Light-Addressable Electrochemical Sensing with Electrodeposited n-Silicon/Gold Nanoparticle Schottky Junctions.

Light-addressable electrochemical sensors (LAESs) are a class of sensors that use light to activate an electrochemical reaction on the surface of a semiconducting photoelectrode. Here, we investigate semiconductor/metal (Schottky) junctions formed between n-type Si and Au nanoparticles as light-addressable electrochemical sensors. To demonstrate this concept, we prepared n-Si/Au nanoparticle Schottky junctions by electrodeposition and characterized them using scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. We found that the sensors behaved almost identically to Au disk electrodes for the oxidation of an outer-sphere redox couple (ferrocene methanol) and two inner-sphere redox couples (potassium ferrocyanide and dopamine). In buffered dopamine solutions, we observed broad linear ranges and submicromolar detection limits. We then used local illumination to generate a virtual array of electrochemical sensors for dopamine as a strategy for circumventing sensor fouling, which is a persistent problem for electrochemical dopamine sensors. By locally illuminating a small portion of the photoelectrode, many measurements of fouling analytes can be made on a single sensor with a single electrical connection by moving the light beam to a fresh area of the sensor. Altogether, these results pave the way for Schottky junction light-addressable electrochemical sensors to be useful for a number of interesting future applications in chemical and biological sensing.

DNA-Hybridization Detection on Si(100) Surfaces Using Light-Activated Electrochemistry: A Comparative Study between Bovine Serum Albumin and Hexaethylene Glycol as Antifouling Layers.

Light can be used to spatially resolve electrochemical measurements on a semiconductor electrode. This phenomenon has been explored to detect DNA hybridization with light-addressable potentiometric sensors and, more recently, with light-addressable amperometric sensors based on organic-monolayer-protected Si(100). Here, a contribution to the field is presented by comparing sensing performances when bovine serum albumin (BSA) and hexaethylene glycol (OEG6) are employed as antifouling layers that resist nonspecific adsorption to the DNA-modified interface on Si(100) devices. What is observed is that both sensors based on BSA or OEG6 initially allow electrochemical distinction among complementary, noncomplementary, and mismatched DNA targets. However, only surfaces based on OEG6 can sustain electroactivity over time. Our results suggest that this relates to accelerated SiO x formation occasioned by BSA proteins adsorbing on monolayer-protected Si(100) surfaces. Therefore, DNA biosensors were analytically explored on low-doped Si(100) electrodes modified on the molecular level with OEG6 as an antifouling layer. First, light-activated electrochemical responses were recorded over a range of complementary DNA target concentrations. A linear semilog relation was obtained from 1.0 × 10-11 to 1.0 × 10-6 mol L-1 with a correlation coefficient of 0.942. Then, measurements with three independent surfaces indicated a relative standard deviation of 4.5%. Finally, selectivity tests were successfully performed in complex samples consisting of a cocktail mixture of four different DNA sequences. Together, these results indicate that reliable and stable light-activated amperometric DNA sensors can be achieved on Si(100) by employing OEG6 as an antifouling layer.

Porous Silicon's Photoactivity in Water: Insights into Environmental Fate.

Interest in porous silicon (pSi) (and, more broadly, silicon nanoparticles (NPs)) has increased along with their concomitant use in various commercial and consumer products, yet little is known about their behavior in the natural environment. In this study, we have investigated the photosensitization, optical, and surface properties of pSi as a function of time in aqueous systems. Samples were prepared via an anodic electrochemical etching procedure, resulting in pSi particles with diameters of ca. 500 nm, composed of a porous network of Si nanocrystallites of 2-4 nm. Initially, pSi particles generated significant amounts of (1)O2, yet they rapidly lost much of this ability due to the formation of an oxide layer on the surface, as determined by X-ray photoelectron spectroscopy, which likely prevented further photosensitization events. Addition of natural organic matter (NOM) did not significantly impact pSi's photosensitization abilities. The pSi lacked any intrinsic bactericidal properties on Escherichia coli and did not produce enough (1)O2 to considerably affect populations of a model virus, PR772, highlighting its relatively benign nature toward microbial communities. Results from this study suggest that the photoactivity of pSi is unlikely to persist in aqueous systems and that it may instead behave more similarly to silica particles from an environmental perspective.

