Voltage- and Metal-assisted Chemical Etching of Micro and Nano Structures in Silicon: A Comprehensive Review.

Sculpting silicon at the micro and nano scales has been game-changing to mold bulk silicon properties and expand, in turn, applications of silicon beyond electronics, namely, in photonics, sensing, medicine, and mechanics, to cite a few. Voltage- and metal-assisted chemical etching (ECE and MaCE, respectively) of silicon in acidic electrolytes have emerged over other micro and nanostructuring technologies thanks to their unique etching features. ECE and MaCE have enabled the fabrication of novel structures and devices not achievable otherwise, complementing those feasible with the deep reactive ion etching (DRIE) technology, the gold standard in silicon machining. Here, a comprehensive review of ECE and MaCE for silicon micro and nano machining is provided. The chemistry and physics ruling the dissolution of silicon are dissected and similarities and differences between ECE and MaCE are discussed showing that they are the two sides of the same coin. The processes governing the anisotropic etching of designed silicon micro and nanostructures are analyzed, and the modulation of etching profile over depth is discussed. The preparation of micro- and nanostructures with tailored optical, mechanical, and thermo(electrical) properties is then addressed, and their applications in photonics, (bio)sensing, (nano)medicine, and micromechanical systems are surveyed. Eventually, ECE and MaCE are benchmarked against DRIE, and future perspectives are highlighted.

Toward a10†dB net-gain waveguide amplifier in an Er3+-Yb3+ co-doped phosphate glass.

High-gain materials and high-quality structures are the two main conditions that determine the amplification performance of optical waveguides. However, it has been hard to balance each other, to date. In this work, we demonstrate breakthroughs in both glass optical gain and optical waveguide structures. We propose a secondary melting dehydration technique that prepares high-quality Er3+-Yb3+ co-doped phosphate glass with low absorption loss. Additionally, we propose a femtosecond laser direct-writing technique that allows controlling the cross section, size, and mode field of waveguides written in glass with high accuracy, leveraging submicron-resolution multi-scan direct-writing optical waveguide technology, which is beneficial for reducing insertion loss. As a proof of concept demonstration, we designed and fabricated two kinds of waveguides, namely, LP01- and LP11-mode waveguides in the Er3+-Yb3+ co-doped phosphate glass, enabling insertion loss as low as 0.9 dB for a waveguide length of 2 mm. Remarkably, we successfully achieved an optical amplification for both the waveguides with a net gain of >7 dB and a net-gain coefficient of >3.5 dB/mm, which is approximately one order of magnitude larger than that in the Er3+-Yb3+ co-doped phosphate glass fabricated by the traditional melt-quenching method. This will open new avenues toward the development of integrated photonic chips.

1D and 2D Field Effect Transistors in Gas Sensing: A Comprehensive Review.

Rapid progress in the synthesis and fundamental understanding of 1D and 2D materials have solicited the incorporation of these nanomaterials into sensor architectures, especially field effect transistors (FETs), for the monitoring of gas and vapor in environmental, food quality, and healthcare applications. Yet, several challenges have remained unaddressed toward the fabrication of 1D and 2D FET gas sensors for real-field applications, which are related to properties, synthesis, and integration of 1D and 2D materials into the transistor architecture. This review paper encompasses the whole assortment of 1D-i.e., metal oxide semiconductors (MOXs), silicon nanowires (SiNWs), carbon nanotubes (CNTs)-and 2D-i.e., graphene, transition metal dichalcogenides (TMD), phosphorene-materials used in FET gas sensors, critically dissecting how the material synthesis, surface functionalization, and transistor fabrication impact on electrical versus sensing properties of these devices. Eventually, pros and cons of 1D and 2D FETs for gas and vapor sensing applications are discussed, pointing out weakness and highlighting future directions.

Vapor-Phase Synthesis of Molecularly Imprinted Polymers on Nanostructured Materials at Room-Temperature.

