Optical Properties of Single Silicon Quantum Dots

For over 60 years silicon (Si) has dominated the semiconductor microelectronics industry mainly due to its abundance and good electrical and material properties. The advanced processing technology of Si has made it the workhorse for photovoltaics industry as well. However, this material has also a big drawback: it is an indirect-bandgap semiconductor in its bulk form, hence an inefficient light emitter. This has hindered the silicon photonics revolution envisioned in 1980s, where photons were thought to replace electrons inside computer chips. In parallel with the exponential scaling of Si transistor's size over the years, the discovery of quantum phenomena at the nanoscale raised new hopes for this semiconductor. In the 1990s bright luminescence from nanostructured porous Si was demonstrated claiming the quantum confinement effect as origin of the emission. Since then, an intense research activity has been focused on Si quantum dots (Si-QDs) due to their potential use as abundant and non-toxic light emitters. More precisely, they could be used as fluorescent biolabels in biomedicine, as light-emitting phosphors in e.g. TV screens or as down-converters in luminescent solar concentrators. Nevertheless, in order to realize such applications, it is necessary not only to improve the fabrication of Si-QDs but also to gain a better understanding of their photo-physics. Among different types of optical measurements, those performed at the single-dot level are free of sample inhomogeneities, hence more accurate for a correct physical description. This doctoral thesis presents a study of the optical properties of single Si-QDs of different type: encapsulated in an oxide matrix, capped with ligands or covered by a thin passivation layer. The homogeneous photoluminescence (PL) linewidth is found to strongly depend on the type of embedding matrix, being narrower for less rigid ones. A record resolution-limited linewidth of ~200 μeV is measured at low temperatures whereas room-temperature values can even compete with direct-bandgap QDs like CdSe. Such narrow PL lines exhibit intensity saturation at high excitation fluxes without any indication of emission from multiexciton states, suggesting the presence of fast non-radiative Auger recombination. Characteristic Auger-related lifetimes extracted from power-dependent decays show a variation from dot-to-dot and confirm the low biexciton quantum efficiency. For the first time, the absorption curve of single Si-QDs is probed by means of photoluminescence excitation in the range 2.0-3.5 eV. A step-like structure is found which depends on the nanocrystal shape considered and agrees well with simulations of the exciton level structure. Rod-like Si-QDs can exhibit ~50 times higher absorption than spherical-like ones due to local field effects and enhanced optical transitions. In contrast with previous studies, evidence of a direct-bandgap red-shift for small Si-QDs is missing at the single dot level, in agreement with atomistic calculations. Low-temperature PL decay measurements reveal no triplet-like emission lines, but two ~μs decay constants appearing at low temperatures. They suggest presence of a temperature-dependent fast blinking process based on trapping/detrapping of carriers in the oxide matrix, leading to delayed emission. The proposed model allows to extract characteristic trapping/de-trapping rates for Si-QDs featuring mono-exponential blinking statistics. From PL saturation curves, ligand-passivated Si-QDs do not exhibit such detrimental phenomenon, in agreement with the proposed model. Last, Si-QDs demonstrate to be very hard against ~10 keV X-ray radiation, in contrast with CdSe-QDs whose PL quenching is correlated with a change in the blinking parameters. This property could be exploited for example in space applications, where radiation-hard materials are required. To conclude, the results achieved in this thesis will help to understand and engineer the properties of Si-QDs whose application potential has increased after several years of research both at the ensemble and at the single-dot level.QC 20181114</p