Precision measurement of the photon detection efficiency of silicon photomultipliers using two integrating spheres.

We report a new and improved photon counting method for the precision PDE measurement of SiPM detectors, utilizing two integrating spheres connected serially and calibrated reference detectors. First, using a ray tracing simulation and irradiance measurement results with a reference photodiode, we investigated irradiance characteristics of the measurement instrument, and analyzed dominating systematic uncertainties in PDE measurement. Two SiPM detectors were then used for PDE measurements between wavelengths of 368 and 850 nm and for bias voltages varying from around 70V. The resulting PDEs of the SiPMs show good agreement with those from other studies, yet with an improved accuracy of 1.57% (1σ). This was achieved by the simultaneous measurement with the NIST calibrated reference detectors, which suppressed the time dependent variation of source light. The technical details of the instrumentation, measurement results and uncertainty analysis are reported together with their implications.

GeSn-on-Si normal incidence photodetectors with bandwidths more than 40 GHz.

GeSn (Sn content up to 4.2%) photodiodes with vertical pin structures were grown on thin Ge virtual substrates on Si by a low temperature (160 °C) molecular beam epitaxy. Vertical detectors were fabricated by a double mesa process with mesa radii between 5 µm and 80 µm. The nominal intrinsic absorber contains carrier densities from below 1 · 10(16) cm(-3) to 1 · 10(17) cm(-3) for Ge reference detectors and GeSn detectors with 4.2% Sn, respectively. The photodetectors were investigated with electrical and optoelectrical methods from direct current up to high frequencies (40 GHz). For a laser wavelength of 1550 nm an increasing of the optical responsivities (84 mA/W -218 mA/W) for vertical incidence detectors with thin (300 nm) absorbers as function of the Sn content were found. Most important from an application perspective all detectors had bandwidth above 40 GHz at enough reverse voltage which increased from zero to -5 V within the given Sn range. Increasing carrier densities (up to 1 · 10(17) cm(-3)) with Sn contents caused the depletion of the nominal intrinsic absorber at increasing reverse voltages.

Mesoscale modeling of photoelectrochemical devices: light absorption and carrier collection in monolithic, tandem, Si|WO3 microwires.

We analyze mesoscale light absorption and carrier collection in a tandem junction photoelectrochemical device using electromagnetic simulations. The tandem device consists of silicon (E(g,Si) = 1.1 eV) and tungsten oxide (E(g,WO3) = 2.6 eV) as photocathode and photoanode materials, respectively. Specifically, we investigated Si microwires with lengths of 100 µm, and diameters of 2 µm, with a 7 µm pitch, covered vertically with 50 µm of WO3 with a thickness of 1 µm. Many geometrical variants of this prototypical tandem device were explored. For conditions of illumination with the AM 1.5G spectra, the nominal design resulted in a short circuit current density, J(SC), of 1 mA/cm(2), which is limited by the WO3 absorption. Geometrical optimization of photoanode and photocathode shape and contact material selection, enabled a three-fold increase in short circuit current density relative to the initial design via enhanced WO3 light absorption. These findings validate the usefulness of a mesoscale analysis for ascertaining optimum optoelectronic performance in photoelectrochemical devices.

Pyramidal surface textures for light trapping and antireflection in perovskite-on-silicon tandem solar cells.

Perovskite-on-silicon tandem solar cells show potential to reach > 30% conversion efficiency, but require careful optical control. We introduce here an effective light-management scheme based on the established pyramidal texturing of crystalline silicon cells. Calculations show that conformal deposition of a thin film perovskite solar cell directly onto the textured front surface of a high efficiency silicon cell can yield front surface reflection losses as low as 0.52mA/cm(2). Combining this with a wavelength-selective intermediate reflector between the cells additionally provides effective light-trapping in the high-bandgap top cell, resulting in calculated absolute efficiency gains of 2 - 4%. This approach provides a practical and effective method to adapt existing high efficiency silicon cell designs for use in tandem cells, with conversion efficiencies approaching 35%.

Crystal orientation dependence of femtosecond laser-induced periodic surface structure on (100) silicon.

