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.

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.

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.

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.

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.

Transparent Wood Biocomposites by Fast UV-Curing for Reduced Light-Scattering through Wood/Thiol-ene Interface Design.

Transparent wood (TW) is an interesting polymer biocomposite with potential for buildings and photonics applications. TW materials need to be eco-friendly and readily processed with few defects, for high optical transmittance and low transmission scattering at wide angles (haze). Two wood templates with different lignin-content are impregnated with a new thiol-ene thermoset system. The more eco-friendly bleached wood template results in transparent wood with high optical transmission and much reduced transmission haze, due to strong reduction of interfacial air gaps. Characterization includes template composition, thiol-ene distribution, and polymerization in wood cell wall by EDX and confocal Raman microscopy, also NMR and DSC, tensile testing and FE-SEM fractography for morphology and wood/thiol-ene interface adhesion assessment. The wood template is a true nanocomposite with thiol-ene polymer located inside the nanoporous wood cell wall. Advanced TW applications require not only appropriate wood template modification and careful polymer matrix selection but also tailoring of the process to impregnation and polymerization mechanisms, in order to reduce optical defects.

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.

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.

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.

Refractive index of delignified wood for transparent biocomposites.

Refractive index (RI) determination for delignified wood templates is vital for transparent wood composite fabrication. Reported RIs in the literature are based on either single plant fibers or wood powder, measured by the immersion liquid method (ILM) combined with mathematical fitting. However, wood structure complexity and the physical background of the fitting were not considered. In this work, RIs of delignified wood templates were measured by the ILM combined with a light transmission model developed from the Fresnel reflection/refraction theory for composite materials. The RIs of delignified balsa wood are 1.536 ± 0.006 and 1.525 ± 0.008 at the wavelength of 589 nm for light propagating perpendicular and parallel to the wood fiber direction, respectively. For delignified birch wood, corresponding values are 1.537 ± 0.005 and 1.529 ± 0.006, respectively. The RI data for delignified wood scaffolds are important for tailoring optical properties of transparent wood biocomposites, and also vital in optical properties investigations by theoretical modelling of complex light propagation in transparent wood and related composites. The developed light transmission model in combination with the immersion liquid method can be used to determine the RI of complex porous or layered solid materials and composites.

Thickness Dependence of Optical Transmittance of Transparent Wood: Chemical Modification Effects.

Transparent wood (TW) is an emerging optical material combining high optical transmittance and haze for structural applications. Unlike nonscattering absorbing media, the thickness dependence of light transmittance for TW is complicated because optical losses are also related to increased photon path length from multiple scattering. In the present study, starting from photon diffusion equation, it is found that the angle-integrated total light transmittance of TW has an exponentially decaying dependence on sample thickness. The expression reveals an attenuation coefficient which depends not only on the absorption coefficient but also on the diffusion coefficient. The total transmittance and thickness were measured for a range of TW samples, from both acetylated and nonacetylated balsa wood templates, and were fitted according to the derived relationship. The fitting gives a lower attenuation coefficient for the acetylated TW compared to the nonacetylated one. The lower attenuation coefficient for the acetylated TW is attributed to its lower scattering coefficient or correspondingly lower haze. The attenuation constant resulted from our model hence can serve as a singular material parameter that facilitates cross-comparison of different sample types, at even different thicknesses, when total optical transmittance is concerned. The model was verified with two other TWs (ash and birch) and is in general applicable to other scattering media.

Size-Dependent Phase Transition in Perovskite Nanocrystals.

The complex structure of halide and oxide perovskites strongly affects their physical properties. Here, the effect of dimensions reduced to the nanoscale has been investigated by a combination of single-dot optical experiments with a phase transition theory. Methylammonium lead bromide (CH3NH3PbBr3) nanocrystals with two average particle sizes of ∼2 and ∼4 nm with blue and green photoluminescence, respectively, were spectrally and temporally probed on a single-particle level from 5 to 295 K. The results show that the abrupt blue shift of the photoluminescence spectra and lifetimes at ∼150 K can be attributed to the cubic-to-tetragonal phase transition in the large 4 nm nanocrystals, while this phase transition is completely absent for the small 2 nm particles in the investigated temperature range. Theoretical calculations based on Landau theory reveal a strong size-dependent effect on temperature-induced phase transitions in individual CH3NH3PbBr3 nanocrystals, corroborating experimental observations. This effect should be considered in structure-property analysis of ultrasmall perovskite crystals.

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.

Photodegradation of Organometal Hybrid Perovskite Nanocrystals: Clarifying the Role of Oxygen by Single-Dot Photoluminescence.

Photostability has been a major issue for perovskite materials. Understanding the photodegradation mechanism and suppressing it are of central importance for applications. By investigating single-dot photoluminescence spectra and the lifetime of MAPbX3 (MA = CH3NH3+, X = Br, I) nanocrystals with quantum confinement under different conditions, we identified two separate pathways in the photodegradation process. The first is the oxygen-assisted light-induced etching process (photochemistry). The second is the light-driven slow charge-trapping process (photophysics), taking place even in oxygen-free environment. We clarified the role of oxygen in the photodegradation process and show how the photoinduced etching can be successfully suppressed by OSTE polymer, preventing an oxygen-assisted reaction.

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.