Kostas Seintis

Solvent and branching effect on the two-photon absorption properties of push–pull triphenylamine derivatives

The photophysical and two-photon absorption (2PA) properties of two tri-podal molecules and of their quadrupolar and dipolar counterparts are reported for a series of solvents with varying polarity. The molecules possess a tri-phenylamine electron donating group and mono-cyano acceptors while olefinic and acetylenic π-linkers have been used. Branching led to an increase of the molar extinction coefficient and to a slight bathochromic shift of the absorption spectra while the fluorescence quantum yields decrease but they are maintained to relatively high values. Solvatochromic measurements in the tri-podal molecules revealed an emitting state with a polar nature. The 2PA cross sections in general increase upon branching but the observed behaviour strongly depends on the type of solvent. The highest 2PA cross sections are obtained in solvents of medium polarity and values as high as 1420 GM are reported.

A silanol-functionalized polyoxometalate with excellent electron transfer mediating behavior to ZnO and TiO 2 cathode interlayers for highly efficient and extremely stable polymer solar cells

Combining high efficiency and long lifetime under ambient conditions still poses a major challenge towards commercialization of polymer solar cells. Here we report a facile strategy that can simultaneously enhance the efficiency and temporal stability of inverted photovoltaic architectures. Inclusion of a silanol-functionalized organic–inorganic hybrid polyoxometalate derived from a PW9O34 lacunary phosphotungstate anion, namely (nBu4N)3[PW9O34(tBuSiOH)3], significantly increases the effectiveness of the electron collecting interface, which consists of a metal oxide such as titanium dioxide or zinc oxide, and leads to a high efficiency of 6.51% for single-junction structures based on poly(3-hexylthiophene):indene-C60 bisadduct (P3HT:IC60BA) blends. The above favourable outcome stems from a large decrease in the work function, an effective surface passivation and a decrease in the surface energy of metal oxides which synergistically result in the outstanding electron transfer mediating capability of the functionalized polyoxometalate. In addition, the insertion of a silanol-functionalized polyoxometalate layer significantly enhances the ambient stability of unencapsulated devices which retain nearly 90% of their original efficiencies (T90) after 1000 hours.

Photophysical and Protonation Time Resolved Studies of Donor-Acceptor Branched Systems with Pyridine Acceptors

A comparative study of the photophysical properties of octupolar pyridyl-terminated triphenylamine molecule, with its quadrupolar and dipolar analogues, by means of ambient and low temperature steady state spectroscopy and femtosecond to nanosecond time-resolved fluorescence spectroscopy is reported. The push-pull molecules bear triphenylamine electron donating core, pyridine peripheral electron acceptors, and acetylene π-bridge. The samples were studied in solvents of varying polarity and also upon addition of small amounts of acetic acid to induce protonation of the pyridine group. All samples exhibit significant positive fluorescence solvatochromism as well as a relaxation of their excited state to a solvent relaxed intramolecular charge transfer state on the picosecond time scale. For the octupolar compound, excited state relaxation occurs simultaneously with excitation energy hopping among the branches. The hopping time is solvent polarity controlled since it becomes slower as the polarity increases. The experimental hopping times are compared to those predicted by Förster and Fermi formulations. The samples are capable of emitting broadband light covering almost the whole visible spectrum by careful control of protonation. Energy transfer from the neutral toward the protonated species on the 1 ps time scale is revealed.

Insights into the passivation effect of atomic layer deposited hafnium oxide for efficiency and stability enhancement in organic solar cells

Atomic layer deposited hafnium oxide is inserted between the zinc oxide electron transport material and the photoactive blend to serve as an ultra-thin passivation interlayer in organic solar cells with an inverted architecture. The deposition of hafnium oxide significantly improves the surface properties of zinc oxide via effective surface passivation and beneficial modification of surface energy; the latter leads to improved nanomorphology of the photoactive blend. As a result, lower recombination losses and improved electron transport/collection at the cathode interface are achieved. A simultaneous increase in open-circuit voltage, short-circuit current density and fill factor is obtained leading to a power conversion efficiency of 6.30% in the ALD-modified cell using a poly(3-hexylthiophene):indene-C60-bisadduct blend as the photoactive layer; this represents a 25% improvement compared to 5.04% of the reference device. Moreover, the incorporation of the passivation interlayer yields a significant stability enhancement in the fabricated solar cells which retain more than 80% of their initial efficiency (T80 lifetime) after 750 hours while the reference cell exhibits a T80 equal to 250 hours.