Luminescent solar concentrator efficiency versus edge solar cell coverage.

This Letter introduces an analytical approach to estimate the waveguiding efficiency of large-area luminescent solar concentrators (LSCs), where the edges are covered by a varied number of mirrors and solar cells. The model provides physically relevant description in the whole range of optical (absorption, scattering) and geometrical (size) parameters of rectangular LSCs. A 19 × 19 cm2 silicon quantum dot-based LSC has been fabricated to verify the theory. Within an experimental error, the predicted waveguiding efficiency matched well the measured one. A critical LSC size, beyond which a part of the device turns inactive, has been determined as N/α for N attached solar cells (one or two) and LSC material absorption coefficient α. This model provides a straightforward waveguiding analysis tool for large-area LSCs with different structural parameters relevant for both high concentration ratio and glazing applications.

Optical center of a luminescent solar concentrator.

This Letter introduces a novel, to the best of our knowledge, approach to estimate the power conversion efficiency (PCE) of a square luminescent solar concentrator (LSC) by point excitations on the "optical centers." Predicted by theoretical calculations, photoluminescence emissions from these optical centers experience almost the same average optical path as those from the whole device under uniform illumination. This is experimentally verified by a 20 × 20 cm2 silicon quantum dot-based LSC, with a negligible error between the predicted PCE and the measured one. This method provides a convenient way to estimate the photovoltaic performance of large-area LSC devices with basic laboratory instruments.

The shell matters: one step synthesis of core-shell silicon nanoparticles with room temperature ultranarrow emission linewidth.

Here we present a one-step synthesis that provides silicon nanocrystals with a thin shell composed of a ceramic-like carbonyl based compound, embedded in a porous organosilicon film. The silicon nanocrystals were synthesised from hydrogen silsesquioxane molecules, modified with organic molecules containing carbonyl groups, which were annealed at 1000 °C in a slightly reducing 5% H2 : 95% Ar atmosphere. The organic character of the shell was preserved after annealing due to trapping of organic molecules inside the HSQ-derived oxide matrix that forms during the annealing. The individual silicon nanocrystals, studied by single dot spectroscopy, exhibited a significantly narrower emission peak at room temperature (lowest linewidth ∼ 17 meV) compared to silicon nanocrystals embedded in a silicon oxide shell (150 meV). Their emission linewidths are even significantly narrower than those of single CdSe quantum dots (>50 meV). It is hypothesized that the Si-core-thin shell structure of the nanoparticle is responsible for the unique optical properties. Its formation within one synthesis step opens new opportunities for silicon-based quantum dots. The luminescence from the produced nanocrystals covers a broad spectral range from 530-720 nm (1.7-2.3 eV) suggesting strong application potential for solar cells and LEDs, following the development of a suitable mass-fabrication protocol.

Tight-binding calculations of the optical properties of Si nanocrystals in a SiO2 matrix.

We develop an empirical tight binding approach for the modeling of the electronic states and optical properties of Si nanocrystals embedded in a SiO2 matrix. To simulate the wide band gap SiO2 matrix we use the virtual crystal approximation. The tight-binding parameters of the material with the diamond crystal lattice are fitted to the band structure of ß-cristobalite. This model of the SiO2 matrix allows us to reproduce the band structure of real Si nanocrystals embedded in a SiO2 matrix. In this model, we compute the absorption spectra of the system. The calculations are in an excellent agreement with experimental data. We find that an important part of the high-energy absorption is defined by the spatially indirect, but direct in k-space transitions between holes inside the nanocrystal and electrons in the matrix.

Wafer-level fabrication of individual solid-state nanopores for sensing single DNAs.

For biomolecule sensing purposes a solid-state nanopore platform based on silicon has certain advantages as compared to nanopores on other substrates such as graphene, silicon nitride, silicon oxide etc Capitalizing on the developed CMOS technology, nanopores on silicon are scalable without any requirement for additional processing, the devices are low cost and the process can be repeatable with a high yield. One of the essential requirements in biomolecule sensing is the ability of the nanopore to interact with the analyte. In this work, we present a method for processing high aspect ratio, single nanopores in the range of 10-30 nm in diameter and approximately 700 nm in length on a silicon-on-insulator (SOI) wafer. The presented method of manufacturing the high aspect ratio individual nanopores combines optical lithography and anisotropic KOH etching with a final electrochemical etching step to form the nanopores and is repeatable and can be processed in batches. We demonstrate electrical detection of dsDNA translocation, where the characteristic time of the process is in the millisecond range. We also analyse the translocation parameters and correlate the enhanced length of the nanopore to a longer translocation time as compared to other substrates.

