18th International Workshop on ECR Ion Sources Chicago, Illinois USA - September 15-18, 2008 Takashi Uchida 1 K. Tanaka 1,2, H. Minezaki 1, M. Muramatsu 1,3, S. Biri 4, T. Asaji 2, A. Kitagawa 3, Y. Kato 5, Y. Yoshida 1 1, Toyo University 2 Tateyama Machine Co., Ltd. 3 National Institute of Radiological Sciences (NIRS) 4 Institute of Nuclear Research (ATOMKI) 5 Osaka University
Introduction Outline Endohedral fullerenes Fullerenes in electron cyclotron resonance (ECR) plasma Design aspect of the Bio-Nano Nano-ECRIS apparatus Concept of the Bio-nano ECRIS apparatus Overview Magnetic system Initial experiments Production and extraction of ions of fullerenes and carbons-loss fullerenes Formation and extraction of fullerene and N 2 mixture plasma (synthesis of NC n or N@C n ) Summary & Future plan 2
Introduction Endohedral fullerene Fullerenes have a unique type of inner empty space with their unusual cage-like structures. Atoms may reside in this space and form endohedral fullerenes. Endohedral fullerenes have novel physical and chemical properties that are very important for their potential applications such as magnetic resonance imaging agents, biological tracing agents, organic ferromagnets and superconductors etc. Endohedral fullerenes are generally produced by an arc discharge, a laser vaporization and a chemical processing methods. 3
Introduction H 2 @C 60 synthesis by molecular surgery method [K. Komatsu et al., Science 307 238-240 (2005).] Open-cage fullerenes, which have a large orifice, are effective for the encapsulation of atoms. 4
Introduction Fullerenes in an ECR plasma [1] S. Biri et al., Rev Sci Instrum 73, 881 (2002). [2] S. Biri et al., Rev Sci Instrum 77, 03A314 (2006). Ionization and fragmentation of fullerenes C 60-2n q+ (C 60+, C 58+, C 56+,, C 60 2+, C 58 2+,, C 60 3+, ) C 60 ion beam spectrum Carbons-loss fullerenes might have an orifice, even though such structure may be unstable and transient. Carbons-loss fullerenes might be effective for the production of endohedral fullerenes. 5
Introduction Endohedral fullerenes production in the mixture plasma of fullerenes and gas or metal C 60 +, C 58 +, C 56 +, A@C n Simultaneous processes of carbons-loss fullerene formation and collision reaction of the carbons-loss fullerenes with gas or metal ions C 2 units Open-cage C-loss fullerene Gas or Metal ion Endohedral C-loss fullerene 6
Introduction Possible effectiveness of ECRIS for the endohedral fullerenes production Long confinement time of ions High Collision probability of fullerene ions and gas or metal ions High ionization efficiency Low feed consumption Low-pressure plasma Low impurity density BUT, There in no ECRIS, which is specialized for the generation of fullerene plasma and the synthesis of endohedral fullerenes. 7
Design concept of the Bio-Nano Nano-ECRIS apparatus Endohedral fullerene synthesis (we aim Fe@C n synthesis) Production of low-charged large-mass plasma and beam!! Several evaporation sources (fullerene vapor and Fe vapor, ) Large plasma chamber to reduce the wall loss of lowcharged large-mass ions and to mount evaporation sources Relatively weak magnetic field in order to reduce the synthesis of high-charged ions Low extraction voltage and large sector magnet to analyze the ion beam with high mass-to-charge ratio Beam deceleration system and substrate holder to produce the deposition 8
Primary differences between Bio-Nano-ECRIS and general ECRIS for multiply charged ions production Extraction voltage Effect of confinement Evaporation source Bio-Nano-ECRIS Low Ion-ion Collision Several sources (fullerene, Fe, ) General ECRIS for multiply charged ions High Ion-electron Collision No source
Bio-Nano Nano-ECRIS apparatus ECRIS Extraction & Einzel Faraday cup 90 o sector magnet Beam deceleration & Substrate Holder Extraction gap 1 6 cm Deceleration voltage 0 5 kv Extraction voltage Analyzing magnet Magnetic field strength 0.5 5 kv Solenoid coil, 90 o sector, r = 50 cm 0 0.8 T Vacuum system Turbo molecular pump (450 l/sec 3) 10
The ECRIS Mirror magnets Solenoid coils Axial magnetic induction peak (500 A) Minimum field strength (500 A) Mirror ratio (500A) 0.442 T Hexapole Magnet Maximum radial magnetic induction in chamber Nd-Fe-B 0.165 T 2.68 0.72 T Microwave (1) Frequency (1) TWT amplifier 8 10 GHz Microwave (2) Frequency (2) Magnetron 2.45 GHz Plasma chamber diameter 14 cm Plasma chamber length 34 cm Fullerene evaporation Resistance heating oven Temperature (normal use) 400 500 oc 11
