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Metal oxide nanocrystals are emerging as an extremely versatile material for addressing many of the current challenging demands of energy-conversion technology. Being able to exploit their full potential is not only an advantage but also a scientific and economic ambition for a more sustainable energy development. In this direction, the photodoping of metal oxide nanocrystals is a very notable process that allows accumulating multiple charge carriers per nanocrystal after light absorption. The reactivity of the photodoped electrons is currently the subject of an intense study. In this context, the possibility to extract efficiently the stored electrons could be beneficial for numerous processes, from photoconversion and sunlight energy storage to photocatalysis and photoelectrochemistry. In this work we provide, via oxidative titration and optical spectroscopy, evidence for multi-electron transfer processes from photodoped Sn : In2O3 nanocrystals to a widely employed organic electron acceptor (F4TCNQ). The results of this study disclose the potential of photodoped electrons to drive chemical reactions involving more than one electron., Photodoped ITO nanocrystals (NCs) enables multi-electron transfer processes unveiled by F4TCNQ titration analysis. Metal oxide NCs are emerging as extremely versatile materials for energy storage and conversion technologies.

In the research field on materials for energy solutions, the exploitation of organic compounds and polymers is of great interest, especially in view of a more eco-sustainable development. In this context, the 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) molecule actively participates in the optimization of manyoptoelectronic devicesbased on such elements, thanks to its electrical properties. In this paper, we report a study on its optical properties, in particular demonstrating fluorescence emission from solutions containing F4TCNQ. This phenomenon is equally relevant, together with the effects on electricalconductivity, in the design of systems for energy technology. The results we present here offer new insights in the phenomenological picture of this molecule and can sharpen its applicability.

Characterizing carrier redistribution due to optical field modulation in a plasmonic hot-electron/semiconductor junction can be used to raise the framework for harnessing the carrier decay of plasmonic metals in more efficient conversion systems. In this work we comprehensively studied the carrier redistribution mechanisms of a 1-dimensional (1D) metal-semiconductor Schottky architecture, holding the dual feature of a hot-electron plasmonic system and a simple metal/semiconductor junction. We obtained a strongly enhanced external quantum efficiency (EQE) of the plasmonic Ag decorated ZnO semiconductor in both the band-edge region of ZnO and the corresponding plasmonic absorption profile of the Ag NPs (visible region). Simultaneously, the insertion of an insulating Al2O3 intermediate layer between Ag NPs and ZnO resulted in a parallel distinction of the two main non-radiative carrier transfer mechanisms of plasmonic NPs, i.e. direct electron transfer (DET) and plasmonic induced resonance energy transfer (PIRET). The multi-wavelength transient pump-probe spectroscopy indicated the very fast plasmonic radiative transfer dynamics of the system in Validerad;2021;Nivå 2;2021-11-29 (johcin);Artikeln har tidigare förekommit som manuskript i avhandling

Ternary I-III-VI 2 nanocrystals (NCs), such as AgInS 2 and CuInS 2 , are garnering interest as heavy-metal-free materials for photovoltaics, luminescent solar concentrators, LEDs, and bioimaging. The origin of the emission and absorption properties in this class of NCs is still a subject of debate. Recent theoretical and experimental studies revealed that the characteristic Stokes-shifted and long-lived luminescence of stoichiometric CuInS 2 NCs arises from the detailed structure of the valence band featuring two sublevels with different parity. The same valence band substructure is predicted to occur in AgInS 2 NCs, yet no experimental confirmation is available to date. Here, we use complementary spectroscopic, spectro-electrochemical, and magneto-optical investigations as a function of temperature to investigate the band structure and the excitonic recombination mechanisms in stoichiometric AgInS 2 NCs. Transient transmission measurements reveal the signatures of two subbands with opposite parity, and photoluminescence studies at cryogenic temperatures evidence a dark state emission due to enhanced exchange interaction, consistent with the behavior of stoichiometric CuInS 2 NCs. Lowering the temperature as well as applying reducing electrochemical potentials further suppress electron trapping, which represents the main nonradiative channel for exciton decay, leading to nearly 100% emission efficiency.

