Co-Sensitization Effects of Indoline and Carbazole Dyes in Solar Cells and Their Neutral-Anion Equilibrium in Solution.

Co-sensitization of two or more light-absorbing compounds on a TiO2 surface has recently become one of the most successful strategies in the development of dye-sensitized solar cells (DSSCs). The specific structure of the dyes for DSSCs implies that they can partly exist in anionic forms in popular solvents used for sensitization. Our study concerns the above two issues being analyzed in detail using the example of the popular carbazole (MK2) and indoline (D205) dyes, studied by stationary absorption and emission, femtosecond transient absorption (in complete cells and in the solutions), current-voltage measurements, DFT and TD-DFT theoretical calculations. After the addition of D205 to DSSC with MK2, the fill factor of the cells was improved, and the electron recombination between TiO2 and the dyes was blocked (observed on sub-nanosecond time scales). Thus, the active co-adsorbent can take the role of the typically used passive additive, like chenodeoxycholic acid. Evidence of the concentration-dependent equilibrium between neutral and anionic forms of dyes with different lifetimes was found in acetonitrile solutions (the best for sensitization), while in ethanol solution the dominant form was the anion (worse for sensitization). Our findings should help in better understanding the operation and optimization of DSSC.

Impact of improvements in mesoporous titania layers on ultrafast electron transfer dynamics in perovskite and dye-sensitized solar cells.

Improvement in the performance of perovskite solar cells (PSC) and dye-sensitized solar cells (DSSC) upon modifications of mesoporous titania layers has been studied. For PSC with triple cation perovskite (FA0.76 MA0.19 Cs0.05 Pb (I0.81 Br0.19)3) about 40% higher photocurrent (up to ∼24 mA cm-2) was found for more homogenous, made of larger particles (30 nm) and thinner (150-200 nm) titania layer. For DSSC (both with liquid cobalt-based electrolyte as well as with solid state hole transporter - spiro-OMeTAD), a greater dye loading, rise in photovoltage, and the enhancement in relative photocurrent were observed for the cells prepared from the diluted titania paste (2 : 1 w/w ratio) with respect to those prepared from undiluted one. The impact of these improvements in titania layers on charge transfer dynamics in the complete solar cells as well as in pristine TiO2 layers was investigated by femtosecond transient absorption. Shorter photocarriers lifetime in perovskite material observed in better PSC, indicated that faster electron transfer at the titania interface was responsible for the higher photocurrent. Moreover, the photoinduced changes close to TiO2 interface were revealed in better PSC, which may indicate that in the efficient devices halide segregation takes place in perovskite material. In liquid DSSC, the fast component of unwanted recombination was slower in the samples with the diluted titania paste than in those made with undiluted ones. In solid state DSSC, hole injection from MK2 dye to spiro-OMeTAD takes place on the very fast ps time scale (comparable to that of electron injection) and the evidence of better penetration of spiro-OMeTAD into thinner and more porous titania layers was provided.

Insights into the limitations of solar cells sensitized with ruthenium dyes revealed in time-resolved spectroscopy studies.

The substitution of iodide electrolytes with cobalt ones has led to the current champion laboratory efficiencies for dye-sensitized solar cells (DSSCs). However, unlike with organic dyes, this strategy does not work with classical ruthenium dyes. Therefore, we compare DSSCs sensitized with a popular Ru dye (N719) using both types of electrolytes by exploring the electron dynamics occurring from sub-ps to seconds. An important limitation in the photocurrent of cobalt-based cells is revealed to be due to electron recombination between titania and oxidized Ru dyes, which is much higher than that in iodide-based cells and occurs on the time scale of tens and hundreds of ps. Electron recombination between titania and the electrolyte, taking place on the millisecond time scale, is responsible for further lowering of the photovoltage and fill factor of cobalt-based cells. Ruthenium dyes also exhibit lower absorption coefficients with respect to their organic counterparts. For this reason, we also investigate the effect of the changes in the titania layer thickness, addition of scattering nanoparticles and modifications in the TiCl4 treatment on DSSC performance.

Effects of Post-Assembly Molecular and Atomic Passivation of Sensitized Titania Surface: Dynamics of Electron Transfer Measured from Femtoseconds to Seconds.

The dynamics of electron transfer at the dye-titania and titania-electrolyte interfaces is investigated in two post-sensitization processes: (i) atomic layer deposition of blocking alumina coating and (ii) hierarchical molecular multicapping. To measure the electron transfer dynamics, time-resolved spectroscopic methods (femtosecond transient absorption on the time scale from femtoseconds to nanoseconds and electrochemical impedance spectroscopy on the time scale from milliseconds to seconds) are applied to the complete dye-sensitized solar cells with cobalt-based electrolyte and champion ADEKA-1 dye (with silyl-anchor unit) or its popular carboxyl-anchor analogue, MK-2 dye. Both molecular capping and alumina blocking layers slow down the electron injection process (the average rate constant decreases from 1.1 ps-1 to 0.4 ps-1) and partial sub-nanosecond back electron transfer from titania to the dye (from ca. 10 ns-1 to 5 ns-1). Very small alumina layers (of 0.1 nm thickness) have the highest impact on reducing the rate constants of these electron transfer processes, and for the thicknesses greater than 0.3 nm the rate constants hardly change. In contrast, the electron recombination between titania and electrolyte, occurring on the millisecond time scale, starts to be significantly suppressed for the blocking layers of 0.3 nm or more in thickness (up to ca. 20 times for 0.5 nm thickness with respect to that for untreated sample), improving open circuit voltage and fill factor of the cells. The amplitude of the relative photocurrent (short circuit current per number of absorbed photons) is found to depend almost exclusively on the ultrafast and fast processes taking place in the first nanoseconds after dye excitation. The positive impact of coadsorbents on the solar cells performance for both ADEKA-1 and MK-2 is also studied.