Ultrafast dynamics in polymeric carbon nitride thin films probed by time-resolved EUV photoemission and UV-Vis transient absorption spectroscopy

The ground- and excited-state electronic structures of four polymeric carbon nitride (PCN) materials have been investigated using a combination of photoemission and optical absorption spectroscopy. To establish the driving forces for photocatalytic water-splitting reactions, the ground-state data was used to produce a band diagram of the PCN materials and the triethanolamine electron scavenger, commonly implemented in water-splitting devices. The ultrafast charge-carrier dynamics of the same PCN materials were also investigated using two femtosecond-time-resolved pump–probe techniques: extreme-ultraviolet (EUV) photoemission and ultraviolet-visible (UV-Vis) transient absorption spectroscopy. The complementary combination of these surface- and bulk-sensitive methods facilitated photoinduced kinetic measurements spanning the sub-picosecond to few nanosecond time range. The results show that 400 nm (3.1 eV) excitation sequentially populates a pair of short-lived transient species, which subsequently produce two different long-lived excited states on a sub-picosecond time scale. Based on the spectro-temporal characteristics of the long-lived signals, they are assigned to singlet-exciton and charge-transfer states. The associated charge-separation efficiency was inferred to be between 65% and 78% for the different studied materials. A comparison of results from differently synthesized PCNs revealed that the early-time processes do not differ qualitatively between sample batches, but that materials of more voluminous character tend to have higher charge separation efficiencies, compared to exfoliated colloidal materials. This finding was corroborated via a series of experiments that revealed an absence of any pump-fluence dependence of the initial excited-state decay kinetics and characteristic carrier-concentration effects that emerge beyond few-picosecond timescales. The initial dynamics of the photoinduced charge carriers in the PCNs are correspondingly determined to be spatially localised in the immediate vicinity of the lattice-constituting motif, while the long-time behaviour is dominated by charge-transport and recombination processes. Suppressing the latter by confining excited species within nanoscale volumes should therefore affect the usability of PCN materials in photocatalytic devices

Charge transfer to solvent dynamics in iodide aqueous solution studied at ionization threshold

We explore the early-time electronic relaxation in NaI aqueous solution exposed to a short UV laser pulse. Rather than initiating the charge transfer reaction by resonant photoexcitation of iodide, in the present time-resolved photoelectron spectroscopy study the charge-transfer-to-solvent (CTTS) states are populated via electronic excitation above the vacuum level. By analyzing the temporal evolution of electron yields from ionization of two transient species, assigned to CTTS and its first excited state, we determine both their ultrafast population and relaxation dynamics. Comparison with resonant- excitation studies shows that the highly excited initial states exhibit similar relaxation characteristics as found for resonant excitation. Implications for structure and dynamical response of the hydration cage are discussed

Charge Transfer Dynamics at Dye-Sensitized ZnO and TiO₂ Interfaces Studied by Ultrafast XUV Photoelectron Spectroscopy

Interfacial charge transfer from photoexcited ruthenium based N3 dye molecules into ZnO thin films received controversial interpretations. To identify the physical origin for the delayed electron transfer in ZnO compared to TiO2, we probe directly the electronic structure at both dye semiconductor interfaces by applying ultrafast XUV photoemission spectroscopy. In the range of pump probe time delays between 0.5 to 1.0 amp; 8201;ps, the transient signal of the intermediate states was compared, revealing a distinct difference in their electron binding energies of 0.4 amp; 8201;eV. This finding strongly indicates the nature of the charge injection at the ZnO interface associated with the formation of an interfacial electron cation complex. It further highlights that the energetic alignment between the dye donor and semiconductor acceptor states appears to be of minor importance for the injection kinetics and that the injection efficiency is dominated by the electronic couplin

Ultrafast kinetics of linkage isomerism in Na₂[Fe(CN)₅NO] aqueous solution revealed by time-resolved photoelectron spectroscopy

The kinetics of ultrafast photoinduced structural changes in linkage isomers is investigated using Na2[Fe(CN)5NO] as a model complex. The buildup of the metastable side-on configuration of the NO ligand, as well as the electronic energy levels of ground, excited, and metastable states, has been revealed by means of time-resolved extreme UV (XUV) photoelectron spectroscopy in aqueous solution, aided by theoretical calculations. Evidence of a short-lived intermediate state in the isomerization process and its nature are discussed, finding that the complete isomerization process occurs in less than 240 fs after photoexcitation

Injection Kinetics and Electronic Structure at the N719/TiO₂ Interface Studied by Means of Ultrafast XUV Photoemission Spectroscopy

The method of transient XUV photoemission spectroscopy is developed to investigate the ultrafast dynamics of heterogeneous electron transfer at the interface between the N719 ruthenium dye complex and TiO₂ nanoparticles. XUV light from high-order harmonic generation is used to probe the electron density distribution among the ground and excited states at the interface after its exposure to a pump laser pulse of 530 nm wavelength. A spectral decomposition of the transient emission signal is used to follow the population and decay dynamics of the involved transient states individually. By comparing results obtained for the N719/TiO₂ and N719/FTO interfaces, we can unambiguously reveal the kinetics of electrons injected to TiO₂ from the singlet metal-to-ligand charge-transfer (MLCT) excited state of the dye. With the developed approach, we characterize both the kinetic constants and the absolute binding energies of the singlet and triplet MLCT states of the dye and the state of electrons injected to the conduction band of TiO₂. The energy levels of the singlet and triplet states are found to lie 0.7 eV above and 0.2 eV below the conduction band minimum, respectively. This energetic structure gives rise to a strong driving force for injection from the singlet state and a slow electron transfer from the triplet state, the latter being possible due to a partial overlap of the triplet state band of N719 and the conduction band of TiO₂