Molecularly imprinted polymers (MIPs) have recently emerged as robust and versatile artificial receptors. MIP synthesis is carried out in liquid phase and optimized on planar surfaces. Application of MIPs to nanostructured materials is challenging due to diffusion-limited transport of monomers within the nanomaterial recesses, especially when the aspect ratio is >10. Here, the room temperature vapor-phase synthesis of MIPs in nanostructured materials is reported. The vapor phase synthesis leverages a >1000-fold increase in the diffusion coefficient of monomers in vapor phase, compared to liquid phase, to relax diffusion-limited transport and enable the controlled synthesis of MIPs also in nanostructures with high aspect ratio. As proof-of-concept application, pyrrole is used as the functional monomer thanks to its large exploitation in MIP preparation; nanostructured porous silicon oxide (PSiO2 ) is chosen to assess the vapor-phase deposition of PPy-based MIP in nanostructures with aspect ratio >100; human hemoglobin (HHb) is selected as the target molecule for the preparation of a MIP-based PSiO2 optical sensor. High sensitivity and selectivity, low detection limit, high stability and reusability are achieved in label-free optical detection of HHb, also in human plasma and artificial serum. The proposed vapor-phase synthesis of MIPs is immediately transferable to other nanomaterials, transducers, and proteins.

High-order mode waveguide amplifier with high mode extinction ratio written in an Er3+-doped phosphate glass.

Inscription of fiber-compatible active waveguides in high-gain glass, followed by direct interconnection with few-mode fibers, is one of the most promising solutions for all-optical mode-division multiplexing. In this work, based on the femtosecond laser writing technique, we propose a general fabrication scheme for inscribing high-order mode waveguides in glass, by carefully tailoring the cross-section of the waveguides to match the mode intensity distribution via an improved multi-scan approach. Specifically, we design and fabricate two kinds of waveguides, namely, LP01-mode waveguide and LP11-mode waveguide in a highly Er3+-doped phosphate glass, enabling the insertion loss of the waveguides to be as low as 1.88 dB, and the mode extraction factor of the LP11-mode waveguide up to ∼24 dB. Importantly, we have successfully achieved optical amplification of the waveguides, with an on-off gain as high as 3.52 dB. This novel high-order mode waveguide amplifier has broad application prospects in monolithic on-chip integrated photonic light sources and optical interconnection with few-mode fiber and/or silicon-based waveguide.

Moldless Printing of Silicone Lenses With Embedded Nanostructured Optical Filters.

Optical lenses are among the oldest technological innovations (3000 years ago) and they have enabled a multitude of applications in healthcare and in our daily lives. The primary function of optical lenses has changed little over time; they serve mainly as a light-collection (e.g. reflected, transmitted, diffracted) element, and the wavelength and/or intensity of the collected light is usually manipulated by coupling with various external optical filter elements or coatings. This generally results in losses associated with multiple interfacial reflections, and increases the complexity of design and construction. In this work we introduce a change in this paradigm, by integrating both light-shaping and image magnification into a single lens element using a moldless procedure that takes advantage of the physical and optical properties of mesoporous silicon (PSi) photonic crystal nanostructures. Casting of a liquid poly(dimethyl) siloxane (PDMS) pre-polymer solution onto a PSi film generates a droplet with contact angle that is readily controlled by the silicon nanostructure, and adhesion of the cured polymer to the PSi photonic crystal allows preparation of lightweight (10 mg) freestanding lenses (4.7 mm focal length) with an embedded optical component (e.g. optical rugate filter, resonant cavity, distributed Bragg reflector). Our fabrication process shows excellent reliability (yield 95%) and low cost and we expect our lens to have implications in a wide range of applications. As a proof-of-concept, using a single monolithic lens/filter element we demonstrate: fluorescence imaging of isolated human cancer cells with rejection of the blue excitation light, through a lens that is self-adhered to a commercial smartphone; shaping the emission spectrum of a white light emitting diode (LED) to tune the color from red through blue; and selection of a narrow wavelength band (bandwidth 5 nm) from a fluorescent molecular probe.

Femtomole Detection of Proteins Using a Label-Free Nanostructured Porous Silicon Interferometer for Perspective Ultrasensitive Biosensing.

