division of molecular materials sciencemms.ltm.kyoto-u.ac.jp/.../120504_for_visitors_100.pdf ·...
TRANSCRIPT
May 16, 2012 for Shoshin Study Tour 2012- Study Association Arago (the University of Twente, Netherlands)
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Division of Molecular Materials ScienceResearch Center for Low Temperature and Materials Sciences, Kyoto University
S
SO
O
S
SO
OS
SO
O
SS
S
SO
O S
S CH3
S
SO
O
S
SCl
S
SO
O S
S
SS
SS
Synthesis of Functional Materials
Structural Analysis & Physical Properties examination
Design of New Materialshttp://mms.ltm.kyoto-u.ac.jp/index_e.html
1980s: Organic Superconductors
Se
Se
Se
SeH3C
H3C CH3
CH3
S
SS
S S
S
S
S
Q1D Superconductorsmax. Tc = 1.4 K (AP)
2D Superconductorsmax. Tc = 12.3 K (AP)
History of Molecular Conductors
1954 Organic Semiconductor
• Br2
1960s 1D Organic Metals
S
S
S
S
NC
NC
CN
CN
Increment of Dimensionality
1990s: 3D Molecular Superconductors
max. Tc = 33 K (AP)
Molecular Degree of Freedom
Lattice point≠ Simply a point
√ Size√ Shape√ Functionality- 2 -
CC S
CSO
H2CH2C
OC
S CCS
H
H
CC S
CSO
H2CH2C
OC
S CCS
H
H CC S
CSO
H2CH2C
OC
S CCS
H
H+
CC S
CSO
H2CH2C
OC
S CCS
H
HPF6
2
+ PF6e
(EDO-TTF)2PF6
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S
SO
O
S
SO
OS
SO
O
SS
S
SO
O S
S CH3
S
SO
O
S
SCl
S
SO
O S
S
SS
SS
Charge-Transfer Complex Formation → Molecular Conductors
To endow the electricalconductivity to molecularbased materials, the charge-transfer complex is formedby treated with donor/acceptor molecules or byelectrochemical method.
Electro-oxidation
for example
Distinct Molecular Deformation
PF6Rotation
Isotropic
(EDO-TTF)2PF6 — Above and Below TMI (280 K)
Overlap Integral
Uniform
from Bond
Length
0.5+
Molecular Deformation is regarded as the Origin to Mix Metal-Insulator Transition Mechanisms (Multi-instability).
Alternate
Peierls
(Overlap Integral × 103)
1+/0
Charge Ordering
Uniaxial
Order-Disorder
- 4 -A. Ota et al., J. Mater. Chem., 12(9), 2600-2602 (2002)
Time Delay
Probe (white light)Pump (1.55 eV= 12.5 × 103 cm-1)
Thermal Transition PIPT
1.55
eV
1.70
eV
1.38
eV
1.55
eV
1.70
eV
1.38
eV
Sample
Photo-Induced Phase Transition (PIPT) of (EDO-TTF)2PF6
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Probe 1.70 eV(13.7 × 103 cm-1)
Probe 1.38 eV(11.1 × 103 cm-1)
Responce < 0.1 psRelaxation to meta-stable state ≈ 1.5 ps
1 photon / 50-500 moleculesUltra-fast & Highly Efficient PIPT Material
M. Chollet et al., Science, 307, 86-89 (2005) [Erratum: 312, 697 (2006)]H. Yamochi, S. Koshihara, Sci. Technol. Adv. Mater., 10(2), 024305/1-6 (2009)
B: Thermally Induced Metal
Three-level Rate Equation
A: (1010) phaseFluctuated Charge Order
C: Charge Randomization+ Photo Induced Carrier+ .....
InsulatorLow Temp. Phase
0.1 - 1 ps
10 ps order
100 ps order
PI Process over 100 ps
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<Recent Result>
PIPT Route is Analyzed.
N. Fukazawa et al., J. Phys. Chem. C, 116(9), 5892-5899 (2012)
208. D.V. Konarev et al., Inorg. Chem., 51(6), 3420–3426 (2012)207. D.V. Konarev et al., New J. Chem., 35(9), 1829-1835 (2011)197. D.V. Konarev et al., Inorg. Chem., 49(8), 3881–3887 (2010)
213. T. Hiramatsu et al., Physica Status Solidi C, 9(5), 1155-1157 (2012)212. M. Ishikawa et al., Physica Status Solidi C, 9(5), 1143-1145 (2012209. N. Fukazawa et al., J. Phys. Chem. C, 116(9), 5892-5899 (2012)204. K. Onda et al., Physica B, 405(11), S350-S352 (2010)202. X.F. Shao et al., Physica B, 405(11), S75-S78 (2010)199. T. Murata et al., Physica B, 405(11), S45-S48 (2010)
211. H. Yamochi et al., Physica Status Solidi B, 249(5), 1012-1016 (2012)210. T Ishikawa et al., J. Phys.: Condens. Matter, 24(19), 195501/1-9 (2012)206. T. Haneda et al., J. Mater. Chem., 21(5), 1621-1626 (2011)205. G. Saito et al., Bull. Chem. Soc. Jpn., 83(12), 1462–1480 (2010)203. Y. Nakano et al., Physica B, 405(11), S198-S201 (2010)201. T. Shirahata et al., Physica B, 405(11), S61-S64 (2010)200. Y. Nakano et al., Physica B, 405(11), S49-S54 (2010)
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Recent Publications ▪ ▪ ▪ ▪ ▪ many corroborations with other laboratories
Other Materials
& the derivatives
(C60) Materials