Optical Properties of Single Silicon Quantum Dots

For over 60 years silicon (Si) has dominated the semiconductor microelectronics industry mainly due to its abundance and good electrical and material properties. The advanced processing technology of Si has made it the workhorse for photovoltaics industry as well. However, this material has also a big drawback: it is an indirect-bandgap semiconductor in its bulk form, hence an inefficient light emitter. This has hindered the silicon photonics revolution envisioned in 1980s, where photons were thought to replace electrons inside computer chips. In parallel with the exponential scaling of Si transistor's size over the years, the discovery of quantum phenomena at the nanoscale raised new hopes for this semiconductor. In the 1990s bright luminescence from nanostructured porous Si was demonstrated claiming the quantum confinement effect as origin of the emission. Since then, an intense research activity has been focused on Si quantum dots (Si-QDs) due to their potential use as abundant and non-toxic light emitters. More precisely, they could be used as fluorescent biolabels in biomedicine, as light-emitting phosphors in e.g. TV screens or as down-converters in luminescent solar concentrators. Nevertheless, in order to realize such applications, it is necessary not only to improve the fabrication of Si-QDs but also to gain a better understanding of their photo-physics. Among different types of optical measurements, those performed at the single-dot level are free of sample inhomogeneities, hence more accurate for a correct physical description. This doctoral thesis presents a study of the optical properties of single Si-QDs of different type: encapsulated in an oxide matrix, capped with ligands or covered by a thin passivation layer. The homogeneous photoluminescence (PL) linewidth is found to strongly depend on the type of embedding matrix, being narrower for less rigid ones. A record resolution-limited linewidth of ~200 μeV is measured at low temperatures whereas room-temperature values can even compete with direct-bandgap QDs like CdSe. Such narrow PL lines exhibit intensity saturation at high excitation fluxes without any indication of emission from multiexciton states, suggesting the presence of fast non-radiative Auger recombination. Characteristic Auger-related lifetimes extracted from power-dependent decays show a variation from dot-to-dot and confirm the low biexciton quantum efficiency. For the first time, the absorption curve of single Si-QDs is probed by means of photoluminescence excitation in the range 2.0-3.5 eV. A step-like structure is found which depends on the nanocrystal shape considered and agrees well with simulations of the exciton level structure. Rod-like Si-QDs can exhibit ~50 times higher absorption than spherical-like ones due to local field effects and enhanced optical transitions. In contrast with previous studies, evidence of a direct-bandgap red-shift for small Si-QDs is missing at the single dot level, in agreement with atomistic calculations. Low-temperature PL decay measurements reveal no triplet-like emission lines, but two ~μs decay constants appearing at low temperatures. They suggest presence of a temperature-dependent fast blinking process based on trapping/detrapping of carriers in the oxide matrix, leading to delayed emission. The proposed model allows to extract characteristic trapping/de-trapping rates for Si-QDs featuring mono-exponential blinking statistics. From PL saturation curves, ligand-passivated Si-QDs do not exhibit such detrimental phenomenon, in agreement with the proposed model. Last, Si-QDs demonstrate to be very hard against ~10 keV X-ray radiation, in contrast with CdSe-QDs whose PL quenching is correlated with a change in the blinking parameters. This property could be exploited for example in space applications, where radiation-hard materials are required. To conclude, the results achieved in this thesis will help to understand and engineer the properties of Si-QDs whose application potential has increased after several years of research both at the ensemble and at the single-dot level.QC 20181114</p

Optical Properties of Single Silicon Quantum Dots

For over 60 years silicon (Si) has dominated the semiconductor microelectronics industry mainly due to its abundance and good electrical and material properties. The advanced processing technology of Si has made it the workhorse for photovoltaics industry as well. However, this material has also a big drawback: it is an indirect-bandgap semiconductor in its bulk form, hence an inefficient light emitter. This has hindered the silicon photonics revolution envisioned in 1980s, where photons were thought to replace electrons inside computer chips. In parallel with the exponential scaling of Si transistor's size over the years, the discovery of quantum phenomena at the nanoscale raised new hopes for this semiconductor. In the 1990s bright luminescence from nanostructured porous Si was demonstrated claiming the quantum confinement effect as origin of the emission. Since then, an intense research activity has been focused on Si quantum dots (Si-QDs) due to their potential use as abundant and non-toxic light emitters. More precisely, they could be used as fluorescent biolabels in biomedicine, as light-emitting phosphors in e.g. TV screens or as down-converters in luminescent solar concentrators. Nevertheless, in order to realize such applications, it is necessary not only to improve the fabrication of Si-QDs but also to gain a better understanding of their photo-physics. Among different types of optical measurements, those performed at the single-dot level are free of sample inhomogeneities, hence more accurate for a correct physical description. This doctoral thesis presents a study of the optical properties of single Si-QDs of different type: encapsulated in an oxide matrix, capped with ligands or covered by a thin passivation layer. The homogeneous photoluminescence (PL) linewidth is found to strongly depend on the type of embedding matrix, being narrower for less rigid ones. A record resolution-limited linewidth of ~200 μeV is measured at low temperatures whereas room-temperature values can even compete with direct-bandgap QDs like CdSe. Such narrow PL lines exhibit intensity saturation at high excitation fluxes without any indication of emission from multiexciton states, suggesting the presence of fast non-radiative Auger recombination. Characteristic Auger-related lifetimes extracted from power-dependent decays show a variation from dot-to-dot and confirm the low biexciton quantum efficiency. For the first time, the absorption curve of single Si-QDs is probed by means of photoluminescence excitation in the range 2.0-3.5 eV. A step-like structure is found which depends on the nanocrystal shape considered and agrees well with simulations of the exciton level structure. Rod-like Si-QDs can exhibit ~50 times higher absorption than spherical-like ones due to local field effects and enhanced optical transitions. In contrast with previous studies, evidence of a direct-bandgap red-shift for small Si-QDs is missing at the single dot level, in agreement with atomistic calculations. Low-temperature PL decay measurements reveal no triplet-like emission lines, but two ~μs decay constants appearing at low temperatures. They suggest presence of a temperature-dependent fast blinking process based on trapping/detrapping of carriers in the oxide matrix, leading to delayed emission. The proposed model allows to extract characteristic trapping/de-trapping rates for Si-QDs featuring mono-exponential blinking statistics. From PL saturation curves, ligand-passivated Si-QDs do not exhibit such detrimental phenomenon, in agreement with the proposed model. Last, Si-QDs demonstrate to be very hard against ~10 keV X-ray radiation, in contrast with CdSe-QDs whose PL quenching is correlated with a change in the blinking parameters. This property could be exploited for example in space applications, where radiation-hard materials are required. To conclude, the results achieved in this thesis will help to understand and engineer the properties of Si-QDs whose application potential has increased after several years of research both at the ensemble and at the single-dot level.QC 20181114</p

