Perovskite solar cells (PSCs) with organic hole transporting layers (o-HTLs) have been widely studied due to their convenient solution processing, but it remains a big challenge to improve the hole mobilities of commercially available organic hole transporting materials without ion doping while maintaining the stability of PSCs. In this work, we demonstrated that the introduction of perovskite quantum dots (QDs) as interlayers between perovskite layers and dopant-free o-HTLs (P3HT, PTAA, Spiro-OMeTAD) resulted in a significantly enhanced performance of PSCs. The universal role of QDs in improving the efficiency and stability of PSCs was validated, exceeding that of lithium doping. After a deep examination of the mechanism, QD interlayers provided the multifunctional roles as follows: (1) passivating the perovskite surface to reduce the overall amount of trap states; (2) promoting hole extraction from perovskite to dopant-free o-HTLs by forming cascade energy levels; (3) improving hole mobilities of dopant-free o-HTLs by regulating their polymer/molecule orientation. What is more, the thermal/moisture/light stabilities of dopant-free o-HTLs-based PSCs were greatly improved with QD interlayers. Finally, we demonstrated the reliability of the QD interlayers by fabricating large-area solar modules with dopant-free o-HTLs, showing great potential in commercial usage.

Lead chalcogenide quantum dot (QD) infrared (IR) solar cells are promising devices for breaking through the theoretical efficiency limit of single‐junction solar cells by harvesting the low‐energy IR photons that cannot be utilized by common devices. However, the device performance of QD IR photovoltaic is limited by the restrictive relation between open‐circuit voltages (VOC) and short circuit current densities (JSC), caused by the contradiction between surface passivation and electronic coupling of QD solids. Here, a strategy is developed to decouple this restriction via epitaxially coating a thin PbS shell over the PbSe QDs (PbSe/PbS QDs) combined with in situ halide passivation. The strong electronic coupling from the PbSe core gives rise to significant carrier delocalization, which guarantees effective carrier transport. Benefited from the protection of PbS shell and in situ halide passivation, excellent trap‐state control of QDs is eventually achieved after the ligand exchange. By a fine control of the PbS shell thickness, outstanding IR JSC of 6.38 mA cm−2 and IR VOC of 0.347 V are simultaneously achieved under the 1100 nm‐filtered solar illumination, providing a new route to unfreeze the trade‐off between VOC and JSC limited by the photoactive layer with a given bandgap.

Interfacial charge transfer from silicon to heterogeneous catalysts plays a key role in silicon-based photoelectrochemical systems. In general, prior to interfacial charge transfer, carriers that are generated by photons with energies above the bandgap dissipate the excess kinetic energy via hot-carrier cooling, and such energy loss limits the maximum power conversion efficiency. The excess energy of hot-carriers, however, could be utilized through hot-carrier transfer from silicon to the catalysts, but such hot-carrier extraction has not yet been demonstrated. Here, we exploit transient reflection spectroscopy to interrogate charge transfer at the interface between silicon and platinum. Quantitative modeling of the surface carrier kinetics indicates that the velocity of charge transfer from silicon to platinum exceeds 2.6 × 107 cm s−1, corresponding to an average carrier temperature of extracted carriers of ∼600 K, two times higher than the lattice temperature. The charge transfer velocity can be controllably reduced by inserting silica spacing layers between silicon and platinum.

The self-trapping of a free carrier in transition-metal oxides can lead to a small polaron, which is responsible for the inadequate performance of the oxide-based optoelectronic applications. Thus, fundamental understanding of the self-trapping mechanism is of key importance for improving the performance of these applications. Herein, the self-trapping in Co 3 O 4 epitaxial monocrystalline films is investigated primarily by transient absorption spectroscopy. The spectral evolution corresponding to the ultrafast transition from free carriers to small polarons is identified, which allows us to extract the self-trapping kinetics. The relationship between the self-trapping rate and temperature suggests a lack of thermal activation energy. A barrierless self-trapping mechanism derived from the small polaron framework is then proposed, which can successfully describe the observation that self-trapping rate decreases linearly with increasing temperature. Given that small polarons are ubiquitous in transition-metal oxides, this self-trapping mechanism is potentially a general phenomenon in these materials.