It is widely believed that laser-induced periodic surface structures (LIPSS) are independent of material crystal structures. This Letter reports an abnormal phenomenon of strong dependence of the anisotropic formation of periodic ripples on crystal orientation, when Si (100) is processed by a linearly polarized femtosecond laser (800 nm, 50 fs, 1 kHz). LIPSS formation sensitivity with a π/2 modulation is found along different crystal orientations with a quasi-cosinusoid function when the angle between the crystal orientation and polarization direction is changed from 0° to 180°. Our experiments indicate that it is much easier (or more difficult) to form ripple structures when the polarization direction is aligned with the lattice axis [011]/[011¯] (or [001]). The modulated nonlinear ionization rate along different crystal orientations, which arises from the direction dependence of the effective mass of the electron is proposed to interpret the unexpected anisotropic LIPSS formation phenomenon. Also, we demonstrate that the abnormal phenomenon can be applied to control the continuity of scanned ripple lines along different crystal orientations.

Polarization-dependent elliptical crater morphologies formed on a silicon surface by single-shot femtosecond laser ablation.

Formation of the elliptical-shaped craters on a silicon surface is investigated comprehensively using a single shot of a femtosecond laser. It is observed that the ablation craters are elongated along the major axis of the polarization direction, while their orientation is parallel to the polarization direction. The ablation area grows and the morphology of the craters evolves from an ellipse to nearly a circle with increasing fluence. The underlying physical mechanism is revealed through numerical simulations that are based on the finite-difference time-domain technique. It is suggested that the initially formed craters or surface defects lead to the redistribution of the electric field on the silicon surface, which plays a crucial role in the creation of the elliptical-shaped craters. In addition, the field intensity becomes enhanced along the incident laser polarization direction, which determines the elliptical crater orientations.

Doping effects on ablation enhancement in femtosecond laser irradiation of silicon.

We have conducted an experimental investigation on highly efficient femtosecond laser micromachining of silicon through N-type doping. We found that the material removal amount has a close relationship with the doping concentration rather than with the doping types. The amount of material removal was enhanced gradually as doping densities increased. When the doping density reached higher than 10(18) cm(-3), the ablation threshold was considerably reduced, up to 15%-20%. The results of the experiment indicate that the high density of initial free electrons by doping is the fundamental reason for efficiency improvement, and bandgap shrinkage also plays an important role. The electrons are excited more easily from the valance band to the conduction band and acquire higher initial kinetic energy, which then promotes the material ablation process.

Highly directional thermal emission from two-dimensional silicon structures.

We simulate, fabricate, and characterize near perfectly absorbing two-dimensional grating structures in the thermal infrared using heavily doped silicon (HdSi) that supports long wave infrared surface plasmon polaritons (LWIR SPP's). The devices were designed and optimized using both finite difference time domain (FDTD) and rigorous coupled wave analysis (RCWA) simulation techniques to satisfy stringent requirements for thermal management applications requiring high thermal radiation absorption over a narrow angular range and low visible radiation absorption over a broad angular range. After optimization and fabrication, characterization was performed using reflection spectroscopy and normal incidence emissivity measurements. Excellent agreement between simulation and experiment was obtained.

Permanent fine tuning of silicon microring devices by femtosecond laser surface amorphization and ablation.

We demonstrate the fine tuning capability of femtosecond laser surface modification as a permanent trimming mechanism for silicon photonic components. Silicon microring resonators with a 15 µm radius were irradiated with single 400 nm wavelength laser pulses at varying fluences. Below the laser ablation threshold, surface amorphization of the crystalline silicon waveguides yielded a tuning rate of 20 ± 2 nm/J · cm(-2)with a minimum resonance wavelength shift of 0.10nm. Above that threshold, ablation yielded a minimum resonance shift of -1.7 nm. There was some increase in waveguide loss for both trimming mechanisms. We also demonstrated the application of the method by using it to permanently correct the resonance mismatch of a second-order microring filter.

Femtosecond laser-irradiated crystallization of amorphous Si2Sb2Te3 films and its in-situ characterization by coherent phonon spectroscopy.

Femtosecond laser-irradiation-induced phase change of a new amorphous Si(2)Sb(2)Te(3) film with a good thermal stability and low reset current is studied by coherent phonon spectroscopy. New coherent optical phonons (COP) occur as laser irradiation fluence reaches some threshold, implying laser-induced phase change emerged. The compositions in phase-changed area revealed by COP modes agree well with ones in reported annealed crystallized film, implying laser-induced phase change as crystallization. Pump fluence dependence of COP dynamics reveals good crystallization quality of the phase-changed film, exhibiting promising application of Si(2)Sb(2)Te(3) films in optical phase change memory. Acoustic phonons are also found and identified.

