Carrier Dynamics in Single Luminescent Silicon Quantum Dots

Bulk silicon as an indirect bandgap semiconductor is a poor light emitter. In contrast, silicon nanocrystals (Si NCs) exhibit strong emission even at room temperature, discovered initially at 1990 for porous silicon by Leigh Canham. This can be explained by the indirect to quasi-direct bandgap modification of nano-sized silicon according to the already well-established model of quantum confinement. In the absence of deep understanding of numerous fundamental optical properties of Si NCs, it is essential to study their photoluminescence (PL) characteristics at the single-dot level. This thesis presents new experimental results on various photoluminescence mechanisms in single silicon quantum dots (Si QDs). The visible and near infrared emission of Si NCs are believed to originate from the band-to-band recombination of quantum confined excitons. However, the mechanism of such process is not well understood yet. Through time-resolved PL decay spectroscopy of well-separated single Si QDs, we first quantitatively established that the PL decay character varies from dot-to-dot and the individual lifetime dispersion results in the stretched exponential decays of ensembles. We then explained the possible origin of such variations by studying radiative and non-radiative decay channels in single Si QDs. For this aim the temperature dependence of the PL decay were studied. We further demonstrated a model based on resonance tunneling of the excited carriers to adjacent trap sites in single Si QDs which explains the well-known thermal quenching effect. Despite the long PL lifetime of Si NCs, which limits them for optoelectronics applications, they are ideal candidates for biomedical imaging, diagnostic purposes, and phosphorescence applications, due to the non-toxicity, biocompability and material abundance of silicon. Therefore, measuring quantum efficiency of Si NCs is of great importance, while a consistency in the reported values is still missing. By direct measurements of the optical absorption cross-section for single Si QDs, we estimated a more precise value of internal quantum efficiency (IQE) for single dots in the current study. Moreover, we verified IQE of ligand-passivated Si NCs to be close to 100%, due to the results obtained from spectrally-resolved PL decay studies. Thus, ligand-passivated silicon nanocrystals appear to differ substantially from oxide-encapsulated particles, where any value from 0 % to 100 % could be measured. Therefore, further investigation on passivation parameters is strongly suggested to optimize the efficiency of silicon nanocrystals systems.QC 201501001</p

Optical absorption cross section and quantum efficiency of a single silicon quantum dot

Direct measurements of the optical absorption cross section (sigma) and exciton lifetime are performed on a single silicon quantum dot fabricated by electron beam lithography (EBL), reactive ion etching (RIE) and oxidation. For this aim, single photon counting using, an avalanche photodiode detector (APD) is applied to record photoluminescence (PL) intensity traces under pulsed excitation. The PL decay is found to be of a mono-exponential character with a lifetime of 6.5 mu s. By recording the photoluminescence rise time at different photon fluxes the absorption cross could be extracted yielding a value of 1.46x10(-14)cm(2) under 405 nm excitation wavelength. The PL quantum efficiency is found to be about 9% for the specified single silicon quantum dot.QC 20130913</p

Oxidation of nanopores in a silicon membrane : self-limiting formation of sub-10nm circular openings

We describe a simple but reliable approach to shrink silicon nanopores with nanometer precision for potential high throughput biomolecular sensing and parallel DNA sequencing. Here, nanopore arrays on silicon membranes were fabricated by a self-limiting shrinkage of inverted pyramidal pores using dry thermal oxidation at 850 degrees C. The shrinkage rate of the pores with various initial sizes saturated after 4 h of oxidation. In the saturation regime, the shrinkage rate is within +/- 2 nm h(-1). Oxidized pores with an average diameter of 32 nm were obtained with perfect circular shape. By careful design of the initial pore size, nanopores with diameters as small as 8 nm have been observed. Statistics of the pore width show that the shrinkage process did not broaden the pore size distribution; in most cases the distribution even decreased slightly. The progression of the oxidation and the deformation of the oxide around the pores were characterized by focused ion beam and electron microscopy. Cross-sectional imaging of the pores suggests that the initial inverted pyramidal geometry is most likely the determining factor for the self-limiting shrinkage.QC 20141013</p

