T. Gregorkiewicz

Silicon nanostructures for photonics and photovoltaics

Silicon has long been established as the material of choice for the microelectronics industry. This is not yet true in photonics, where the limited degrees of freedom in material design combined with the indirect bandgap are a major constraint. Recent developments, especially those enabled by nanoscale engineering of the electronic and photonic properties, are starting to change the picture, and some silicon nanostructures now approach or even exceed the performance of equivalent direct-bandgap materials. Focusing on two application areas, namely communications and photovoltaics, we review recent progress in silicon nanocrystals, nanowires and photonic crystals as key examples of functional nanostructures. We assess the state of the art in each field and highlight the challenges that need to be overcome to make silicon a truly high-performing photonic material.

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.

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.

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.

Direct bandgap optical transitions in Si nanocrystals

The effect of quantum confinement on the direct bandgap of spherical Si nanocrystals has been modelled theoretically. We conclude that the energy of the direct bandgap at the Γ-point decreases with size reduction: quantum confinement enhances radiative recombination across the direct bandgap and introduces its “red“ shift for smaller grains. We postulate to identify the frequently reported efficient blue emission (F-band) from Si nanocrystals with this zero-phonon recombination. In a dedicated experiment, we confirm the “red“ shift of the F-band, supporting the proposed identification.

Ultrahigh throughput plasma processing of free standing silicon nanocrystals with lognormal size distribution

We demonstrate a method for synthesizing free standing silicon nanocrystals in an argon/silane gas mixture by using a remote expanding thermal plasma. Transmission electron microscopy and Raman spectroscopy measurements reveal that the distribution has a bimodal shape consisting of two distinct groups of small and large silicon nanocrystals with sizes in the range 2–10 nm and 50–120 nm, respectively. We also observe that both size distributions are lognormal which is linked with the growth time and transport of nanocrystals in the plasma. Average size control is achieved by tuning the silane flow injected into the vessel. Analyses on morphological features show that nanocrystals are monocrystalline and spherically shaped. These results imply that formation of silicon nanocrystals is based on nucleation, i.e., these large nanocrystals are not the result of coalescence of small nanocrystals. Photoluminescence measurements show that silicon nanocrystals exhibit a broad emission in the visible region peaked at 725 nm. Nanocrystals are produced with ultrahigh throughput of about 100 mg/min and have state of the art properties, such as controlled size distribution, easy handling, and room temperature visible photoluminescence.

Microscopic Origin of the Fast Blue‐Green Luminescence of Chemically Synthesized Non‐oxidized Silicon Quantum Dots

The microscopic origin of the bright nanosecond blue-green photoluminescence (PL), frequently reported for synthesized organically terminated Si quantum dots (Si-QDs), has not been fully resolved, hampering potential applications of this interesting material. Here a comprehensive study of the PL from alkyl-terminated Si-QDs of 2-3 nm size, prepared by wet chemical synthesis is reported. Results obtained on the ensemble and those from the single nano-object level are compared, and they provide conclusive evidence that efficient and tunable emission arises due to radiative recombination of electron-hole pairs confined in the Si-QDs. This understanding paves the way towards applications of chemical synthesis for the development of Si-QDs with tunable sizes and bandgaps.

Energy transfer in Er-doped SiO2 sensitized with Si nanocrystals

We present a high-resolution photoluminescence study of Er-doped SiO2 sensitized with Si nanocrystals (Si NCs). Emission bands originating from recombination of excitons confined in Si NCs and of internal transitions within the 4f-electron core of Er3+ ions, and a band centered at lambda = 1200nm have been identified. Their kinetics have been investigated in detail. Based on these measurements, we present a comprehensive model for energy transfer mechanisms responsible for light generation in this system. A unique picture of energy flow between subsystems of Er3+ and Si NCs is developed, yielding truly microscopic information on the sensitization effect and its limitations. In particular, we show that most of the Er3+ ions available in the system are participating in the energy exchange. The long standing problem of apparent loss of optical activity of majority of Er dopants upon sensitization with Si NCs is clarified and assigned to appearance of a very efficient energy exchange mechanism between Si NCs and Er3+ ions. Application potential of SiO2:Er sensitized by Si NCs is discussed in view of the newly acquired microscopic insight.

Direct spectral probing of energy storage in Si:Er by a free-electron laser

Results of a two-color spectroscopy in the visible and the mid-infrared on erbium-doped silicon (Si:Er) are presented. In the experiments, pulsed beam provided by a free-electron laser is directed on a sample under primary above-band-gap excitation with another laser. It is shown that the powerful infrared beam can be ionize carriers localized at shallow traps. Liberation of these carriers makes them available for excitation of erbium and thereby enhances the luminescence intensity. Identification of shallow levels responsible for the effect is discussed.

Optical excitation and external photoluminescence quantum efficiency of Eu3+ in GaN

We investigate photoluminescence of Eu-related emission in a GaN host consisting of thin layers grown by organometallic vapor-phase epitaxy. By comparing it with a reference sample of Eu-doped Y2O3, we find that the fraction of Eu3+ ions that can emit light upon optical excitation is of the order of 1%. We also measure the quantum yield of the Eu-related photoluminescence and find this to reach (~10%) and (~3%) under continuous wave and pulsed excitation, respectively.