Theoretical Investigation on Copper(I) Complexes Featuring a Phosphonic Acid Anchor with Asymmetric Ligands for DSSC

Abstract

A series of heteroleptic copper­(I) complexes featuring a phosphonic acid anchor with asymmetric ligands has been studied using density functional theory (DFT) and time-dependent DFT (TD-DFT). Results showed that the absorption spectra of all copper­(I) complexes covered the visible light region with typical metal-to-ligand charge transfer characteristics. The modification of functionalized asymmetric ligands by introducing phenyl, anisole, N,N-diethyl-4-vinylaniline, and bromobenzene groups can reduce the energy gap (ΔH–L), form an effective charge-separated state, and lead to red-shifted absorption within the 350–650 nm range compared to the reference complex. The copper­(I) complexes with functionalized N,N-diethyl-4-vinylaniline ligands displayed the smallest ΔH–L and highest light-harvesting efficiency (LHE), exhibiting excellent light-harvesting capabilities. The introduction of isoquinoline ligands increased the excited singlet state lifetimes, the number of transferred electrons, and electron transfer distances. The electron injection time and driving force revealed efficient interfacial electron injection and regeneration of oxidized dyes. The photoelectronic properties of copper­(I) complexes featuring a pyridine ring with asymmetric ancillary ligands were superior to those of the reference complex. These copper­(I) complexes exhibited desirable electronic and spectral characteristics for future DSSC applications.

Solar energy conversion using first row d-block metal coordination compound sensitizers and redox mediators

“…This work concluded that the use of these ancillaries coupled with appropriate functionalization (ligands 49-51) is effective in reducing the HOMO-LUMO energy gap and enhancing the lightharvesting of the dye. 214 However, the latter is offset by a low transport resistance, leading to a high J SC and V OC . DSCs with [Cu(11)(48)] + have the lowest transport resistance of this family of dyes.…”

“…This work concluded that the use of these ancillaries coupled with appropriate functionalization (ligands 49-51) is effective in reducing the HOMO-LUMO energy gap and enhancing the light-harvesting of the dye. 214 45)] + , the device exhibited a high chemical capacitance and a low recombination resistance. However, the latter is offset by a low transport resistance, leading to a high J SC and V OC .…”

“…This work concluded that the use of these ancillaries coupled with appropriate functionalization (ligands 49–51) is effective in reducing the HOMO–LUMO energy gap and enhancing the light-harvesting of the dye. 214 Indeed, DSCs sensitized with [Cu(11)(45)] + , [Cu(11)(46)] + , [Cu(11)(47)] + and [Cu(11)(48)] + gave some of the highest values of V OC and J SC ( Table 5 ) observed for heteroleptic copper( i ) dyes, and the PCE for [Cu(11)(45)] + exceeded 3% for fully masked cells. Electrochemical impedance spectroscopy (EIS) was used to understand the striking DSC performances with [Cu(11)(45)] + and [Cu(11)(48)] + .…”

Simultaneous Enhancement of Charge Separation and Hole Transportation in a W:α-Fe2O3/MoS2 Photoanode: A Collaborative Approach of MoS2 as a Heterojunction and W as a Metal Dopant

“…As shown in Figure b, the light-harvesting efficiency (LHE) values of the α-Fe 2 O 3 , 0.5W:α-Fe 2 O 3 , and 0.5W:α-Fe 2 O 3 /MoS 2 thin films show enhanced light absorption, which is effective for catching more photons and generating more charge carriers; the LHE is obtained using eq where A (λ) is the absorbance at different wavelengths. The higher absorbance of the photoelectrode led to higher LHE values.…”

Enhanced Efficiency of Dye-Sensitized Solar Cells Based on Polymer-Assisted Dispersion of Platinum Nanoparticles/Carbon Nanotubes Nanohybrid Films as FTO-Free Counter Electrodes

“…Renewable energy, including hydropower, wind power, tidal energy, geothermal energy, and solar energy, has shown significant development [ 6 , 7 ], among which solar energy has shown great industrial development [ 8 ]. Dye-sensitized solar cells (DSSCs) have the advantages of transparency, colorfulness, simplicity in manufacturing, and low production cost, making them one of the most promising devices for solar power generation [ 9 , 10 ]. The main components of a typical DSSC are redox electrolytes (such as iodide/triiodide in an organic solvent), a dye-fixed photoelectrode (PE), and a counter electrode (CE) [ 11 ], where an ideal CE should have a high exchange current density and low charge transfer resistance [ 12 ].…”