Optoelectronic devices based on all-inorganic perovskite systems are an energy-efficient source of lighting due to their high photoluminescence quantum yield (QY). However, dominant surface trapping continues to plague the field, despite their high defect tolerance, as evidenced by the several-fold improvements in the external quantum efficiency of perovskite nanocrystals (NCs) upon appropriate surface passivation or physical confinement between high-band-gap materials. Here, we introduce the concept of drip-feeding of photoexcited electrons from an impurity-induced spin-forbidden state to address this major shortcoming. An increased and delayed (about several milliseconds) excitonic QY, Raman spectroscopy demonstrating specific vibrational modes of the PbX6 octahedra, and density functional theory establish the electron back-transfer, signifying an efficient recombination. We term this electron back-transfer from Mn2+ to the host conduction band in this prototypical example of Mn-doped CsPbX3 (X = Cl, Br) NCs through vibrational coupling as vibrationally assisted delayed fluorescence (VADF).

The interfacial structure in "giant" PbS/CdS quantum dots (QDs) was engineered by modulating the Cd:S molar ratio during in situ growth. The control of the gradient interfacial layer could facilitate hole transfer, regulate the transition from double- to single-color emission, as a consequence. These QDs are optically active close-to-the near-infrared (NIR) spectral region and are candidates as absorber materials in solar energy conversion. Photoinduced charge transfer from "giant" QDs to electron scavenger can still take place despite the ultra-thick (~5 nm) shell. The hybrid architecture based on a TiO2 mesoporous framework sensitized by the "giant" QDs with alloyed interface can produce a saturated photocurrent density as high as ~5.3 mA/cm2 in a photoelectrochemical (PEC) cell under 1 Sun illumination, which is around 2 times higher than that of bare PbS and core/thin-shell PbS/CdS QDs sensitizer. The as-prepared PEC device presented very good stability thanks to the "giant" core/shell QDs architecture with tailored interfacial layer and a further coating of the ZnS shell. 78% of the initial current density is kept after 2-h irradiation at 1 Sun. Engineering of electronic band structure plays a key role in boosting the functional properties of these composite systems, which hold great potential for H2 production in PEC devices.

The nature of the transient species leading to emission from the spin/orbital-forbidden Mn d–d transition in doped semiconductor quantum dots has intrigued scientists for a long time. This understanding is important in the quest for energy efficiency as the energy from the conduction band is transferred efficiently to Mn in the femtosecond time scale overcoming other nonradiative recombination pathways. In this work, we have shown the presence of the transient species using materials with band gaps in resonance with the energy of the Mn emission to understand the nature of the absorbing, transient, and emitting species. Detailed studies lead to the emergence of a transient Mn3+ state that is further corroborated with spin-dependent density functional theory calculations. This opens up a unique opportunity to realize a reversible photochemical reaction and high radiative efficiency in a semiconductor nanostructure by controlling the spin state of the magnetic ion by external illumination.

Electronic doping of colloidal semiconductor nanostructures holds promise for future device concepts in optoelectronic and spin-based technologies. Ag+ is an emerging electronic dopant in III-V and II-VI nanostructures, introducing intragap electronic states optically coupled to the host conduction band. With its full 4d shell Ag+ is nonmagnetic, and the dopant-related luminescence is ascribed to decay of the conduction-band electron following transfer of the photoexcited hole to Ag+. This optical activation process and the associated modification of the electronic configuration of Ag+ remain unclear. Here, we trace a comprehensive picture of the excitonic process in Ag-doped CdSe nanocrystals and demonstrate that, in contrast to expectations, capture of the photohole leads to conversion of Ag+ to paramagnetic Ag2+. The process of exciton recombination is thus inextricably tied to photoinduced magnetism. Accordingly, we observe strong optically activated magnetism and diluted magnetic semiconductor behaviour, demonstrating that optically switchable magnetic nanomaterials can be obtained by exploiting excitonic processes involving nonmagnetic impurities.

Two-dimensional transition metal dichalcogenide (MX 2 ) are receiving lot of attention in recent years due to their excellent electronic and optical properties which make them feasible for advanced photonics applications [1]. In particular Molybdenum-Disulfide (MoS 2 ) has shown large exciton binding energy, strong spin-orbit interaction, and high carrier mobilities.

We study the optical properties of Molybdenum Disulphide nanosheets deposited by chemical vapor deposition onto a nanopatterned substrate endowed with a uniaxial corrugation. The uniaxial nanocorrugation leads to a polarization dependence in steady state and an anisotropic relaxation around the C resonance. Finite element numerical simulations allow to better disclose the scenario. Our findings point towards new possibilities for the manipulation of the optical properties of two-dimensional transition metal dichalcogenides via substrate nanopatterning.

