In this paper, we assess the utility
of complementary routes to
silsesquioxane based compounds using F– catalyzed
coupling to synthesize [vinylSiO1.5]
x
PhSiO1.5]10‑x/12‑x
mixtures followed by copolymerization with divinylbenzene
(via ADMET), or using reverse Heck coupling with 1,4-dibromobenzene
and 4,4′-dibromo-stilbene to prepare lightly branched, nonlinear
BOC systems. In another paper, we describe the use of Heck and Suzuki
coupling to synthesize model conjugated p-R-stilbeneSQ
BOCs starting from [p-IPh8SiO1.5]8 and coupling with divinylbenzene (DVB) and 1,4-diethynylbenzene
(DEB) finding extended 3-D conjugation in the DEB polymers. We find
that the reverse Heck coupling (where the linker contains the bromo
moieties) works best for these systems giving BoC oligomers with M
n of ∼6 kDa, in which extended excited
state conjugation is observed for 1,4-dibromobenzene linked systems
through ∼50+ nm red shifts in the emission spectra compared
with DVB linked systems and model compounds. We compare and contrast
the photophysical properties of the two sets of BOCs and the system
where the conjugation length of the linker changes from divinylbenzene
to divinylstilbene. We find that for a linker with a longer conjugation
length, a red-shifted absorption and emission is observed; however,
the difference in emission is much larger for the 1,4-dibromobenzene-linked
system as compared to the model compounds, suggesting that a more
rigid linker contributes to better orbital overlap with the cage and/or
phenyl groups, increasing excited state conjugation interactions.
A rapid, low-temperature, solution-based photonic-annealing method is developed to prepare tin oxide electron transport layers for efficient perovskite solar cells.
Hybrid organic-inorganic halide perovskite solar cells have emerged as leading candidates for third-generation photovoltaic technology. Despite the rapid improvement in power conversion efficiency (PCE) for perovskite solar cells in recent years, the low frequency carrier kinetics that underlie practical roadblocks such as hysteresis and degradation remain relatively poorly understood. In an effort to bridge this knowledge gap, we perform here correlated low frequency noise (LFN) and impedance spectroscopy (IS) characterization that elucidates carrier kinetics in operating perovskite solar cells. Specifically, we focus on planar cell geometries with a SnO2
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