Efficient optical extraction of hot-carrier energy.

Light-induced generation of free charge carriers in semiconductors constitutes the physical basis of photodetection and photovoltaics. To maximize its efficiency, the energy of the photons must be entirely used for this purpose. This is highly challenging owing to the ultrafast thermalization of 'hot' carriers, which are created by absorption of high-energy photons. Thermalization leads to heat generation, and hence efficiency loss. To circumvent this, dedicated schemes such as photovoltaic hot-carrier cells are being explored. Here we consider optical extraction of the excess energy of hot carriers by emission of infrared photons, using erbium ions in combination with silicon nanocrystals. We determine the external quantum yield of the infrared photon generation by the erbium ions, and demonstrate that cooling of the hot carriers induces a steep, step-like, increase in erbium-related external quantum yield by up to a factor of 15 towards higher excitation energies. Finally, we comment on the potential of our findings for future photovoltaics in the form of an optical ultraviolet-to-infrared spectral converter.

Silicon quantum dots: surface matters.

Silicon quantum dots (SiQDs) hold great promise for many future technologies. Silicon is already at the core of photovoltaics and microelectronics, and SiQDs are capable of efficient light emission and amplification. This is crucial for the development of the next technological frontiers-silicon photonics and optoelectronics. Unlike any other quantum dots (QDs), SiQDs are made of non-toxic and abundant material, offering one of the spectrally broadest emission tunabilities accessible with semiconductor QDs and allowing for tailored radiative rates over many orders of magnitude. This extraordinary flexibility of optical properties is achieved via a combination of the spatial confinement of carriers and the strong influence of surface chemistry. The complex physics of this material, which is still being unraveled, leads to new effects, opening up new opportunities for applications. In this review we summarize the latest progress in this fascinating research field, with special attention given to surface-induced effects, such as the emergence of direct bandgap transitions, and collective effects in densely packed QDs, such as space separated quantum cutting.

Step-like enhancement of luminescence quantum yield of silicon nanocrystals.

Carrier multiplication by generation of two or more electron-hole pairs following the absorption of a single photon may lead to improved photovoltaic efficiencies and has been observed in nanocrystals made from a variety of semiconductors, including silicon. However, with few exceptions, these reports have been based on indirect ultrafast techniques. Here, we present evidence of carrier multiplication in closely spaced silicon nanocrystals contained in a silicon dioxide matrix by measuring enhanced photoluminescence quantum yield. As the photon energy increases, the quantum yield is expected to remain constant, or to decrease as a result of new trapping and recombination channels being activated. Instead, we observe a step-like increase in quantum yield for larger photon energies that is characteristic of carrier multiplication. Modelling suggests that carrier multiplication is occurring with high efficiency and close to the energy conservation limit.

Femtosecond luminescence spectroscopy of core states in silicon nanocrystals.

We present a study of ultrafast carrier transfer from highly luminescent states inside the core of silicon nanocrystal (due to quasidirect transitions) to states on the nanocrystal-matrix interface. This transfer leads to a sub-picosecond luminescence decay, which is followed by a slower decay component induced by carrier relaxation to lower interface states. We investigate the luminescence dynamics for two different surface passivation types and we propose a general model describing spectral dependence of ultrafast carrier dynamics. Our results stress the crucial role of the energy distribution of the interface states on surface-related quenching of quasidirect luminescence in silicon nanocrystals. We discuss how to avoid this quenching in order to bring the attractive properties of the quasidirect recombination closer to exploitation.

Red spectral shift and enhanced quantum efficiency in phonon-free photoluminescence from silicon nanocrystals.

Crystalline silicon is the most important semiconductor material in the electronics industry. However, silicon has poor optical properties because of its indirect bandgap, which prevents the efficient emission and absorption of light. The energy structure of silicon can be manipulated through quantum confinement effects, and the excitonic emission from silicon nanocrystals increases in intensity and shifts to shorter wavelengths (a blueshift) as the size of the nanocrystals is reduced. Here we report experimental evidence for a short-lived visible band in the photoluminescence spectrum of silicon nanocrystals that increases in intensity and shifts to longer wavelengths (a redshift) with smaller nanocrystal sizes. This higher intensity indicates an increased quantum efficiency, which for 2.5-nm-diameter nanocrystals is enhanced by three orders of magnitude compared to bulk silicon. We assign this band to the radiative recombination of non-equilibrium electron-hole pairs in a process that does not involve phonons.

Data processing correction of the irising effect of a fast-gating intensified charge-coupled device on laser-pulse-excited luminescence spectra.

Intensified charge-coupled devices (ICCDs) comprise the advantages of both fast gating detectors and spectrally broad CCDs into one device that enables temporally and spectrally resolved measurements with a few nanosecond resolution. Gating of the measured signal occurs in the image intensifier tube, where a high voltage is applied between the detector photocathode and a microchannel plate electron multiplier. An issue arises in time-resolved luminescence spectroscopy when signal onset characterization is required. In this case, the transient gate closing process that causes the detected signal always arises in the middle of the ICCD chip regardless of the spectral detection window--the so-called irising effect. We demonstrate that in case when the detection gate width is comparable to the opening/closing time and the gate is pretriggered with respect to the signal onset, the irising effect causes the obtained data to be strongly distorted. At the same time, we propose a software procedure that leads to the spectral correction of the irising effect and demonstrate its validity on the distorted data.