The charge-recombination kinetics and band edge
movement in dye-sensitized nanocrystalline TiO2
solar
cells are investigated by intensity modulated photovoltage spectroscopy
(IMVS). A theoretical model of
IMVS for dye-sensitized nanocrystalline semiconductor electrodes is
developed, and analytical expressions
for the frequency dependence of the photovoltage response at open
circuit are derived. The model considers
charge trapping/detrapping and electron transfer from the conduction
band and surface states of the
semiconductor to redox species at the solid/solution interface.
IMVS is shown to be valuable in elucidating
the contributions of band edge shift and recombination kinetics to
changes of the open-circuit photovoltage
(V
oc) resulting from surface modifications of
the semiconductor. IMVS measurements indicate that
surface
treatment of [RuL2(NCS)2] (L =
2,2‘-bipyridyl-4,4‘-dicarboxylic acid)-sensitized TiO2
electrodes with 4-tert-butylpyridine or ammonia leads to a significant band edge shift
concomitant with a more negative V
oc.
Surface-modified dye-covered TiO2 electrodes exhibit a much higher
photovoltage, for a given concentration of
accumulated photogenerated electrons, than the unmodified dye-covered
electrode. The accumulated charge
in the TiO2 electrode is not sufficient to induce a major
potential drop across the Helmholtz layer and cannot
thus explain the observed photovoltage. The surface charge density
is also not sufficient to support an
accumulation layer strong enough to have a major influence on the
photovoltage. The movement of the
Fermi level of the TiO2 electrode, arising from the
accumulation of photogenerated electrons in the conduction
band, accounts for the observed V
oc. The
second-order nature of the recombination reaction with respect
to
I3
- concentration is confirmed.
Furthermore, the IMVS study indicates that recombination at the
nanocrystallite/redox electrolyte interface occurs predominantly via trapped electrons
in surface states.
Low bandgap lead-tin mixed perovskite solar cells have achieved high power conversion efficiency in excess of 17%. However, methylammonium (MA) cation was usually contained, and the thermal stability of MA is always a great concern. In this work, accoring to composition engineering, we tried to explore a nearly formamidinium (FA) based lowbandgap Pb-Sn mixed perovskite FAPb 0.75 Sn 0.25 I 3 as the absorber layer. Combined with interface enginering by replacing PEDOT:PSS layer with NiO x as hole transport layer, a power conversion efficiency of 17.25% has been obtained. This low-bandgap perovskite solar cell maintains about 91% of its original efficiency at 80 O C for 20 hours, and 92% of its initial performance after 46 days storage at the room temperature. The good thermal stability of nearly FA based low-bandgap perovskite could be good for delivering efficient and stable perovskite-perovskite tandem solar cells.
The four complex, almost degenerate, second-order eigenmodes of a two-mode fiber having a circular core are reduced to two nondegenerate, linearly polarized second-order eigenmodes with stable-intensity lobe positions in a highly elliptical core fiber. Existing two-mode-fiber devices can be improved by this stabilization of the second-order modes. Practical sensors employing the two spatial modes as the two arms of an interferometer are described. The two arms of an interferometer of this type can have the same group delays, while the difference in phase delays is large.
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