Asymmetric femtosecond laser ablation of silicon surface governed by the evolution of surface nanostructures.

The femtosecond laser ablation of silicon surface near the ablation threshold was investigated and the preferential ablation along different directions was observed in different stages. It was found that the ripples formed in the initial stage facilitate the ablation along the direction perpendicular to the ripples, leading to the formation of an elliptical ablation area. With increasing length and depth of the ripples, however, nanohole arrays formed in the ripples will modify the distribution of electric field which benefits the ablation along the direction parallel to the ripples. Consequently, the ablation area is gradually changed to a circular one after irradiating sufficient number of pulses.

Fabrication of high-aspect-ratio grooves in silicon using femtosecond laser irradiation and oxygen-dependent acid etching.

We demonstrated a new method to fabricate micron-sized grooves with high aspect ratios in silicon wafers by combining femtosecond laser irradiation and oxygen-dependent acid etching. Femtosecond laser was employed to induce structure changes and incorporate oxygen into silicon, and then materials in oxygen-containing regions were etched by hydrofluoric acid (HF) solution to form grooves. The etching could be attributed to the reaction between HF and silicon oxides formed by femtosecond laser irradiation. The dependences of the aspect ratios of grooves on the laser fluence and the scanning velocity were also investigated.

Silicon avalanche photodiode operation and lifetime analysis for small satellites.

Silicon avalanche photodiodes (APDs) are sensitive to operating temperature fluctuations and are also susceptible to radiation flux expected in satellite-based quantum experiments. We introduce a low power voltage adjusting mechanism to overcome the effects of in-orbit temperature fluctuations. We also present data on the performance of Si APDs after irradiation (γ-ray and proton beam). Combined with an analysis of expected orbital irradiation, we propose that a Si APD in a 400 km equatorial orbit may operate beyond the lifetime of the satellite.

Ge/Si heterojunction photodiodes fabricated by low temperature wafer bonding.

We report on the photoresponse of an asymmetrically doped p(-)-Ge/n(+)-Si heterojunction photodiode fabricated by wafer bonding. Responsivities in excess of 1 A/W at 1.55 µm are measured with a 5.4 µm thick Ge layer under surface-normal illumination. Capacitance-voltage measurements show that the interfacial band structure is dependent on both temperature and light level, moving from depletion of holes at -50 °C to accumulation at 20 °C. Interface traps filled by photo-generated and thermally-generated carriers are shown to play a crucial role. Their filling alters the potential barrier height at the interface leading to increased flow of dark current and the above unity responsivity.

Dramatic size reduction of waveguide bends on a micron-scale silicon photonic platform.

We demonstrate theoretically and experimentally how highly multimodal high index contrast waveguides with micron-scale cores can be bent, on an ultra-broad band of operation, with bending radii below 10 µm and losses for the fundamental mode below 0.02 dB/90°. The bends have been designed based on the Euler spiral and fabricated on 4 µm thick SOI. The proposed approach enabled also the realization of 180° bends with 1.27 µm effective radii and 0.09 dB loss, which are the smallest low-loss bends ever reported for an optical waveguide. These results pave the way for unprecedented integration density in most semiconductor platforms.

Two-photon laser-assisted device alteration in silicon integrated-circuits.

Optoelectronic imaging of integrated-circuits has revolutionized device design debug, failure analysis and electrical fault isolation; however modern probing techniques like laser-assisted device alteration (LADA) have failed to keep pace with the semiconductor industry's aggressive device scaling, meaning that previously satisfactory techniques no longer exhibit a sufficient ability to localize electrical faults, instead casting suspicion upon dozens of potential root-cause transistors. Here, we introduce a new high-resolution probing technique, two-photon laser-assisted device alteration (2pLADA), which exploits two-photon absorption (TPA) to provide precise three-dimensional localization of the photo-carriers injected by the TPA process, enabling us to implicate individual transistors separated by 100 nm. Furthermore, we illustrate the technique's capability to reveal speed-limiting transistor switching evolution with an unprecedented timing resolution approaching <10 ps. Together, the exceptional spatial and temporal resolutions demonstrated here now make it possible to extend optical fault localization to sub-14 nm technology nodes.