Nanostructured porous silicon (PS) is a promising material for label-free optical detection of biomolecules, though it currently suffers of limited clinical diagnostic applications due to insufficient sensitivity. In this regard, here we introduce an ultrasensitive and robust signal processing strategy for PS biosensors that relies on the calculation of the average value over wavelength of spectral interferograms, namely IAW, obtained on PS interferometer by subtraction (wavelength by wavelength) of reflection spectra acquired after adsorption of biomolecules inside the nanopores from a reference reflection spectrum recorded in acetate buffer. As a case study, we choose to monitor bovine serum albumin (BSA) unspecific adsorption, which has been often employed in the literature as a model for proof-of-concept studies of perspective biosensing applications. The proposed IAW signal processing strategy enables reliable detection of BSA at concentrations in the range from 150 pM to 15 µM (down to 3 orders of magnitude lower than those targeted in the current literature) using a PS interferometer operating in label-free mode without any amplification strategies, with good sample-to-sample reproducibility over the whole range of tested concentrations (%CV = 16% over 5 replicates) and good signal-to-noise ratio also at the lowest tested concentration (S/N ≈ 4.6 at 150 pM). A detection limit (DL) of 20 pM (20 femtomoles, 1 mL) is estimated from the sigmoidal function best fitting (R(2) = 0.989) IAW experimental data over the whole range of tested concentrations. This is the lowest DL that has been reported in the literature since the seminal paper of Sailor and co-workers (1997) on the use of PS interferometer for biosensing, and lowers of 4 orders of magnitude DL attained with label-free PS interferometers using conventional effective optical thickness (EOT) calculation through reflective interferometric Fourier transform spectroscopy. Accordingly, the IAW signal processing strategy envisage bringing PS optical transduction at the forefront of ultrasensitive label-free biosensing techniques, especially for point-of-care clinical analysis where low analyte concentrations have to be detected in a small amount of biological samples.

On the performance of label-free biosensors based on vertical one-dimensional photonic crystal resonant cavities.

In this work three Fabry-Perot (FP) resonant cavities based on vertical silicon/air one-dimensional photonic crystals (1DPhCs) featuring different architectures and fluidic functionalities are designed, and the role of key design parameters on their ideal biosensing performance, i.e. surface sensitivity, limit of detection, range of linearity, is investigated. Numerical calculations of the transmission spectra of the 1DPhC FP resonant cavities using the Transfer Matrix Method (TMM), versus thickness of a biolayer simulating biomolecules (e.g. proteins) adsorbed on the 1DPhC FP cavity surfaces, show that biosensors with surface sensitivity up to 300 pm/nm, limit of detection down to 0.07 nm, and high linearity over the range 0-50 nm of biolayer thickness can be achieved.

Ultrathin Ambipolar Polyelectrolyte Capacitors Prepared via Layer-by-Layer Assembling.

Miniaturized solid state capacitors leveraging migration of unipolar ions in a single polyelectrolyte layer sandwiched between metal electrodes, namely, polyelectrolyte capacitors (PECs), have been recently reported with areal capacitance up to 100-200 nF mm-2. Nonetheless, application of PECs in consumer and industrial electronics has been hindered so far by their small operational frequency range, up to a few kHz, due to the resistive behavior (phase angle >-45°) of PECs in the range kHz-to-MHz. Here, it is reported on multilayer polyelectrolyte capacitors (mPECs) that leverage as dielectric an ambipolar nanometer-thick (down to 10 nm) stack of anionic and cationic polyelectrolytes assembled layer-by-layer between metal electrodes to eliminate the resistive behavior at frequencies from kHz to MHz. This significantly extends the operational range of mPECs over PECs. mPECs with areal capacitance as high as 25 nF mm-2 at 20 Hz and full capacitive behavior from 100 mHz to 10 MHz are demonstrated using different assembling conditions and anionic/cationic polyelectrolyte pairs. The mPECs reliably operate over time for >300 million cycles, at different biasing voltages up to 3 V, and temperatures up to 80 °C, showing a reversible capacitive behavior without significant hysteresis. Application of mPECs in flexible electronics, also operating at high frequency, is envisaged.

Reconfigurable Optical Sensor for Metal-Ion-Mediated Label-Free Recognition of Different Biomolecular Targets.

