Cis Vs. Trans: Squaraine Molecules as Potential Sensitizers for Dye Sensitized Solar Cells
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Cis Vs. Trans: Squaraine Molecules as Potential Sensitizers for Dye Sensitized Solar Cells NSF Science and Technology Center on Materials and Devices for Information Technology Research No. DMR 0120967 NSF Research Experiences for Undergraduates Program Hooked on Photonics No. CHE 0851730 www.hookedonphotonics.org Daniel Morales Salazar, Iryna Davydenko, and Seth Marder Conclusions/Future work References 1. Chun-Guey Wu et al. Org. Lett. 2013, 10, 5455. 2. Chuanjiang Qin et al. Adv. Funct. Mater. 2013, 1, 1. 3. Maeda et al. J. Mater. Chem. A 2013, 1, 1303. 4. Dualeh et al. Appl. Phys. Lett. 2012, 100, 173512. 5. Shi et al. Angew. Chem. Int. Ed. 2011, 50, 6619. 6. Delcamp et al. Chem. Eur. J. 2013, 19, 1819. 7. Ronca et al. Energy Environ. Sci. 2013, 6, 183. 8. Hagfeldt et al. Chem. Rev. 2010, 110, 6595. 9. Qin et al. Chem. Asian J. 2013, 00, 0. 10. Pandey et al. J. Photochem. Photobiol. A 2010, 214, 269. 11. Volker et al. Chem. Eur. J. 2011, 17, 14147. Acknowledgments Dr. Iryna Davydenko Dr. Seth Marder Dr. Denise Bale Janos Simon (HPLC, and UV-Vis-NIR spectrometer training) Georgia Tech, NSF (CHE-1156598), CMDITR (NSF DMR- 0120967) Abstract To investigate the relationship between structural conformation and photovoltaic response of symmetrical squaraine dyes, we have incorporated an electron-withdrawing dicyanovinyl group on the squaric acid core. The functionalized squaraine molecule is locked in a cis-like geometry, and presents absorption bands in the high-energy area of the visible- light region, which could result in panchromatic sensitization. Herein, we report the synthesis, electrochemical, electronic and optical properties of a squaraine sensitizer. Georgia Institute of Technology, Department of Chemistry and Biochemistry, 901 Atlantic Drive, Atlanta, GA 30332, U.S.A. [email protected] Squaraine Dyes Large absorption coefficients in red to NIR region. Can be used as NIR cosensitizers unless panchromatic response is achieved. Cis vs. Trans Can a cis-like symmetrical squaraine outperform the efficiency of asymmetrical squaraines? Synthetic Route of Sensitizer Photophysical and Computational Studies Dye λ max (nm) CHCl 3 ε (M -1 cm -1 ) E 0-0 (eV) YR6 671 275,000 1.76 DMS-II-22 698 210,000 1.70 DMS-II-33 733 230,000 1.62 Electrochemical Properties Dye E 0-0 (eV) E ox (V) E ox -E 0-0 (V) YR6 1.76 0.80 -0.96 DMS-II-22 1.70 0.87 -0.83 DMS-II-33 1.62 0.85 -0.77 Measured in 0.1M nBu 4 NPF 6 in DCM solution with decamethylferrocene as an internal standard. Tabulated values are reported versus NHE. First oxidation potential corresponds to HOMO level of dye. DFT calculations of DMS-II-44 with the B3LYP functional and 6-31G** basis set using Spartan. The absorption and electrochemical properties of the synthesized intermediates and DMS-II-44 show a red-shift of absorption maxima into the NIR region, intense absorption bands in the high-energy region, as well as reversible redox behavior, which may all positively influence the photovoltaic response of a sensitizer in a dye-sensitized solar cell . MSQ, η=2.2%, λ max 642nm (CHCl 3 ) SQM1a, η=3.6%, λ max 705 nm (CHCl 3 ) YR6, η=6.74%, λ max 671nm (CHCl 3 ) HOMO LUMO E ox Introduction Dye-Sensitized solar cells Low-cost, flexible, colorful, efficient (15%). Basic Functioning Photon excites an electron. Excited electron is injected in the TiO 2 CB. Oxidized sensitizer is regenerated by an electrolyte. Electrolyte is reduced at the cathode, closing the circuit.