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 °C for 1 h in an atmosphere of 5% H2 in Ar, forming a thin oxide passivating layer due to trace amounts of oxygen. Isolated Si QDs covering large areas (∼mm2) 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 [[Formula: see text]] and [[Formula: see text]]. In addition, system resolution-limited (250 µeV) 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.

Geometry effects on luminescence solar concentrator efficiency: analytical treatment.

Luminescence solar concentrators act as semitransparent photovoltaic cells of interest for modern urban environments. Here, their efficiencies were analytically derived for different regular unit shapes as simple, integral-free expressions. This allowed analysis of the shape and size effect on the device performance. All regular shapes appear to have a similar efficiency as revealed by optical path distribution formulas, despite differences in the perimeter length. Rectangles of the same area feature higher efficiency due to reduced average optical path. It comes with the cost of a longer perimeter, and the relation between these two is provided. An explicit formula for the critical size of an LSC unit, above which its inner part becomes inactive, has been obtained. For square geometry with matrix absorption coefficient α this critical size is ∼2.7/α, corresponding to 70-90 cm for common polymer materials. Obtained results can be used for treatment of individual units as well as for analysis of tiling for large areas.

Effect of transparent wood on the polarization degree of light.

We report on the study of polarization properties of light propagating through transparent wood (TW), which is an anisotropically scattering medium, and consider two cases: completely polarized and totally unpolarized light. It was demonstrated that scattered light distribution is affected by the polarization state of incident light. Scattering is the most efficient for light polarized parallel to cellulose fibers. Furthermore, unpolarized light becomes partially polarized (with a polarization degree of 50%) after propagating through the TW. In the case of totally polarized incident light, however, the degree of polarization of transmitted light is decreased, in an extreme case to a few percent, and reveals an unusual angular dependence on the material orientation. The internal hierarchical complex structure of the material, in particular cellulose fibrils organized in lamellae, is believed to be responsible for the change of the light polarization degree. It was demonstrated that the depolarization properties are determined by the angle between the polarization of light and the wood fibers, emphasizing the impact of their internal structure, unique for different wood species.

Non-stationary analysis of molecule capture and translocation in nanopore arrays.

Analytical formulas for the ON- and OFF-time distributions as well as for the autocorrelation function were derived for the case of single molecule translocation through nanopore arrays. The obtained time-dependent expressions describe very well experimentally recorded statistics of DNA translocations through an array of solid state nanopores, which allows us to extract molecule and system related physical parameters from the experimental traces. The necessity of non-stationary analysis as opposite to the steady-state approximation has been vindicated for the molecule capture process, where different time-dependent regimes were identified. A long tail in the distribution of translocation times has been rationalized invoking Markov jumps, where a possible sequential ordering of events was elucidated through autocorrelation function analysis.

Probing silicon quantum dots by single-dot techniques.

Silicon nanocrystals represent an important class of non-toxic, heavy-metal free quantum dots, where the high natural abundance of silicon is an additional advantage. Successful development in mass-fabrication, starting from porous silicon to recent advances in chemical and plasma synthesis, opens up new possibilities for applications in optoelectronics, bio-imaging, photovoltaics, and sensitizing areas. In this review basic physical properties of silicon nanocrystals revealed by photoluminescence spectroscopy, lifetime, intensity trace and electrical measurements on individual nanoparticles are summarized. The fabrication methods developed for accessing single Si nanocrystals are also reviewed. It is concluded that silicon nanocrystals share many of the properties of direct bandgap nanocrystals exhibiting sharp emission lines at low temperatures, on/off blinking, spectral diffusion etc. An analysis of reported results is provided in comparison with theory and with direct bandgap material quantum dots. In addition, the role of passivation and inherent interface/matrix defects is discussed.