Reconfiguration of chemical sensors, intended as the capacity of the sensor to adapt to novel operational scenarios, e.g., new target analytes, is potentially game changing and would enable rapid and cost-effective reaction to dynamic changes occurring at healthcare, environmental, and industrial levels. Yet, it is still a challenge, and rare examples of sensor reconfiguration have been reported to date. Here, we report on a reconfigurable label-free optical sensor leveraging the versatile immobilization of metal ions through a chelating agent on a nanostructured porous silica (PSiO2) optical transducer for the detection of different biomolecules. First, we show the reversible grafting of different metal ions on the PSiO2 surface, namely, Ni2+, Cu2+, Zn2+, and Fe3+, which can mediate the interaction with different biomolecules and be switched under mild conditions. Then, we demonstrate reconfiguration of the sensor at two levels: 1) switching of the metal ions on the PSiO2 surface from Cu2+ to Zn2+ and testing the ability of Cu2+-functionalized and Zn2+-reconfigured devices for the sensing of the dipeptide carnosine (CAR), leveraging the well-known chelating ability of CAR toward divalent metal ions; and 2) reconfiguration of the Cu2+-functionalized PSiO2 sensor for a different target analyte, namely, the nucleotide adenosine triphosphate (ATP), switching Cu2+ with Fe3+ ions to exploit the interaction with ATP through phosphate groups. The Cu2+-functionalized and Zn2+-reconfigured sensors show effective sensing performance in CAR detection, also evaluated in tissue samples from murine brain, and so does the Fe3+-reconfigured sensor toward ATP, thus demonstrating effective reconfiguration of the sensor with the proposed surface chemistry.

3D Laser Writing of Low-Loss Cross-Section-Variable Type-I Optical Waveguide Passive/Active Integrated Devices in Single Crystals.

Optical waveguides fabricated in single crystals offer crucial passive/active optical components for photonic integrated circuits. Single crystals possess inherent advantages over their amorphous counterpart, such as lower optical losses in visible-to-mid-infrared band, larger peak emission cross-section, higher doping concentration. However, the writing of Type-I positive refractive index modified waveguides in single crystals using femtosecond laser technology presents significant challenges. Herein, this work introduces a novel femtosecond laser direct writing technique that combines slit-shaping with an immersion oil objective to fabricate low-loss Type-I waveguides in single crystals. This approach allows for precise control of waveguide shape, size, mode-field, and refractive index distribution, with a spatial resolution as high as 700 nm and a high positive refractive index variation on the order of 10-2, introducing new degrees of freedom to design and fabricate passive/active optical waveguide devices. As a proof-of-concept, this work successfully produces a 7 mm-long circular-shaped gain waveguide (≈10 µm in diameter) in an Er3+-doped YAG single crystal, exhibiting a propagation loss as low as 0.23 dB cm-1, a net gain of ≈3 dB and a polarization-insensitive character. The newly-developed technique is theoretically applicable to arbitrary single crystals, holding promising potential for various applications in integrated optics, optical communication, and photonic quantum circuits.

Treatment of Canine Disc-Associated Cervical Spondylomyelopathy with a Cervical Distraction-Stabilization Technique (C-LOX Combined with LCP Plate) and Clinical Outcomes.

Canine disc-associated cervical spondylomyelopathy (DA-CSM) is a form of caudal CSM, characterized by the compression of the spinal cord and nerve roots due to an intervertebral disc protrusion. It is more frequent in large canine breeds. A variety of surgical techniques has been proposed for DA-CSM. The aim of the study was to evaluate the outcomes of a cervical distraction-stabilization technique using an intervertebral anchored fusion device (C-LOX) combined with a locking compression plate (LCP plate) for the treatment of DA-CSM in dogs, based on clinical and radiographical follow-up data. Thirteen dogs affected by DA-CSM were included in the study. After the surgical procedure, an improvement in neurological status was documented in 9/13 cases. This cervical distraction-stabilization technique seems to be a valuable surgical alternative to treat this canine pathology.

In situ controlled and conformal coating of polydimethylsiloxane foams with silver nanoparticle networks with tunable piezo-resistive properties.

Nanoparticle-polymer composites hold promise in enabling material functionalities that are difficult to achieve otherwise, yet are hampered to date by the scarce control and tunability of the nanoparticle collective properties on the polymer surface, especially for polymer foams featuring a complex three-dimensional pore network. Here we report on the controlled and conformal in situ coating of polydimethylsiloxane (PDMS) foams with silver nanoparticles (AgNPs) with surface coverage finely tunable over a large range, from 0 to 75%, via the one-step room temperature reduction of AgF directly on the PDMS surface. This enables the design of AgNP electrical networks on the PDMS foam surface with piezo-resistive properties tunable up to a factor of 1000. We leveraged the control of the piezoresistive properties of the AgNP electrical network formed on PDMS foams to fabricate flexible and wearable pressure sensors with sensitivity of 0.41 kPa-1, an operation range >120 kPa, and a detection limit of 25 Pa. As a proof-of-concept application in wearable biomedical electronics, we successfully used the sensors to monitor the real-time radial artery pulse wave on the human wrist of a young male with high resolution.