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Transcript of Cis Vs. Trans: Squaraine Molecules as Potential Sensitizers for Dye Sensitized Solar Cells
Cis Vs. Trans: Squaraine Molecules as Potential Sensitizers for Dye Sensitized Solar Cells
NSF Science and Technology Center on Materials and Devices for Information Technology Research No. DMR 0120967
NSF Research Experiences for Undergraduates Program Hooked on Photonics No. CHE 0851730
www.hookedonphotonics.org
Daniel Morales Salazar, Iryna Davydenko, and Seth Marder
Conclusions/Future work
References1. Chun-Guey Wu et al. Org. Lett. 2013, 10, 5455.
2. Chuanjiang Qin et al. Adv. Funct. Mater. 2013, 1, 1.
3. Maeda et al. J. Mater. Chem. A 2013, 1, 1303.
4. Dualeh et al. Appl. Phys. Lett. 2012, 100, 173512.
5. Shi et al. Angew. Chem. Int. Ed. 2011, 50, 6619.
6. Delcamp et al. Chem. Eur. J. 2013, 19, 1819.
7. Ronca et al. Energy Environ. Sci. 2013, 6, 183.
8. Hagfeldt et al. Chem. Rev. 2010, 110, 6595.
9. Qin et al. Chem. Asian J. 2013, 00, 0.
10. Pandey et al. J. Photochem. Photobiol. A 2010, 214, 269.
11. Volker et al. Chem. Eur. J. 2011, 17, 14147.
AcknowledgmentsDr. Iryna Davydenko
Dr. Seth Marder
Dr. Denise Bale
Janos Simon (HPLC, and UV-Vis-NIR spectrometer training)
Georgia Tech, NSF (CHE-1156598), CMDITR (NSF DMR-
0120967)
AbstractTo investigate the relationship between structural
conformation and photovoltaic response of
symmetrical squaraine dyes, we have incorporated an
electron-withdrawing dicyanovinyl group on the
squaric acid core. The functionalized squaraine
molecule is locked in a cis-like geometry, and presents
absorption bands in the high-energy area of the visible-
light region, which could result in panchromatic
sensitization. Herein, we report the synthesis,
electrochemical, electronic and optical properties of a
squaraine sensitizer.
Georgia Institute of Technology, Department of Chemistry and Biochemistry, 901 Atlantic Drive, Atlanta, GA 30332, U.S.A.
Squaraine Dyes
Large absorption
coefficients in red to
NIR region. Can be
used as NIR
cosensitizers unless
panchromatic response
is achieved.
Cis vs. Trans
Can a cis-like
symmetrical squaraine
outperform the
efficiency of
asymmetrical
squaraines?
Synthetic Route of Sensitizer
Photophysical and Computational Studies
Dye λmax
(nm)
CHCl3
ε
(M-1 cm-1)
E0-0
(eV)
YR6 671 275,000 1.76
DMS-II-22 698 210,000 1.70
DMS-II-33 733 230,000 1.62
Electrochemical Properties
Dye E0-0
(eV)
Eox
(V)Eox - E0-0
(V)
YR6 1.76 0.80 -0.96
DMS-II-22 1.70 0.87 -0.83
DMS-II-33 1.62 0.85 -0.77
Measured in 0.1M nBu4NPF6 in DCM solution with
decamethylferrocene as an internal standard. Tabulated values
are reported versus NHE. First oxidation potential
corresponds to HOMO level of dye.
DFT calculations of DMS-II-44 with the B3LYP functional and 6-31G** basis set using Spartan.
The absorption and electrochemical
properties of the synthesized
intermediates and DMS-II-44 show a
red-shift of absorption maxima into
the NIR region, intense absorption
bands in the high-energy region, as
well as reversible redox behavior,
which may all positively influence the
photovoltaic response of a sensitizer in
a dye-sensitized solar cell .
MSQ, η=2.2%, λmax 642nm (CHCl3)
SQM1a, η=3.6%, λmax 705 nm (CHCl3)
YR6, η=6.74%, λmax 671nm (CHCl3)
HOMO LUMO
Eox
Introduction
Dye-Sensitized solar cells
Low-cost, flexible, colorful, efficient (15%).
Basic Functioning
Photon excites an
electron. Excited
electron is injected
in the TiO2 CB.
Oxidized sensitizer
is regenerated by
an electrolyte.
Electrolyte is
reduced at the
cathode, closing the
circuit.