Colloidal semiconductor nanocrystals (NCs) emitting simultaneously at two distinct wavelengths are of great interest for multiple applications ranging from ultrasensitive self-calibrating nanoscale sensing to light-emitting diodes and white-light emission. The physical mechanism governing dual emission in core/shell NCs composed of two materials is still under investigation; in particular, the roles of the volume of the shell and of the core/shell interface are not well understood. Here we compare three different PbS/CdS NCs with identical cores, but shells of different thicknesses and different core/shell interfaces. We study photoluminescence (PL) characteristics and ultrafast exciton dynamics with subpicosecond time resolution. We find that dual emission is possible for both thick and thin quantum-confined shells, and for different core/shell interfaces. We show that very thick shells allow the decoupling of shell excitons from core ones and we fully describe the dynamic exciton barrier, connected to efficient shell PL. We discuss the efficiency of shell PL in relation to the properties of the NCs and show that it can give rise to optical gain. Our results provide a comprehensive understanding of the physical phenomena governing dual-emission mechanisms in NCs.

Semiconducting nanocrystals optically active in the infrared region of the electromagnetic spectrum enable exciting avenues in fundamental research and novel applications compatible with the infrared transparency windows of biosystems such as chemical and biological optical sensing, including nanoscale thermometry. In this context, quantum dots (QDs) with double color emission may represent ultra-accurate and self-calibrating nanosystems. We present the synthesis of giant core/shell/shell asymmetric QDs having a PbS/CdS Zincblende (Zb)/CdS Wurtzite (Wz) structure with double color emission close to the near-infrared (NIR)region. We show that the double emission depends on the excitation condition and analyze the electron-hole distribution responsible of the independent and simultaneous radiative exciton recombination in the PbS core and in the CdS Wz shell, respectively. These results highlight the importance of the driving force leading to preferential crystal growth in asymmetric QDs, and provide a pathway for a rational control of the synthesis of double color emitting giant QDs, leading to the effective exploitation of visible/NIR transparency windows. Validerad; 2016; Nivå 2; 20160119 (jacnas)

Two-color emitting colloidal semiconductor nanocrystals (NCs) are of interest for applications in multimodal imaging, sensing, lighting, and integrated photonics. Dual color emission from core- and shell-related optical transitions has been recently obtained using so-called dot-in-bulk (DiB) CdSe/CdS NCs comprising a quantum-confined CdSe core embedded into an ultrathick (similar to 7-9 nm) CdS shell. The physical mechanism underlying this behavior is still under debate. While a large shell volume appears to be a necessary condition for dual emission, comparison between various types of thick-shell CdSe/CdS NCs indicates a critical role of the interface "sharpness" and the presence of potential barriers. To elucidate the effect of the interface morphology on the dual emission, we perform side-by-side studies of CdSe/CdS DiB-NCs with nominally identical core and shell dimensions but different structural properties of the core/shell interface arising from the crystal structure of the starting CdSe cores (zincblende vs wurtzite). While both structures exhibit dual emission under comparable pump intensities, NCs with a zincblende core show a faster growth of shell luminescence with excitation fluence and a more readily realized regime of amplified spontaneous emission (ASE) even under "slow" nanosecond excitation. These distinctions can be linked to the structure of the core/shell interface: NCs grown from the zincblende cores contain a similar to 3.5 nm thick zincblende CdS interlayer, which separates the core from the wurtzite CdS shell and creates a potential barrier for photoexcited shell holes inhibiting their relaxation into the core. This helps maintain a higher population of shell states and simplifies the realization of dual emission and ASE involving shell-based optical transitions.

2D semiconducting nanoplatelets (NPLs) are an emerging class of photo-active materials. They can be used as building blocks in optoelectronic devices thanks to their large absorption coefficient, high carrier mobility, and unique thickness-dependent optical transitions. The main drawback of NPLs is their large lateral size, which results in unfavorable band energy levels and low quantum yield (QY). Here, ultrasmall lead chalcogenide PbSe1-xSx NPLs are prepared, which exhibit an unprecedented QY of approximate to 60%, the highest ever reported for this structure. The NPLs are applied as light absorber in a photoelectrochemical system, leading to a saturated photocurrent density of approximate to 5.0 mA cm(-2) (44 mL cm(-2) d(-1)), which is a record for NPL-based photo-electrodes in solar-driven hydrogen generation. Ultrasmall NPLs hold the potential for breakthrough developments in the field of optically active nanomaterials.