Bioresorbable Nanostructured Chemical Sensor for Monitoring of pH Level In Vivo.

Here, the authors report on the manufacturing and in vivo assessment of a bioresorbable nanostructured pH sensor. The sensor consists of a micrometer-thick porous silica membrane conformably coated layer-by-layer with a nanometer-thick multilayer stack of two polyelectrolytes labeled with a pH-insensitive fluorophore. The sensor fluorescence changes linearly with the pH value in the range 4 to 7.5 upon swelling/shrinking of the polymer multilayer and enables performing real-time measurements of the pH level with high stability, reproducibility, and accuracy, over 100 h of continuous operation. In vivo studies carried out implanting the sensor in the subcutis on the back of mice confirm real-time monitoring of the local pH level through skin. Full degradation of the pH sensor occurs in one week from implant in the animal model, and its biocompatibility after 2 months is confirmed by histological and fluorescence analyses. The proposed approach can be extended to the detection of other (bio)markers in vivo by engineering the functionality of one (at least) of the polyelectrolytes with suitable receptors, thus paving the way to implantable bioresorbable chemical sensors.

Impact of Fabrication and Bioassay Surface Roughness on the Performance of Label-Free Resonant Biosensors Based On One-Dimensional Photonic Crystal Microcavities.

Micro- and nanofabrication offer remarkable opportunities for the preparation of label-free biosensors exploiting optical resonances to improve sensitivity and reduce detection limit once specificity is imparted through surface biofunctionalization. Nonetheless, both surface roughness, peculiar of fabrication processes, and bioassay roughness, resulting from uneven molecular coverage of the sensing surfaces, produce light scattering and, in turn, deterioration of biosensing capabilities, especially in resonant cavities where light travels forth and back thousands to million times. Here, we present a quantitative theoretical analysis about the impact of fabrication and bioassay surface roughness on the performance of optical biosensors exploiting silicon-based, vertical one-dimensional (1D) photonic crystal resonant cavities, also taking noise sources into account. One-dimensional photonic crystal resonant cavities with different architectures and quality factors ranging from 102 to 106 are considered. The analysis points out that whereas sensitivity and linearity of the biosensors are not affected by the roughness level, either due to fabrication or bioassay, the limit of detection can be significantly degraded by both of them, depending on the quality factor of the cavity and noise level of the measurement system. The paper provides important insights into performance versus design, fabrication, and readout of biosensors based on resonant 1D photonic crystal cavities for real-setting operation.

Bioresorbable Materials on the Rise: From Electronic Components and Physical Sensors to In Vivo Monitoring Systems.

Over the last decade, scientists have dreamed about the development of a bioresorbable technology that exploits a new class of electrical, optical, and sensing components able to operate in physiological conditions for a prescribed time and then disappear, being made of materials that fully dissolve in vivo with biologically benign byproducts upon external stimulation. The final goal is to engineer these components into transient implantable systems that directly interact with organs, tissues, and biofluids in real-time, retrieve clinical parameters, and provide therapeutic actions tailored to the disease and patient clinical evolution, and then biodegrade without the need for device-retrieving surgery that may cause tissue lesion or infection. Here, the major results achieved in bioresorbable technology are critically reviewed, with a bottom-up approach that starts from a rational analysis of dissolution chemistry and kinetics, and biocompatibility of bioresorbable materials, then moves to in vivo performance and stability of electrical and optical bioresorbable components, and eventually focuses on the integration of such components into bioresorbable systems for clinically relevant applications. Finally, the technology readiness levels (TRLs) achieved for the different bioresorbable devices and systems are assessed, hence the open challenges are analyzed and future directions for advancing the technology are envisaged.

Decoration of Porous Silicon with Gold Nanoparticles via Layer-by-Layer Nanoassembly for Interferometric and Hybrid Photonic/Plasmonic (Bio)sensing.

