Rapid hot carrier cooling is the key loss channel overriding all possible energy loss pathways that limit achievable solar conversion efficiency. Thus, delayed hot carrier cooling in the cell absorber layer can make hot carrier extraction a less cumbersome task, assisting in the realization of hot carrier solar cells. There have been plentitude of reports concerning the slow carrier cooling in perovskite materials, which eventually triggered interest in radical understanding of the native photophysics driving the device design. Here in this finding, a further dramatic dip in the cooling rate has been discerned upon a growing Cs 4 PbBr 6 shell over CsPbBr 3 core nanocrystals (NCs), in contrast to the bare CsPbBr 3 core NCs. Using transient absorption spectroscopy, we investigated the disparity in the hot carrier thermalization pathways in the CsPbBr 3 and CsPbBr 3 @Cs 4 PbBr 6 core−shell NCs under the same laser fluence, which can be validated as a corollary of polaron formation in the later NCs.

The performance of the high-end optoelectronic devices is essentially influenced by the intrinsic relaxation mechanisms pursued by the hot carriers. Therefore, the key toward achieving progression in such fields lies in developing a complete understanding of the involved carrier cooling dynamics. In this work, an endeavor has been made to highlight the difference in the cooling mechanisms in 2D CsPbBr 3 nanosheets (NSs) and their 3D counterpart nanocrystals (NCs) with the aid of femtosecond broad-band pump− probe spectroscopy, varying the excitation energies. The exciton and biexciton dynamics in both systems are found to be retarded upon increasing the excitation energy. However, in contrast to 3D NCs, carrier cooling is found to be faster in the 2D system, regardless of the excitation energy used, attributing this to less efficient charge screening by Froḧlich interaction in low-dielectric medium. A similar trend is replicated in the biexciton formation rate since the formation is also found to be faster in NSs compared to NCs.

Many-body states like excitons, biexcitons, and trions play an important role in optoelectronic and photovoltaic applications in 2D materials. Herein, we studied carrier dynamics of excitons and trions in monolayer MoS2 deposited on a SiO2/Si substrate, before and after Au NP deposition, using femtosecond transient absorption spectroscopy. Luminescence measurements confirm the presence of both an exciton and trion in MoS2, which are drastically quenched after deposition of Au NPs, indicating electron transfer from photoexcited MoS2 to Au. Ultrafast study reveals that photogenerated free carriers form excitons with a time scale of ∼500 fs and eventually turn into trions within ∼1.2 ps. Dissociation of excitons and trions has been observed in the presence of Au, with time scales of ∼600 fs and ∼3.7 ps, respectively. Understanding the formation and dissociation dynamics of the exciton and trion in monolayer MoS2 is going to help immensely to design and develop many new 2D devices.

Elemental doping has already been established to be one of the most effective approaches for band-gap engineering and controlled material response for improved photocatalytic activity. Herein atomically thin ZnIn2S4 (ZIS) nanosheets were doped with O and N separately, and the effects of doping were spectroscopically investigated for photocatalytic H2 evolution. Steady-state photoluminescence studies revealed an enhanced charge-carrier population in the doped systems along with a defect-state-induced broad peak in the red region of the spectra. Transient absorption (TA) spectroscopy demonstrated that the conduction-band-edge electrons are transferred on an ultrafast time scale to the inter-band-gap defect states. TA analysis suggests that O and N doping contributes to the defect state concentration and ensures an enhanced photocatalytic activity of the system. This detailed spectroscopic analysis uncovers the role of inter-band-gap defect states in the photocatalytic activity of ZIS and will open new avenues for the construction of nanosheet-based optical devices.

To improve the constraints of kesterite Cu 2 ZnSnS 4 (CZTS) solar cell, such as undesirable band alignment at p–n interfaces, bandgap tuning, and fast carrier recombination, cadmium (Cd) is introduced into CZTS nanocrystals forming Cu 2 Zn 1– x Cd x SnS 4 through cost-effective solution-based method without postannealing or sulfurization treatments. A synergetic experimental–theoretical approach was employed to characterize and assess the optoelectronic properties of Cu 2 Zn 1– x Cd x SnS 4 materials. Tunable direct band gap energy ranging from 1.51 to 1.03 eV with high absorption coefficient was demonstrated for the Cu 2 Zn 1– x Cd x SnS 4 nanocrystals with changing Zn/Cd ratio. Such bandgap engineering in Cu 2 Zn 1– x Cd x SnS 4 helps in effective carrier separation at interface. Ultrafast spectroscopy reveals a longer lifetime and efficient separation of photoexcited charge carriers in Cu 2 CdSnS 4 (CCTS) nanocrystals compared to that of CZTS. We found that there exists a type-II staggered band alignment at the CZTS (CCTS)/CdS interface, from cyclic voltammetric (CV) measurements, corroborated by first-principles density functional theory (DFT) calculations, predicting smaller conduction band offset (CBO) at the CCTS/CdS interface as compared to the CZTS/CdS interface. These results point toward efficient separation of photoexcited carriers across the p–n junction in the ultrafast time scale and highlight a route to improve device performances.