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

Thermophoresis-Controlled Size-Dependent DNA Translocation through an Array of Nanopores

Large arrays of nanopores can be used for high-throughput biomolecule translocation with applications toward size discrimination and sorting at the single-molecule level. In this paper, we propose to discriminate DNA length by the capture rate of the molecules to an array of relatively large nanopores (50–130 nm) by introducing a thermal gradient by laser illumination in front of the pores balancing the force from an external electric field. Nanopore arrays defined by photolithography were batch processed using standard silicon technology in combination with electrochemical etching. Parallel translocation of single, fluorophore-labeled dsDNA strands is recorded by imaging the array with a fast CMOS camera. The experimental data show that the capture rates of DNA molecules decrease with increasing DNA length due to the thermophoretic effect of the molecules. It is shown that the translocation can be completely turned off for the longer molecule using an appropriate bias, thus allowing a size discrimination of the DNA translocation through the nanopores. A derived analytical model correctly predicts the observed capture rate. Our results demonstrate that by combining a thermal and a potential gradient at the nanopores, such large nanopore arrays can potentially be used as a low-cost, high-throughput platform for molecule sensing and sorting

Thermophoresis-Controlled Size-Dependent DNA Translocation through an Array of Nanopores

Large arrays of nanopores can be used for high-throughput biomolecule translocation with applications toward size discrimination and sorting at the single-molecule level. In this paper, we propose to discriminate DNA length by the capture rate of the molecules to an array of relatively large nanopores (50–130 nm) by introducing a thermal gradient by laser illumination in front of the pores balancing the force from an external electric field. Nanopore arrays defined by photolithography were batch processed using standard silicon technology in combination with electrochemical etching. Parallel translocation of single, fluorophore-labeled dsDNA strands is recorded by imaging the array with a fast CMOS camera. The experimental data show that the capture rates of DNA molecules decrease with increasing DNA length due to the thermophoretic effect of the molecules. It is shown that the translocation can be completely turned off for the longer molecule using an appropriate bias, thus allowing a size discrimination of the DNA translocation through the nanopores. A derived analytical model correctly predicts the observed capture rate. Our results demonstrate that by combining a thermal and a potential gradient at the nanopores, such large nanopore arrays can potentially be used as a low-cost, high-throughput platform for molecule sensing and sorting

Photostable Polymer/Si Nanocrystal Bulk Hybrids with Tunable Photoluminescence

Solid polymer/Si nanocrystal bulk nanocomposites were fabricated from solutions of alkene- and hydride-terminated silicon nanocrystals (NCs) in toluene. The photoluminescence peak position of hydride-terminated SiNCs before polymerization was tuned by photoassisted hydrofluoric acid etching. Optical properties of obtained PMMA/NC hybrids, such as quantum yield, luminescence lifetime, and dispersion factor, were evaluated over time. Photostability of these transparent bulk polymer/SiNC hybrids over months was confirmed. The emission covers the visible to near-infrared range with a quantum yield of ∼30–40% for yellow-red nanocomposites

Light-Converting Polymer/Si Nanocrystal Composites with Stable 60–70% Quantum Efficiency and Their Glass Laminates

Thiol–ene polymer/Si nanocrystal bulk hybrids were synthesized from alkyl-passivated Si nanocrystal (Si NC) toluene solutions. Radicals in the polymer provided a copassivation of “dark” Si NCs, making them optically active and leading to a substantial ensemble quantum yield increase. Optical stability over several months was confirmed. The presented materials exhibit the highest photoluminescence quantum yield (∼65%) of any solid-state Si NC hybrid reported to date. The broad tunability of thiol–ene polymer reactivity provides facile glass integration, as demonstrated by a laminated structure. This, together with extremely fast polymerization, makes the demonstrated hybrid material a promising candidate for light converting applications

Evolution of the Ultrafast Photoluminescence of Colloidal Silicon Nanocrystals with Changing Surface Chemistry

The role of surface species in the optical properties of silicon nanocrystals (SiNCs) is the subject of intense debate. Changes in photoluminescence (PL) energy following hydrosilylation of SiNCs with alkyl-terminated surfaces are most often ascribed to enhanced quantum confinement in the smaller cores of oxidized NCs or to oxygen-induced defect emission. We have investigated the PL properties of alkyl-functionalized SiNCs prepared using two related methods: thermal and photochemical hydrosilylation. Photochemically functionalized SiNCs exhibit higher emission energies than the thermally functionalized equivalent. While microsecond lifetime emission attributed to carrier recombination within the NC core was observed from all samples, much faster, size-independent nanosecond lifetime components were only observed in samples prepared using photochemical hydrosilylation that possessed substantial surface oxidation. In addition, photochemically modified SiNCs exhibit higher absolute photoluminescent quantum yields (AQY), consistent with radiative recombination processes occurring at the oxygen-based defects. Correlating spectrally- and time-resolved PL measurements and XPS-derived relative surface oxidation for NCs prepared using different photoassisted hydrosilylation reaction times provides evidence the PL blue-shift as well as the short-lived PL emission observed for photochemically functionalized SiNCs are related to the relative concentration of oxygen surface defects