The ideal driving force for dye regeneration is an important parameter for the design of efficient dye-sensitized solar cells. Here, nanosecond laser transient absorption spectroscopy was used to measure the rates of regeneration of six organic carbazole-based dyes by nine ferrocene derivatives whose redox potentials vary by 0.85 V, resulting in 54 different driving-force conditions. It was found that the reaction follows the behavior expected for the Marcus normal region for driving forces below 29 kJ mol(-1) (ΔE = 0.30 V). Driving forces of 29-101 kJ mol(-1) (ΔE = 0.30-1.05 V) resulted in similar reaction rates, indicating that dye regeneration is diffusion controlled. Quantitative dye regeneration (theoretical regeneration yield 99.9%) can be achieved with a driving force of 20-25 kJ mol(-1) (ΔE ≈ 0.20-0.25 V).
An electrolyte based on the tris(acetylacetonato)iron(III)/(II) redox couple ([Fe(acac)3](0/1-)) was developed for p-type dye-sensitized solar cells (DSSCs). Introduction of a NiO blocking layer on the working electrode and the use of chenodeoxycholic acid in the electrolyte enhanced device performance by improving the photocurrent. Devices containing [Fe(acac)3](0/1-) and a perylene-thiophene-triphenylamine sensitizer (PMI-6T-TPA) have the highest reported short-circuit current (J(SC)=7.65 mA cm(-2)), and energy conversion efficiency (2.51%) for p-type DSSCs coupled with a fill factor of 0.51 and an open-circuit voltage V(OC)=645 mV. Measurement of the kinetics of dye regeneration by the redox mediator revealed that the process is diffusion limited as the dye-regeneration rate constant (1.7×10(8) M(-1) s(-1)) is very close to the maximum theoretical rate constant of 3.3×10(8) M(-1) s(-1). Consequently, a very high dye-regeneration yield (>99%) could be calculated for these devices.
Monodisperse cadmium sulphide (CdS) quantum dots (QDs) with a tunable size from 1.4 to 4.3 nm were synthesized by a non-injection method, and their surface states were characterized by photoluminescence spectroscopy and X-ray Photoelectron Spectroscopy (XPS). The steady state photoluminescence study identified that the proportion of the trap state emission increased with the QD size decrease, while from the photoluminescence decay study, it appeared that the trap state emission results from the emission via a surface deep trap state. The XPS measurements revealed the existence of surface Cd with sulfur vacancy sites which act as electron trap sites, and the population of these sites increases with the QD size decrease. These results are consistent to conclude that the trap state emission mainly originates from the surface deep trapped electrons at the surface Cd with sulfur vacancy sites.
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