Single-dot absorption spectroscopy and theory of silicon nanocrystals

Photoluminescence excitation measurements have been performed on single, unstrained oxide-embedded Si nanocrystals. Having overcome the challenge of detecting weak emission, we observe four broad peaks in the absorption curve above the optically emitting state. Atomistic calculations of the Si nanocrystal energy levels agree well with the experimental results and allow identification of some of the observed transitions. An analysis of their physical nature reveals that they largely retain the indirect band-gap structure of the bulk material with some intermixing of direct band- gap character at higher energies.QC 20160512</p

Wafer-scale fabrication of isolated luminescent silicon quantum dots using standard CMOS technology

A wafer-scale fabrication method for isolated silicon quantum dots (Si QDs) using standard CMOS technology is presented. Reactive ion etching was performed on the device layer of a silicon-on-insulator wafer, creating nano-sized silicon islands. Subsequently, the wafer was annealed at 1100 degrees C for 1 h in an atmosphere of 5% H(2)in Ar, forming a thin oxide passivating layer due to trace amounts of oxygen. Isolated Si QDs covering large areas (similar to mm(2)) were revealed by photoluminescence (PL) measurements. The emission energies of such Si QDs can span over a broad range, from 1.3 to 2.0 eV and each dot is typically characterized by a single emission line at low temperatures. Most of the Si QDs exhibited a high degree of linear polarization along Si crystallographic directions [110] abd [(1) over bar 10]. In addition, system resolution-limited (250 mu eV) PL linewidths (full width at half maximum) were measured for several Si QDs at 10 K, with no clear correlation between emission energy and polarization. The initial part of PL decays was measured at room temperature for such oxide-embedded Si QDs, approximately several microseconds long. By providing direct access to a broad size range of isolated Si QDs on a wafer, this technique paves the way for the future fabrication of photonic structures with Si QDs, which can potentially be used as single-photon sources with a long coherence length.QC 20201027</p

Single-dot absorption spectroscopy and theory of silicon nanocrystals

Photoluminescence excitation measurements have been performed on single, unstrained oxide-embedded Si nanocrystals. Having overcome the challenge of detecting weak emission, we observe four broad peaks in the absorption curve above the optically emitting state. Atomistic calculations of the Si nanocrystal energy levels agree well with the experimental results and allow identification of some of the observed transitions. An analysis of their physical nature reveals that they largely retain the indirect band-gap structure of the bulk material with some intermixing of direct band- gap character at higher energies.QC 20160512</p

Ultranarrow Luminescence Linewidth of Silicon Nanocrystals and Influence of Matrix

The luminescence linewidth of individual silicon nanocrystals was characterized by single-dot spectroscopy, and an ultranarrow linewidth of similar to 200 mu eV at 10 K was found. This value is, in fact, limited by system resolution and represents only the upper limit of the homogeneous linewidth. In addition, the effect of the matrix was investigated for nanocrystals coated with organic ligands, embedded in silicon dioxide, as well as for nanocrystals with only a thin passivating layer. It was found that, depending on the matrix, the room-temperature bandwidth may vary by an order of magnitude, where values as small as similar to 12 meV (similar to 5 nm) at 300 K were detected for nanocrystals with a thin passivation. The observed values for silicon nanocrystals are similar and even surpass some of those for direct-band-gap quantum dots. The narrow linewidth at room temperature enables the use of silicon nanocrystals for nontoxic narrow-band labeling of biomolecules and for application as phosphors in white-light-emitting devices.QC 20141114</p

Ultranarrow Luminescence Linewidth of Silicon Nanocrystals and Influence of Matrix

The luminescence linewidth of individual silicon nanocrystals was characterized by single-dot spectroscopy, and an ultranarrow linewidth of similar to 200 mu eV at 10 K was found. This value is, in fact, limited by system resolution and represents only the upper limit of the homogeneous linewidth. In addition, the effect of the matrix was investigated for nanocrystals coated with organic ligands, embedded in silicon dioxide, as well as for nanocrystals with only a thin passivating layer. It was found that, depending on the matrix, the room-temperature bandwidth may vary by an order of magnitude, where values as small as similar to 12 meV (similar to 5 nm) at 300 K were detected for nanocrystals with a thin passivation. The observed values for silicon nanocrystals are similar and even surpass some of those for direct-band-gap quantum dots. The narrow linewidth at room temperature enables the use of silicon nanocrystals for nontoxic narrow-band labeling of biomolecules and for application as phosphors in white-light-emitting devices.QC 20141114</p