色素増感太陽電池への応用に向けてリンフタロシアニンの合成、特性評価および会合の研究

Synthesis, Characterization and Aggregation Studies of Phosphorous Phthalocyanine

Towards its Application in Dye Sensitized Solar Cells

Kyushu Institute of Technology, 2-4 Hibikino, Wakamatsu, Kitakyushu 808-0196, Japan

Nippon Steel Chemical Co. Ltd., 46-80 Nakabaru, Sakinohama, Tobata, Kitakyushu 804-8503, Japan

Gururaj M. Shivashimpi, Shyam S. Pandey, Hayat Azwar,

Naotaka Fujikawa, Yuhei Ogomi, Yoshihiro Yamaguchi and

Shuzi Hayase

Spectral Response in high efficiency DSSCs

Dye YD2-O-C8

Efficiency = 11.9 %

Ru-dye-N719

Efficiency = 11 %

Dye Perovskite

Efficiency = 15 %

R & D of Novel

Sensitizers

M. Gratzel , et al., J. Am. Chem. Soc. (2005) 127 16835 Ashwini Yella , et al., Science.

(2011), 334, 629

J. Burschka, et al., Nature. (2013), 499, 316

Development of NIR Dyes !

Potentiality of Phthalocyanine sensitizers

1. Macrocyclic pi-extended framework

2. Thermal, Chemical and photochemical stability

3. Sharp and Intense light absorption with High molar extinction

coefficient

4. Capability of sensitization of wide band gap semiconductors

5. Possibility to tailor the optical absorption window from visible to

NIR wavelength region

Yanagisawa, et al;

J. Porp. Phthal. 6 (2002) 217-224.

Efficiency = 0.61%

DSSCs Based on Phthalocyanine Dyes !

Efficiency = 3.52%

Cid, J.-J. et al;

Angew. Chem., Int. Ed. Engl., 46

(2007) 8358–8362.

Efficiency = 0.11%

Yanagisawa, et al;

J. Porp. Phthal. 6 (2002) 217-224.

Efficiency = 6.49%

Ragoussi. et al;

ChemPhysChem (2014) Early

Park, S. Hayase et al,;

ECS JSS, 2 (2012) Q6-Q11.

Efficiency = 0.5% (On SnO2)

Phthalocyanine based on Axial Ligation

Phosphorous Phthalocyanine

Axial Ligation by Phosphorous Phthalocyanine

Photovoltaic Performance

Design of Novel Phosphorous Phthalocyanine

Compound HOMO LUMO Band gap

TBC-A - 4.60 eV - 2.52 eV 2.08 eV

TBC-B - 6.00 eV - 3.72 eV 2.28 eV

Comp. 4 - 4.75 eV - 2.67 eV 2.08 eV

Target Phosphorous Phthalocyanine

HR-FAB MS: Observed 1554.3662 [M]+ for C64H57F24N7O9P (calcd 1554.3572)

Structure confirmed by 1H-NMR, FT-IR and 31P-NMR

Phosphorous 3,6,10,13,17,20,24,27-octatrifluorobutoxy-

triazatetrabenzcorrole

Synthesis of Phosphorous Phthalocyanine

Characterization of Phosphorous Phthalocyanine

Electronic Absorption Spectra Energy Band Diagram

Table 1. List of solvents used with their

Dielectric constants.

Solvent Dielectric constant

CCl4 2.24

THF 7.58

Pyridine 12.4

1-Pentanol 15.13

1-Propanol 20.4

Acetone 20.52

Ethanol 24.85

Methanol 32.7 Figure 2. Electronic absorption spectra of Dye 4

in various solvents.

Aggregation

Aggregation Studies

Solvent e Q-band Aggregate band % of

aggregation

CCl4 2.24 722 nm 679 nm 39.99%

THF 7.58 713 nm 670 nm 41.88%

Pyridine 12.4 714 nm 673 nm 46.51%

1-Pentanol 15.13 710 nm 673 nm 48.63%

1-Propanol 20.4 709 nm 673 nm 49.10%

Acetone 20.52 708 nm 670 nm 48.65%

Ethanol 24.85 709 nm 673 nm 52.39%

Methanol 32.7 714 nm 682 nm 57.25%

Optical absorption data and percentage of aggregation values in

various solvents.

Plot of aggregation vs dielectric constant.

Aggregation Studies

% Aggregation = Avibronic-band/AQ-band

Conclusions

Phosphorus-Phthalocyanine was found to be attached on TiO2 surface

without having special anchoring group.

Attachment takes place via axial ligation through Ti-O-P linkage

New Phosphorous Phthalocyanine was designed, synthesized and

characterized.

It is fairly soluble in common organic solvents and shows energetic

matching with TiO2 conduction band and Iodine based redox couple.

Aggregation behavior in various organic solvent was investigated and

shows linear dependence with the dielectric constant of the solvents.

Thank you very much for your

kind attention !