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Acetonitrile Solution Effect on Ru N749 Dye Adsorption and Excitation at TiO2 Anatase Interface
journal contribution
posted on 2014-07-31, 00:00 authored by Yoshitaka Tateyama, Masato Sumita, Yusuke Ootani, Koharu Aikawa, Ryota Jono, Liyuan Han, Keitaro SodeyamaWe investigated stable structures
and photoexcitation character of Ru N749 dye (black dye (BD)) adsorption
to TiO2 anatase (101) interface immersed in bulk acetonitrile
(AN) solution, a most representative electrode interface in dye-sensitized
solar cells (DSCs). Density-functional-theory-based molecular dynamics
(DFT-MD) with explicit solvent molecules was used to take into account
the fluctuations of solvation shells and adsorbed molecules. We demonstrated
that BD adsorption via deprotonated carboxylate two anchors (d2) is
the most stable at the interface, while the one protonated carboxyl
anchor (p1) has the average energy only slightly higher than the d2.
This indicates that the p1 state can still coexist with the d2 under
equilibrium. It is in contrast with the calculated large stability
of the p1 in vacuo. Inhomogeneous charge distribution and anchor fluctuation
enhanced by AN solution causes this d2 stabilization. The calculated
projected densities of states and the photoabsorption spectra clearly
show that the d2 state has larger driving force of the electron injection
into the TiO2, whereas the photoabsorption in the wavelength
region over 800 nm, a characteristic of BD sensitizer, is mainly
attributed to the p1 state even in the AN solution. Consequently,
the better performance of BD DSC can be understood in terms of the
cosensitizer framework of the d2 and p1 states.
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Keywords
p 1 statebulk acetonitrile2 stabilizationcosensitizer frameworkp 1representative electrode interfaceRu N 749 dyeBD DSCsolution causesTiO 2 Anatase InterfaceWeprotonated carboxyl anchorphotoabsorption spectrawavelength region800 nmelectron injectionBD sensitizerBD adsorption2 statedeprotonated carboxylateanchor fluctuationAcetonitrile Solution EffectmoleculeRu N 749 Dye Adsorptionp 1 statesphotoexcitation charactersolvation shellsInhomogeneous charge distribution
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