Influence of swift heavy ion irradiation on the photoluminescence of Si-nanoparticles and defects in SiO2.

The influence of swift heavy ion (SHI) irradiation on the photoluminescence (PL) of silicon nanoparticles (SiNPs) and defects in SiO2-film is investigated. SiNPs were formed by implantation of 70 keV Si+ and subsequent thermal annealing to produce optically active SiNPs and to remove implantation-induced defects. Seven different ion species with energy between 3-36 MeV and fluence from 1011-1014 cm-2 were employed for irradiation of the implanted samples prior to the thermal annealing. Induced changes in defect and SiNP PL were characterized and correlated with the specific energy loss of the employed SHIs. We find that SHI irradiation, performed before the thermal annealing process, affects both defect and SiNP PL. The change of defect and SiNP PL due to SHI irradiation is found to show a threshold-like behaviour with respect to the electronic stopping power, where a decrease in defect PL and an anticorrelated increase in SiNP PL after the subsequent thermal annealing are observed for electronic stopping exceeding 3-5 keV nm-1. PL intensities are also compared as a function of total energy deposition and nuclear energy loss. The observed effects can be explained by ion track formation as well as a different type of annealing mechanisms active for SHI irradiation compared to the thermal annealing.

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.

Nanopore arrays in a silicon membrane for parallel single-molecule detection: fabrication.

Solid state nanopores enable translocation and detection of single bio-molecules such as DNA in buffer solutions. Here, sub-10 nm nanopore arrays in silicon membranes were fabricated by using electron-beam lithography to define etch pits and by using a subsequent electrochemical etching step. This approach effectively decouples positioning of the pores and the control of their size, where the pore size essentially results from the anodizing current and time in the etching cell. Nanopores with diameters as small as 7 nm, fully penetrating 300 nm thick membranes, were obtained. The presented fabrication scheme to form large arrays of nanopores is attractive for parallel bio-molecule sensing and DNA sequencing using optical techniques. In particular the signal-to-noise ratio is improved compared to other alternatives such as nitride membranes suffering from a high-luminescence background.

Nanopore arrays in a silicon membrane for parallel single-molecule detection: DNA translocation.

Optical nanopore sensing offers great potential in single-molecule detection, genotyping, or DNA sequencing for high-throughput applications. However, one of the bottle-necks for fluorophore-based biomolecule sensing is the lack of an optically optimized membrane with a large array of nanopores, which has large pore-to-pore distance, small variation in pore size and low background photoluminescence (PL). Here, we demonstrate parallel detection of single-fluorophore-labeled DNA strands (450 bps) translocating through an array of silicon nanopores that fulfills the above-mentioned requirements for optical sensing. The nanopore array was fabricated using electron beam lithography and anisotropic etching followed by electrochemical etching resulting in pore diameters down to ∼7 nm. The DNA translocation measurements were performed in a conventional wide-field microscope tailored for effective background PL control. The individual nanopore diameter was found to have a substantial effect on the translocation velocity, where smaller openings slow the translocation enough for the event to be clearly detectable in the fluorescence. Our results demonstrate that a uniform silicon nanopore array combined with wide-field optical detection is a promising alternative with which to realize massively-parallel single-molecule detection.

Oxidation of nanopores in a silicon membrane: self-limiting formation of sub-10 nm 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 °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.

Plasmon-Enhanced Fluorescence of Single Quantum Dots Immobilized in Optically Coupled Aluminum Nanoholes.

Fluorescence-based optical sensing techniques have continually been explored for single-molecule detection targeting myriad biomedical applications. Improving signal-to-noise ratio remains a prioritized effort to enable unambiguous detection at single-molecule level. Here, we report a systematic simulation-assisted optimization of plasmon-enhanced fluorescence of single quantum dots based on nanohole arrays in ultrathin aluminum films. The simulation is first calibrated by referring to the measured transmittance in nanohole arrays and subsequently used for guiding their design. With an optimized combination of nanohole diameter and depth, the variation of the square of simulated average volumetric electric field enhancement agrees excellently with that of experimental photoluminescence enhancement over a large range of nanohole periods. A maximum 5-fold photoluminescence enhancement is statistically achieved experimentally for the single quantum dots immobilized at the bottom of simulation-optimized nanoholes in comparison to those cast-deposited on bare glass substrate. Hence, boosting photoluminescence with optimized nanohole arrays holds promises for single-fluorophore-based biosensing.

