5 research outputs found
Kinetic Evidence of Two Pathways for Charge Recombination in NiO-Based Dye-Sensitized Solar Cells
Mesoporous nickel oxide has been
used as electrode material for
p-type dye-sensitized solar cells (DSCs) for many years but no high
efficiency cells have yet been obtained. One of the main issues that
lowers the efficiency is the poor fill factor, for which a clear reason
is still missing. In this paper we present the first evidence for
a relation between applied potential and the charge recombination
rate of the NiO electrode. In particular, we find biphasic recombination
kinetics: a fast (15 ns) pathway attributed to the reaction with the
holes in the valence band and a slow (1 ms) pathway assigned to the
holes in the trap states. The fast component is the most relevant
at positive potentials, while the slow component becomes more important
at negative potentials. This means that at the working condition of
the cell, the fast recombination is the most important. This could
explain the low fill factor of NiO-based DSCs
Injection and Ultrafast Regeneration in Dye-Sensitized Solar Cells
Injection of an electron from the
excited dye molecule to the semiconductor is the initial charge separation
step in dye-sensitized solar cells (DSC’s). Though the dynamics
of the forward injection process has been widely studied, the results
reported so far are controversial, especially for complete DSC’s.
In this work, the electron injection in titanium dioxide (TiO<sub>2</sub>) films sensitized with ruthenium bipyridyl dyes N3 and N719
was studied both in neat solvent and in a typical iodide/triiodide
(I<sup>–</sup>/I<sub>3</sub><sup>–</sup>) DSC electrolyte.
Transient absorption (TA) spectroscopy was used to monitor both the
formation of the oxidized dye and the arrival of injected electrons
to the conduction band of TiO<sub>2</sub>. Emission lifetime of the
dye-sensitized films was recorded with time-correlated single photon
counting to reveal nanosecond time scales of injection. It was found
that the injection dynamics of the N3 and N719 dyes are similar. In
solvent the injection from both dyes occurs in the femto- to picosecond
time scale while in the I<sup>–</sup>/I<sub>3</sub><sup>–</sup> electrolyte, it slows down significantly, extending to the nanosecond
time domain. The presence of the electrolyte was found to increase
the excited state lifetime of the dyes, implying that injection efficiency
remains high despite the slower kinetics of injection compared to
neat solvent. A remarkable new finding was that the prominent absorption
signal of the oxidized dye observed in neat solvent vanished almost
completely in the presence of the electrolyte, while the arrival of
electrons to the conduction band of TiO<sub>2</sub> was practically
unaltered, only slowed down. The observed disappearance of the oxidized
dye population in the I<sup>–</sup>/I<sub>3</sub><sup>–</sup> electrolyte is most likely related to the reduction of the oxidized
dye by iodide I<sup>–</sup>, which is the first step of the
dye regeneration process. To the best of our knowledge, this is the
first time initial dye regeneration has been shown to occur in a few
picoseconds after injection
Ultrafast Electron Transfer Between Dye and Catalyst on a Mesoporous NiO Surface
The combination of molecular dyes
and catalysts with semiconductors
into dye-sensitized solar fuel devices (DSSFDs) requires control of
efficient interfacial and surface charge transfer between the components.
The present study reports on the light-induced electron transfer processes
of p-type NiO films cosensitized with coumarin C343 and a bioinspired
proton reduction catalyst, [FeFe](mcbdt)(CO)<sub>6</sub> (mcbdt =
3-carboxybenzene-1,2-dithiolate). By transient optical spectroscopy we find that ultrafast interfacial
electron transfer (τ ≈ 200 fs) from NiO to the excited
C343 (“hole injection”) is followed by rapid (<i>t</i><sub>1/2</sub> ≈ 10 ps) and efficient surface electron
transfer from C343<sup>–</sup> to the coadsorbed [FeFe](mcbdt)(CO)<sub>6</sub>. The reduced catalyst has a clear spectroscopic signature
that persists for several tens of microseconds, before charge recombination
with NiO holes occurs. The demonstration of rapid surface electron
transfer from dye to catalyst on NiO, and the relatively long lifetime
of the resulting charge separated state, suggests the possibility
to use these systems for photocathodes on DSSFDs
Time-Resolved IR Spectroscopy Reveals a Mechanism with TiO<sub>2</sub> as a Reversible Electron Acceptor in a TiO<sub>2</sub>–Re Catalyst System for CO<sub>2</sub> Photoreduction
Attaching
the phosphonated molecular catalyst [Re<sup>I</sup>Br(bpy)(CO)<sub>3</sub>]<sup>0</sup> to the wide-bandgap semiconductor TiO<sub>2</sub> strongly enhances the rate of visible-light-driven reduction of
CO<sub>2</sub> to CO in dimethylformamide with triethanolamine (TEOA)
as sacrificial electron donor. Herein, we show by transient mid-IR
spectroscopy that the mechanism of catalyst photoreduction is initiated
by ultrafast electron injection into TiO<sub>2</sub>, followed by
rapid (ps-ns) and sequential two-electron oxidation of TEOA that is
coordinated to the Re center. The injected electrons can be stored
in the conduction band of TiO<sub>2</sub> on an ms-s time scale, and
we propose that they lead to further reduction of the Re catalyst
and completion of the catalytic cycle. Thus, the excited Re catalyst
gives away one electron and would eventually get three electrons back.
The function of an electron reservoir would represent a role for TiO<sub>2</sub> in photocatalytic CO<sub>2</sub> reduction that has previously
not been considered. We propose that the increase in photocatalytic
activity upon heterogenization of the catalyst to TiO<sub>2</sub> is
due to the slow charge recombination and the high oxidative power
of the Re<sup>II</sup> species after electron injection as compared
to the excited MLCT state of the unbound Re catalyst or when immobilized
on ZrO<sub>2</sub>, which results in a more efficient reaction with
TEOA
Suppression of Forward Electron Injection from Ru(dcbpy)<sub>2</sub>(NCS)<sub>2</sub> to Nanocrystalline TiO<sub>2</sub> Film As a Result of an Interfacial Al<sub>2</sub>O<sub>3</sub> Barrier Layer Prepared with Atomic Layer Deposition
Subnanometer-thick Al<sub>2</sub>O<sub>3</sub> barrier layers on nanocrystalline TiO<sub>2</sub> film were prepared with atomic layer deposition (ALD). The method allowed variation of barrier thicknesses at atomic resolution also deep in nanoporous structures, which makes it a superior method as compared to, e.g., sol−gel techniques. In this letter we present results on the effect of Al<sub>2</sub>O<sub>3</sub> barriers of various thicknesses on forward electron injection in dye-sensitized solar cells. A decrease in the amplitude of the oxidized Ru(dcbpy)<sub>2</sub>(NCS)<sub>2</sub> dye absorption signal due to singlet injection was observed already after one deposition cycle that produces a discontinuous layer with nominal thickness of 1 Å. More than two layer coatings also slowed down the triplet injection. The findings indicate suppression of total electron injection, which is probably due to the Al<sub>2</sub>O<sub>3</sub>-induced weakening of electronic coupling between the dye and TiO<sub>2</sub> as well as modification of the TiO<sub>2</sub> electronic structure