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Carrier multiplication (CM) is an interesting fundamental phenomenon with application potential in optoelectronics and photovoltaics, and it has been shown to be promoted by quantum confinement effects in nanostructures. However, mostly due to the short lifetimes of additional electron–hole (e-h) pairs generated by CM, major improvements of quantum dot devices that exploit CM are limited. Here we investigate CM in SiO2 solid state dispersions of phosphorus and boron codoped Si nanocrystals (NCs): an exotic variant of Si NCs whose photoluminescence (PL) emission energy, the optical bandgap, is significantly red-shifted in comparison to undoped Si NCs. By combining the results obtained by ultrafast induced absorption (IA) with PL quantum yield (PL QY) measurements, we demonstrate CM with a long (around 100 μs) lifetime of the additional e-h pairs created by the process, similar as previously reported for undoped Si NCs, but with a significantly lower CM threshold energy. This constitutes a significant step toward the practical implementation of Si-based NCs in optoelectronic devices: we demonstrate efficient CM at the energy bandgap optimal for photovoltaic conversion.

We investigated experimentally optical generation of electronhole pairs in layers of silicon nanocrystals co-doped with phosphor and boron, dispersed in a solid-state matrix of silicon dioxide. The study was performed at room temperature. From the red-shift of the photoluminescence spectrum and the enhanced absorption at low energies appearing upon doping, the formation of additional levels inside the bandgap has been confirmed. By comparing the transient induced absorption at two excitation energies, below and well above twice the emission energy, the evidence of carrier multiplication in co-doped silicon nanocrystals has been obtained for the first time.Effect of doping on optical characteristics of silicon nanocrystals

Carrier multiplication in nanostructures promises great improvements in a number of widely used technologies, among others photodetectors and solar cells. The decade since its discovery was ridden with fierce discussions about its true existence, magnitude, and mechanism. Here, we introduce a novel, purely spectroscopic approach for investigation of carrier multiplication in nanocrystals. Applying this method to silicon nanocrystals in an oxide matrix, we obtain an unambiguous spectral signature of the carrier multiplication process and reveal details of its size-dependent characteristics-energy threshold and efficiency. The proposed method is generally applicable and suitable for both solid state and colloidal samples, as well as for a great variety of different materials.

energy exchange with defects. [2,12] The strength of the cooperative processes and their effect on the optical properties of an NC ensemble depend on the characteristics of the individual NCs themselves as well as on the ensemble properties, such as NC density and proximity, [13] confining potential of the embedding matrix [14] and its quality, etc. [6] The cooperative processes typically involve an energy barrier for their activation, and therefore will change with the excitation energy. On the other hand, it is well known that the Kasha-Vavilov rule, [15] which states that the PL QY is independent of the excitation energy, is frequently violated for colloidal semiconductor NCs, [16] since carriers that are photogenerated higher in the conduction/ valence bands experience an increased probability of capturing at defect states and/or escape to the outside of an NC, leading to its ionization [10] and a temporal loss of optical activity. In result, the PL QY of the NCs decreases typically at short pump wavelengths. In this study, we investigate the excitation energy dependence of the PL QY for Si NC layers and find that it varies strongly in different samples. We investigate and discuss possible physical mechanisms influencing the PL QY at different excitation energies and conclude on an important role of impact excitation and parasitic absorption. Sample PreparationThe samples used in this study were produced by a co-sputtering method in the form of multilayer (ML) structures, featuring multiple stacks (up to 100) of 3.5 nm thin active layers of Si NCs separated by SiO 2 barriers. In this process, two sputtering guns, with Si and SiO 2 targets, are used. By operating both guns simultaneously, an Si-rich substoichiometric SiO x "active" layer can be grown, while solely the gun with silicon dioxide is applied to develop a barrier layer of pure SiO 2 . The atomic composition of the active layer can be tuned by adjusting the power of the guns, and the layer thickness is controlled by the exposure time. For the samples investigated in this study, the silicon excess of 15%, 25%, and 30% was used in the active layer. The barrier thickness between two adjacent active layers was set at 5 nm to avoid exciton diffusion between these layers. [17] Extensive past research [18,19] has shown that, in contrast to thick homogeneous layers of Si NCs in SiO 2 , ML structures allow for a better size control and therefore yield ensembles with a more narrow size distribution.This study investigates the photoluminescence quantum yield for cosputtered solid-state dispersions of Si nanocrystals in SiO 2 with different size and density, and concludes that the absolute value of the photoluminescence quantum yield shows a varied dependence on the excitation energy. Physical mechanisms influencing the photoluminescence quantum yield at different excitation energy ranges are considered. Based on the experimental evidence, this study proposes a generalized description of the excitation dependence of photoluminescence quantum yield of Si nanocrys...