Spectroscopy of carrier multiplication in nanocrystals.
Ontology highlight
ABSTRACT:
SUBMITTER: Bruhn B
PROVIDER: S-EPMC4744935 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:The all-inorganic perovskite nanocrystals are currently in the research spotlight owing to their physical stability and superior optical properties-these features make them interesting for optoelectronic and photovoltaic applications. Here, we report on the observation of highly efficient carrier multiplication in colloidal CsPbI3 nanocrystals prepared by a hot-injection method. The carrier multiplication process counteracts thermalization of hot carriers and as such provides the potential to increase the conversion efficiency of solar cells. We demonstrate that carrier multiplication commences at the threshold excitation energy near the energy conservation limit of twice the band gap, and has step-like characteristics with an extremely high quantum yield of up to 98%. Using ultrahigh temporal resolution, we show that carrier multiplication induces a longer build-up of the free carrier concentration, thus providing important insights into the physical mechanism responsible for this phenomenon. The evidence is obtained using three independent experimental approaches, and is conclusive.
| S-EPMC6180104 | biostudies-literature
Project description:Carrier multiplication (CM) is a process in which a single photon excites two or more electrons. CM is of interest to enhance the efficiency of a solar cell. Until now, CM in thin films and solar cells of semiconductor nanocrystals (NCs) has been found at photon energies well above the minimum required energy of twice the band gap. The high threshold of CM strongly limits the benefits for solar cell applications. We show that CM is more efficient in a percolative network of directly connected PbSe NCs. The CM threshold is at twice the band gap and increases in a steplike fashion with photon energy. A lower CM efficiency is found for a solid of weaker coupled NCs. This demonstrates that the coupling between NCs strongly affects the CM efficiency. According to device simulations, the measured CM efficiency would significantly enhance the power conversion efficiency of a solar cell.
| S-EPMC6150730 | biostudies-literature
Project description:Carrier multiplication describes an interesting optical phenomenon in semiconductors whereby more than one electron-hole pair, or exciton, can be simultaneously generated upon absorption of a single high-energy photon. So far, it has been highly debated whether the carrier multiplication efficiency is enhanced in semiconductor nanocrystals as compared with their bulk counterpart. The controversy arises from the fact that the ultrafast optical methods currently used need to correctly account for the false contribution of charged excitons to the carrier multiplication signals. Here we show that this charged exciton issue can be resolved in an energy transfer system, where biexcitons generated in the donor nanocrystals are transferred to the acceptor dyes, leading to an enhanced fluorescence from the latter. With the biexciton Auger and energy transfer lifetime measurements, an average carrier multiplication efficiency of ~17.1% can be roughly estimated in CdSe nanocrystals when the excitation photon energy is ~2.46 times of their energy gap.
| S-EPMC3493642 | biostudies-literature
Project description:Light-induced hot carriers derived from the surface plasmons of metal nanostructures have been shown to be highly promising agents for photocatalysis. While both nonthermal and thermalized hot carriers can potentially contribute to this process, their specific role in any given chemical reaction has generally not been identified. Here, we report the observation that the H2-D2 exchange reaction photocatalyzed by Cu nanoparticles is driven primarily by thermalized hot carriers. The external quantum yield shows an intriguing S-shaped intensity dependence and exceeds 100% for high light intensities, suggesting that hot carrier multiplication plays a role. A simplified model for the quantum yield of thermalized hot carriers reproduces the observed kinetic features of the reaction, validating our hypothesis of a thermalized hot carrier mechanism. A quantum mechanical study reveals that vibrational excitations of the surface Cu-H bond is the likely activation mechanism, further supporting the effectiveness of low-energy thermalized hot carriers in photocatalyzing this reaction.
| S-EPMC8157927 | biostudies-literature
Project description:Semiconductor nanocrystals are promising for use in cheap and highly efficient solar cells. A high efficiency can be achieved by carrier multiplication (CM), which yields multiple electron-hole pairs for a single absorbed photon. Lead chalcogenide nanocrystals are of specific interest, since their band gap can be tuned to be optimal to exploit CM in solar cells. Interestingly, for a given photon energy CM is more efficient in bulk PbS and PbSe, which has been attributed to the higher density of states. Unfortunately, these bulk materials are not useful for solar cells due to their low band gap. Here we demonstrate that two-dimensional PbS nanosheets combine the band gap of a confined system with the high CM efficiency of bulk. Interestingly, in thin PbS nanosheets virtually the entire excess photon energy above the CM threshold is used for CM, in contrast to quantum dots, nanorods and bulk lead chalcogenide materials.
