In this paper, we
present results from the detailed investigations
on the synthesis, optical, emission, electrochemical, and ultrafast
nonlinear optical (NLO) properties along with the excited state dynamics
of zinc(II) 2,10,16,24-tetrakis(9-phenyl-9H-carbazol-2-yl)phthalocyanine
(CBZPC1) and zinc(II) 2,10,16,24-tetrakis(4-(9H-carbazol-9-yl)phenyl)phthalocyanine (CBZPC2). Due to the presence of carbazole moieties, the Soret band was
found to be broadened. The emission studies performed using different
solvents revealed the fluorescence yields in the range of 0.10–0.27
and the time-resolved fluorescence data revealed radiative lifetimes
of, typically, a few nanoseconds. Femtosecond transient absorption
measurements indicated the formation of triplet states within the
first nanosecond of photoexcitation. From the cyclic voltametric studies,
the oxidation and reduction processes were found to be ring centered.
Spectral changes in the UV–visible absorption were recorded
by means of spectro-electrochemical analysis at an applied potential.
The DFT and TD-DFT analysis was employed using B3LYP hybrid functional
theory and 6-31G(d,p) basis set in the Gaussian 09 package. The NLO
properties of CBZPC1 and CBZPC2 were investigated
using the Z-scan technique and femtosecond (fs) pulses
with kHz and MHz repetition rates. Closed and open aperture Z-scan data were recorded at three different wavelengths
of 600, 700, and 800 nm, and the NLO coefficients were extracted from
both types of data. Two-photon absorption (TPA) was the dominant mechanism
observed in the open aperture Z-scan data. The real
and imaginary parts of the χ(3) along with the two-photon
absorption cross sections were evaluated. Our NLO data and large 2PA
coefficients and cross sections obtained indicate the potential of
these compounds for applications in optical limiting and optical switching
applications.
It is common knowledge that poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blend, a prototype system for bulk heterojunction (BHJ) solar cells, consists of a network of tens of nanometers-large donor-rich and acceptor-rich phases separated by extended finely intermixed border regions where PCBM diffuse into P3HT. Here we specifically address the photo-induced dynamics in a 10 nm thin P3HT/PCBM blend that consists of the intermixed region only. Using the multi-pass transient absorption technique (TrAMP) that enables us to perform ultra high sensitive measurements, we find that the primary process upon photoexcitation is ultrafast energy transfer from P3HT to PCBM. The expected charge separation due to hole transfer from PCBM to P3HT occurs in the 100 ps timescale. The derived picture is much different from the accepted view of ultra-fast electron transfer at the polymer/PCBM interface and provides new directions for the development of efficient devices.
Antimony(III) halide based zero dimensional hybrids have gained interest as broadband emitters. Until now, quadrangular pyramidal SbX5 based and octahedral SbX6 based 0D hybrids have been reported utilizing different organic...
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