The ECRIS 2.45 GHz waveguide Iron evaporation oven Biased disk Fullerene evaporation oven Gas feed through 8 10 GHz waveguide Mirror magnets Solenoid coils Axial magnetic induction peak (500 A) Minimum field strength (500 A) Mirror ratio (500A) 0.442 T Hexapole Magnet Maximum radial magnetic induction in chamber Nd-Fe-B 0.165 T 2.68 0.72 T Microwave (1) Frequency (1) TWT amplifier 8 10 GHz Microwave (2) Frequency (2) Magnetron 2.45 GHz Plasma chamber diameter 14 cm Plasma chamber length 34 cm Fullerene evaporation Resistance heating oven Temperature (normal use) 400 500 oc 12
Magnetic field of the Hexapole magnet Maximum radial magnetic induction in chamber : 0.72 Tesla 13
Magnetic field of the mirror coils (500 A) [T] ECR magnetic field for 10 GHz 1.69 0.442 1.50 1.33 0.358 B (T) 1.13 0.274 0.95 0.75 0.190 0.57 0.38 0.106 0.19 0 0.022 32 24 16 8 0 8 z (mm) 16 24 32 ECR zone for 10 GHz Field strength along the chamber axis (500 A), maximum: 0.442 Tesla minimum : 0.165 Tesla ECR zone (500 A, 10GHz), diameter : 10 cm length : 23 cm 14
Fullerene ion beam spectra C60 C60-2n2+ 1.0 Pure C60 powder (99.5%) Toven = 430 oc Pchamber = 5 10-5 Pa Microwave frequency = 9.75 GHz power =5W Mirror coil current = 500 A Intensity (μ A) C602+ 0.8 0.6 C502+ C60+ C603+ 0.4 C56+ C44+ 0.2 C50+ 0 IC60+ = 400 na, IC60 = 800 na. 2+ C60-2n+ C60-2n3+ 0 10 20 0 0 30 0 40 0 50 0 60 0 70 0 80 m/q Very clear fullerene spectrum was obtained using a new ECRIS apparatus. The C60 ion beam consists of ions of C60 and carbons-loss C60. Multi-charged species are also observed. 15
Fullerene ion beam spectra C70 Pure C70 powder (98%) Toven = 430 oc Pchamber = 6 10-5 Pa Microwave frequency = 9.75 GHz power = 10 W Mirror coil current = 500 A IC70+ = 0.2 na Very clear spectrum was also obtained for C70 source. The C70 plasma consists of ions of C70 and carbons-loss C70. Multi-charged species are also observed. 16
General characteristics of fullerene ion beam spectra Comparison of Cn ion current with dissociation energy C70, C60, C50, C44 Io n C u r r e n t (ar b. u n it s ) D is s o c iat io n En e r gy (e V ) 12 10 8 6 C 60 C 70 Stable! 4000 4 30 40 50 60 70 N u m b e r o f C ar b o n A t o m s High ion current Calculated Value from [3]. [3] S. Díaz-Tendero et al., Int. J. Mass Spectrom. 250, 133-141 (2006). 17
Structure of carbons-loss fullerenes Structure of the most stable isomer for Cn [3] No orifice (<7-membered ring) But, for C58, the structure including 7-membered ring is possible. Figure from [4] [3] S. Díaz-Tendero et al., Int. J. Mass Spectrom. 250, 133 (2006). [4] S. Díaz-Tendero et al., J. Chem Phys. 123, 184306 (2005). 18
Formation and extraction of fullerene and N2 mixture plasma Significant broadening Pchamber (N2 pressure) 10 Complex feature of: C60 = 720, N + C60 = 734 C58 = 696, N + C58 = 710 C56 = 672, N + C56 = 686 NCn (N@Cn)?? Beam deposition and characterization of the deposit are needed. Future work 19
Deposit in the plasma chamber 20
MALDI-TOF mass spectrum of deposit in the plasma chamber Intensity (arb. units) Intensity (arb. units) OC60 690 700 710 m/z 620 640 730 NC58 (N@C58) C58 600 720 N + C60 = 734 C60 = 720 N + C58 = 710 C58 = 696 660 680 m/z 700 720 740 No peak at NC60 = 734 The peak of NC58 = 710 is observed! 21
Summary & Future plan We have developed a new ECRIS apparatus for the synthesis of endohedral fullerenes. Fullerene (C60 and C70) ions beam spectra were successfully obtained, and specific C-loss fullerene ions are separable. High beam intensity was obtained for C60; IC60+ = 400 na, IC602+ = 800 na. NCn, in particular NC58 (and/or N@C58) are produced in the mixture plasma of C60 and N2. Future work Separation and collection of NCn. Mechanisms of carbons-loss fullerenes formation and encapsulation of atom in carbons-loss fullerenes. Fe ion formation and encapsulation in carbons-loss fullerenes 22
Acknowledgements We would like to thank Dr. Fukuda and Mr. Kurosu for MALDI-TOF-MS measurements. Part of this study has been supported by a Grant for the 21st Century Center of Excellence Program since 2003 and a Grant for the High-Tech Research Center Fund since 2006. Both funds were organized by the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. 23
Thank you for your attention! 24
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MALDI-TOF mass spectrum of pure C60 powder 500 In t e n s it y (ar b. u n it s ) 400 300 200 100 0 600 620 640 660 680 m/ z 700 720 740 26
MALDI-TOF mass spectrum of deposit in the plasma chamber In t e n s it y (ar b. u n it s ) 400 300 200 100 0 690 700 710 720 730 m/ z 27
In t e n s it y (ar b. u n it s ) MALDI-TOF mass spectrum of deposit in the plasma chamber 20 0 1440 1450 1460 1470 1480 m/ z 28