The iodide/triiodide redox shuttle has limited the efficiencies accessible in dye-sensitized solar cells. Here, we report mesoscopic solar cells that incorporate a Co((II/III))tris(bipyridyl)-based redox electrolyte in conjunction with a custom synthesized donor-π-bridge-acceptor zinc porphyrin dye as sensitizer (designated YD2-o-C8). The specific molecular design of YD2-o-C8 greatly retards the rate of interfacial back electron transfer from the conduction band of the nanocrystalline titanium dioxide film to the oxidized cobalt mediator, which enables attainment of strikingly high photovoltages approaching 1 volt. Because the YD2-o-C8 porphyrin harvests sunlight across the visible spectrum, large photocurrents are generated. Cosensitization of YD2-o-C8 with another organic dye further enhances the performance of the device, leading to a measured power conversion efficiency of 12.3% under simulated air mass 1.5 global sunlight.
In recent years, hybrid perovskite solar cells (PSCs) have attracted much attention owing to their low cost, easy fabrication, and high photoelectric conversion efficiency. Nevertheless, solution‐processed perovskite films usually show substantial structural disorders, resulting in ion defects on the surface of lattice and grain boundaries. Herein, a series of D–π–A porphyrins coded as CS0, CS1, and CS2 that can effectively passivate the perovskite surface, increase VOC and FF, reduce the hysteresis effect, enhance power conversion efficiency to be higher than 22%, and improve the device stability is developed. The results in this study demonstrated that the donor–π–acceptor type porphyrin derivatives are promising passivators that can improve the cell performance of PSCs.
Co-sensitization of two or more dyes with complementary absorption spectra on a semiconductor film
is an effective approach to enhance the performance of a dye-sensitized solar cell (DSSC). Porphyrin
sensitizer YD2-oC8 showed outstanding photovoltaic performance co-sensitized with an organic dye to
cover the entire visible spectral region, 400–700 nm. To promote the light-harvesting capability beyond
700 nm, a porphyrin dimer (YDD6) was synthesized for a co-sensitized system. We report a systematic
approach for engineering of molecular co-sensitization of TiO2 films in a cocktail solution containing
YD2-oC8, an organic dye (CD4) and YDD6 in a specific molar ratio to optimize the photovoltaic
performance of the device. The resulting device showed panchromatic spectral features in the IPCE
action spectrum in the region 400–700 nm attaining efficiencies of 75–80%; the spectrum is extended to
the near-IR region attaining 40–45% in 700–800 nm region, giving JSC/mA cm
2 ¼ 19.28, VOC/mV ¼
753, FF ¼ 0.719, and h ¼ 10.4% under standard AM 1.5 G one-sun irradiation. This performance is
superior to what is obtained from the individual single-dye devices and the two-dye co-sensitized
systems. The shifts of TiO2 potential upon dye uptake and the kinetics of charge recombination were
examined through measurements of the charge extraction (CE) and intensity-modulated photovoltage
spectroscopy (IMVS), respectively. Five co-sensitized systems were investigated to demonstrate that
suppression of dye aggregation of YDD6 in the co-sensitized film is a key factor to further improve the
device performance
Three alkoxy-wrapped push-pull porphyrins were designed and synthesized for dye-sensitized solar cell (DSSC) applications. Spectral, electrochemical, photovoltaic and electrochemical impedance spectroscopy properties of these porphyrin sensitizers were well investigated to provide evidence for the molecular design.
A series of zinc porphyrin dyes YD22-YD28 were synthesized and used for dye-sensitized solar cells. Dyes YD26-YD28 consist of zinc porphyrin (ZnP) as core unit, arylamine (Am) as electron-donating group, and p-ethynylbenzoic acid (EBA) as an electron-withdrawing/-anchoring group. The dyes YD22-YD25 contain additional phenylethynylene group (PE) bridged between Am and ZnP units. The influence of the PE unit on molecular properties as well as photovoltaic performances were investigated via photophysical and electrochemical studies and density functional calculations. With the insertion of PE unit, the dyes YD22-YD25 possess better light-harvesting properties in terms of significantly red-shifted Q-band absorption. The conversion efficiencies for dyes YD22-YD25 are better than those of dyes YD26-YD28 owing to larger J(SC) output. Natural transition orbitals and Mulliken charge analysis were used to analyze the electron injection efficiency for porphyrin dyes upon time-dependent DFT calculations. The results indicated that insertion of additional PE unit is beneficial to higher J(SC) by means of improved light-harvesting property due to broadened and red-shifted absorption.
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