Trion Formation Resolves Observed Peak Shifts in the Optical Spectra of Transition-Metal Dichalcogenides.

Monolayer transition-metal dichalcogenides (ML-TMDs) have the potential to unlock novel photonic and chemical technologies if their optoelectronic properties can be understood and controlled. Yet, recent work has offered contradictory explanations for how TMD absorption spectra change with carrier concentration, fluence, and time. Here, we test our hypothesis that the large broadening and shifting of the strong band-edge features observed in optical spectra arise from the formation of negative trions.

Hot carrier extraction from 2D semiconductor photoelectrodes.

Hot carrier-based energy conversion systems could double the efficiency of conventional solar energy technology or drive photochemical reactions that would not be possible using fully thermalized, "cool" carriers, but current strategies require expensive multijunction architectures. Using an unprecedented combination of photoelectrochemical and in situ transient absorption spectroscopy measurements, we demonstrate ultrafast (<50 fs) hot exciton and free carrier extraction under applied bias in a proof-of-concept photoelectrochemical solar cell made from earth-abundant and potentially inexpensive monolayer (ML) MoS. Our approach facilitates ultrathin 7 Å charge transport distances over 1 cm areas by intimately coupling ML-MoS to an electron-selective solid contact and a hole-selective electrolyte contact.

The N3/TiO interfacial structure is dependent on the pH conditions during sensitization.

The electronic structure of the N3/TiO interface can directly influence the performance of a dye sensitized solar cell (DSSC). Therefore, it is crucial to understand the parameters that control the dye's orientation on the semiconductor's surface. A typical step in DSSC fabrication is to submerge the nanoparticulate semiconductor film in a solution containing the dye, the sensitizing solution.

The pH-dependent orientation of N3 dye on a gold substrate is revealed using heterodyne-detected vibrational sum frequency generation spectroscopy.

We report on systematic changes to the adsorption geometry of the dye N3 {[cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato ruthenium(II)]} on a gold substrate as the pH of the deposition environment is altered. The protonation states of the four -COOH groups of the N3 dye change according to the modified pH conditions, thus affecting the number of -COOH and -NCS functional groups that participate in the adsorption to gold. Here, we use heterodyne detected vibrational sum frequency generation (HD-VSFG) spectroscopy to obtain surface specific vibrational information on both -COOH and -NCS groups as a function of pH of the deposition conditions.