Color-Switchable Nanosilicon Fluorescent Probes.

Fluorescent probes are vital to cell imaging by allowing specific parts of cells to be visualized and quantified. Color-switchable probes (CSPs), with tunable emission wavelength upon contact with specific targets, are particularly powerful because they not only eliminate the need to wash away all unbound probe but also allow for internal controls of probe concentrations, thereby facilitating quantification. Several such CSPs exist and have proven very useful, but not for all key cellular targets. Here we report a pioneering CSP for in situ cell imaging using aldehyde-functionalized silicon nanocrystals (SiNCs) that switch their intrinsic photoluminescence from red to blue quickly when interacting with amino acids in live cells. Though conventional probes often work better in cell-free extracts than in live cells, the SiNCs display the opposite behavior and function well and fast in universal cell lines at 37 °C while requiring much higher temperature in extracts. Furthermore, the SiNCs only disperse in cytoplasm not nucleus, and their fluorescence intensity correlated linearly with the concentration of fed amino acids. We believe these nanosilicon probes will be promising tools to visualize distribution of amino acids and potentially quantify amino acid related processes in live cells.

Low-Cost Synthesis of Silicon Quantum Dots with Near-Unity Internal Quantum Efficiency.

As a cost-effective batch synthesis method, Si quantum dots (QDs) with near-infrared photoluminescence, high quantum yield (>50% in polymer nanocomposite), and near-unity internal quantum efficiency were fabricated from an inexpensive commercial precursor (triethoxysilane, TES), using optimized annealing and etching processes. The optical properties of such QDs are similar to those prepared from state-of-the-art precursors (hydrogen silsesquioxane, HSQ) yet featuring an order of magnitude lower cost. To understand the effect of synthesis parameters on QD optical properties, we conducted a thorough comparison study between common solid precursors: TES, HSQ, and silicon monoxide (SiO), including chemical, structural, and optical characterizations. We found that the structural nonuniformity and abundance of oxide inherent to SiO limited the resultant QD performance, while for TES-derived QDs this drawback can be avoided. The presented low-cost synthetic approach would significantly favor applications requiring high loading of good-quality Si QDs, such as light conversion for photovoltaics.

Reversible Dual-Stimuli-Responsive Chromic Transparent Wood Biocomposites for Smart Window Applications.

Transparent wood (TW)-based composites are of significant interest for smart window applications. In this research, we demonstrate a facile dual-stimuli-responsive chromic TW where optical properties are reversibly controlled in response to changes in temperature and UV-radiation. For this functionality, bleached wood was impregnated with solvent-free thiol and ene monomers containing chromic components, consisting of a mixture of thermo- and photoresponsive chromophores, and was then UV-polymerized. Independent optical properties of individual chromic components were retained in the compositional mixture. This allowed to enhance the absolute optical transmission to 4 times above the phase change temperature. At the same time, the transmission at 550 nm could be reduced 11-77%, on exposure to UV by changing the concentration of chromic components. Chromic components were localized inside the lumen of the wood structure, and durable reversible optical properties were demonstrated by multiple cycling testing. In addition, the chromic TW composites showed reversible energy absorption capabilities for heat storage applications and demonstrated an enhancement of 64% in the tensile modulus as compared to a native thiol-ene polymer. This study elucidates the polymerization process and effect of chromic components distribution and composition on the material's performance and perspectives toward the development of smart photoresponsive windows with energy storage capabilities.

Manifold enhancement of electron beam induced deposition rate at grazing incidence.

It is shown how a significant drawback of the electron beam induced deposition technique, namely its low deposition rate, can be circumvented. By tilting a sample, a larger part of the primary electron beam energy becomes dissipated closer to the interface. This in turn increases the emission of secondary electrons, largely responsible for the deposition of the adsorbed molecule components on the surface. An order of magnitude increase in the deposition rate is reported in the fabrication of metal nanowires from organic precursor gas.