| S-EPMC4015322 | biostudies-literature
Project description:Carrier multiplication (i.e. generation of multiple electron-hole pairs from a single high-energy electron, CM) in graphene has been extensively studied both theoretically and experimentally, but direct application of hot carrier multiplication in graphene has not been reported. Here, taking advantage of efficient CM in graphene, we fabricated graphene/TiO2 Schottky nanodiodes and found CM-driven enhancement of quantum efficiency. The unusual photocurrent behavior was observed and directly compared with Fowler's law for photoemission on metals. The Fowler's law exponent for the graphene-based nanodiode is almost twice that of a thin gold film based diode; the graphene-based nanodiode also has a weak dependence on light intensity-both are significant evidence for CM in graphene. Furthermore, doping in graphene significantly modifies the quantum efficiency by changing the Schottky barrier. The CM phenomenon observed on the graphene/TiO2 nanodiodes can lead to intriguing applications of viable graphene-based light harvesting.
| S-EPMC4897609 | biostudies-literature
Project description:Carrier multiplication, the generation of multiple electron-hole pairs by a single photon, is of great interest for solar cells as it may enhance their photocurrent. This process has been shown to occur efficiently in colloidal quantum dots, however, harvesting of the generated multiple charges has proved difficult. Here we show that by tuning the charge-carrier mobility in quantum-dot films, carrier multiplication can be optimized and may show an efficiency as high as in colloidal dispersion. Our results are explained quantitatively by the competition between dissociation of multiple electron-hole pairs and Auger recombination. Above a mobility of ~1 cm(2) V(-1) s(-1), all charges escape Auger recombination and are quantitatively converted to free charges, offering the prospect of cheap quantum-dot solar cells with efficiencies in excess of the Shockley-Queisser limit. In addition, we show that the threshold energy for carrier multiplication is reduced to twice the band gap of the quantum dots.
| S-EPMC3759061 | biostudies-literature
Project description:Dynamic semiconductor diode generators (DDGs) offer a potential portable and miniaturized energy source, with the advantages of high current density, low internal impedance, and independence of the rectification circuit. However, the output voltage of DDGs is generally as low as 0.1-1 V, owing to energy loss during carrier transport and inefficient carrier collection, which requires further optimization and a deeper understanding of semiconductor physical properties. Therefore, this study proposes a vertical graphene/silicon DDG to regulate the performance by realizing hot carrier transport and collection. With instant contact and separation of the graphene and silicon, hot carriers are generated by the rebounding process of built-in electric fields in dynamic graphene/silicon diodes, which can be collected within the ultralong hot electron lifetime of graphene. In particular, monolayer graphene/silicon DDG outputs a high voltage of 6.1 V as result of ultrafast carrier transport between the monolayer graphene and silicon. Furthermore, a high current of 235.6 nA is generated due to the carrier multiplication in graphene. A voltage of 17.5 V is achieved under series connection, indicating the potential to supply electronic systems through integration design. The graphene/silicon DDG has applications as an in situ energy source for harvesting mechanical energy from the environment.
| S-EPMC9313483 | biostudies-literature
Project description:Carrier multiplication (CM) is a process in which high-energy free carriers relax by generation of additional electron-hole pairs rather than by heat dissipation. CM is promising disruptive improvements in photovoltaic energy conversion and light detection technologies. Current state-of-the-art nanomaterials including quantum dots and carbon nanotubes have demonstrated CM, but are not satisfactory owing to high-energy-loss and inherent difficulties with carrier extraction. Here, we report CM in van der Waals (vdW) MoTe2 and WSe2 films, and find characteristics, commencing close to the energy conservation limit and reaching up to 99% CM conversion efficiency with the standard model. This is demonstrated by ultrafast optical spectroscopy with independent approaches, photo-induced absorption, photo-induced bleach, and carrier population dynamics. Combined with a high lateral conductivity and an optimal bandgap below 1 eV, these superior CM characteristics identify vdW materials as an attractive candidate material for highly efficient and mechanically flexible solar cells in the future.
| S-EPMC6889496 | biostudies-literature
Project description:Carrier multiplication (CM) is the process in which multiple electron-hole pairs are created upon absorption of a single photon in a semiconductor. CM by an initially hot charge carrier occurs in competition with cooling by phonon emission, with the respective rates determining the CM efficiency. Up until now, CM rates have only been calculated theoretically. We show for the first time how to extract a distinct CM rate constant from experimental data of the relaxation time of hot charge carriers and the yield of CM. We illustrate this method for PbSe quantum dots. Additionally, we provide a simplified method using an estimated energy loss rate to estimate the CM rate constant just above the onset of CM, when detailed experimental data of the relaxation time is missing.
| S-EPMC6354726 | biostudies-literature