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We describe a simple but reliable approach to shrink silicon nanopores with nanometer precision for potential high throughput biomolecular sensing and parallel DNA sequencing. Here, nanopore arrays on silicon membranes were fabricated by a self-limiting shrinkage of inverted pyramidal pores using dry thermal oxidation at 850 degrees C. The shrinkage rate of the pores with various initial sizes saturated after 4 h of oxidation. In the saturation regime, the shrinkage rate is within +/- 2 nm h(-1). Oxidized pores with an average diameter of 32 nm were obtained with perfect circular shape. By careful design of the initial pore size, nanopores with diameters as small as 8 nm have been observed. Statistics of the pore width show that the shrinkage process did not broaden the pore size distribution; in most cases the distribution even decreased slightly. The progression of the oxidation and the deformation of the oxide around the pores were characterized by focused ion beam and electron microscopy. Cross-sectional imaging of the pores suggests that the initial inverted pyramidal geometry is most likely the determining factor for the self-limiting shrinkage.QC 20141013</p

Strong Absorption Enhancement in Si Nanorods

We report two orders of magnitude stronger absorption in silicon nanorods relative to bulk in a wide energy range. The local field enhancement and dipole matrix element contributions were disentangled experimentally by single-dot absorption measurements on differently shaped particles as a function of excitation polarization and photon energy. Both factors substantially contribute to the observed effect as supported by simulations of the light-matter interaction and atomistic calculations of the transition matrix elements. The results indicate strong shape dependence of the quasidirect transitions in silicon nanocrystals, suggesting nanostructure shape engineering as an efficient tool for overcoming limitations of indirect band gap materials in optoelectronic applications, such as solar cells

Biexciton Emission as a Probe of Auger Recombination in Individual Silicon Nanocrystals

Biexciton emission from individual silicon nanocrystals was detected at room temperature by time-resolved, single-particle luminescence measurements. The efficiency of this process, however, was found to be very low, about 10–20 times less than the single exciton emission efficiency. It decreases even further at low temperature, explaining the lack of biexciton emission line observations in silicon nanocrystal single-dot spectroscopy under high excitation. The poor efficiency of the biexciton emission is attributed to the dominant nonradiative Auger process. Corresponding measured biexciton decay times then represent Auger lifetimes, and the values obtained here, from tens to hundreds of nanoseconds, reveal strong dot-to-dot variations, while the range compares well with recent calculations taking into account the resonant nature of the Auger process in semiconductor nanocrystals

Rapid Trapping as the Origin of Nonradiative Recombination in Semiconductor Nanocrystals

We demonstrate that nonradiative recombination in semiconductor nanocrystals can be described by a rapid luminescence intermittency, based on carrier tunneling to resonant traps. Such process, we call it “rapid trapping (blinking)”, leads to delayed luminescence and promotes Auger recombination, thus lowering the quantum efficiency. To prove our model, we probed oxide- (containing static traps) and ligand- (trap-free) passivated silicon nanocrystals emitting at similar energies and featuring monoexponential blinking statistics. This allowed us to find analytical formulas and to extract characteristic trapping/detrapping rates, and quantum efficiency as a function of temperature and excitation power. Experimental single-dot temperature-dependent decays, supporting the presence of one or few resonant static traps, and ensemble saturation curves were found to be very well described by this effect. The model can be generalized to other semiconductor nanocrystals, although the exact interplay of trapping/detrapping, radiative, and Auger processes may be different, considering the typical times of the processes involved

Near-Unity Internal Quantum Efficiency of Luminescent Silicon Nanocrystals with Ligand Passivation

Spectrally resolved photoluminescence (PL) decays were measured for samples of colloidal, ligand-passivated silicon nanocrystals. These samples have PL emission energies with peak positions in the range ∼1.4–1.8 eV and quantum yields of ∼30–70%. Their ensemble PL decays are characterized by a stretched-exponential decay with a dispersion factor of ∼0.8, which changes to an almost monoexponential character at fixed detection energies. The dispersion factors and decay rates for various detection energies were extracted from spectrally resolved curves using a mathematical approach that excluded the effect of homogeneous line width broadening. Since nonradiative recombination would introduce a random lifetime variation, leading to a stretched-exponential decay for an ensemble, we conclude that the observed monoexponential decay in size-selected ensembles signifies negligible nonradiative transitions of a similar strength to the radiative one. This conjecture is further supported as extracted decay rates agree with radiative rates reported in the literature, suggesting 100% internal quantum efficiency over a broad range of emission wavelengths. The apparent differences in the quantum yields can then be explained by a varying fraction of “dark” or blinking nanocrystals