Gold nanoparticle layers (AuNPLs) enable the coupling of morphological, optical, and electrical properties of gold nanoparticles (AuNPs) with tailored and specific surface topography, making them exploitable in many bioapplications (e.g., biosensing, drug delivery, and photothermal therapy). Herein, we report the formation of AuNPLs on porous silicon (PSi) interferometers and distributed Bragg reflectors (DBRs) for (bio)sensing applications via layer-by-layer (LbL) nanoassembling of a positively charged polyelectrolyte, namely, poly(allylamine hydrochloride) (PAH), and negatively charged citrate-capped AuNPs. Decoration of PSi interferometers with AuNPLs enhances the Fabry-Pérot fringe contrast due to increased surface reflectivity, resulting in an augmented sensitivity for both bulk and surface refractive index sensing, namely, about 4.5-fold using NaCl aqueous solutions to infiltrate the pores and 2.6-fold for unspecific bovine serum albumin (BSA) adsorption on the pore surface, respectively. Sensitivity enhancing, about 2.5-fold, is also confirmed for affinity and selective biosensing of streptavidin using a biotinylated polymer, namely, negatively charged poly(methacrylic acid) (b-PMAA). Further, decoration of PSi DBR with AuNPLs envisages building up a hybrid photonic/plasmonic optical sensing platform. Both photonic (DBR stop-band) and plasmonic (localized surface plasmon resonance, LSPR) peaks of the hybrid structure are sensitive to changes of bulk (using glucose aqueous solutions) and surface (due to BSA unspecific adsorption) refractive index. To the best of our knowledge, this is the first report about the formation of AuNPLs via LbL nanoassembly on PSi for (i) the enhancing of the interferometric performance in (bio)sensing applications and (ii) the building up of hybrid photonic/plasmonic platforms for sensing and perspective biosensing applications.

Electrical Double Layer-Induced Ion Surface Accumulation for Ultrasensitive Refractive Index Sensing with Nanostructured Porous Silicon Interferometers.

Herein, we provide the first experimental evidence on the use of electrical double layer (EDL)-induced accumulation of charged ions (using both Na+ and K+ ions in water as the model) onto a negatively charged nanostructured surface (e.g., thermally growth SiO2)-Ion Surface Accumulation, ISA-as a means of improving performance of nanostructured porous silicon (PSi) interferometers for optical refractometric applications. Nanostructured PSi interferometers are very promising optical platforms for refractive index sensing due to PSi huge specific surface (hundreds of m2 per gram) and low preparation cost (less than $0.01 per 8 in. silicon wafer), though they have shown poor resolution ( R) and detection limit (DL) (on the order of 10-4-10-5 RIU) compared to other plasmonic and photonic platforms ( R and DL on the order of 10-7-10-8 RIU). This can be ascribed to both low sensitivity and high noise floor of PSi interferometers when bulk refractive index variation of the solution infiltrating the nanopores either approaches or is below 10-4 RIU. Electrical double layer-induced ion surface accumulation (EDL-ISA) on oxidized PSi interferometers allows the interferometer output signal (spectral interferogram) to be impressively amplified at bulk refractive index variation below 10-4 RIU, increasing, in turn, sensitivity up to 2 orders of magnitude and allowing reliable measurement of refractive index variations to be carried out with both DL and R of 10-7 RIU. This represents a 250-fold-improvement (at least) with respect to the state-of-the-art literature on PSi refractometers and pushes PSi interferometer performance to that of state-of-the-art ultrasensitive photonics/plasmonics refractive index platforms.

Near-Infrared Silicon Photonic Crystals with High-Order Photonic Bandgaps for High-Sensitivity Chemical Analysis of Water-Ethanol Mixtures.

Aqueous solutions of alcohols are used in several applications, from pharmaceutics and biology, to chemical, biofuel, and food industries. Nonetheless, development of a simple, inexpensive, and portable sensing device for the quantification of water in water-ethanol mixtures remains a significant challenge. Photonic crystals (PhCs) operating at very high-order photonic bandgaps (PBGs) offer remarkable opportunities for the realization of chemical sensors with high sensitivity and low detection limit. However, high-order PhC structures have been mostly confined to mere theoretical speculations so far, their effective realization requiring microfabrication tools enabling the control of periodic refractive index modulations at the submicrometric scale with extremely high accuracy and precision. Here, we report both experimental and theoretical results on high-sensitivity chemical analysis using vertical, silicon/air 1D-PhCs with spatial period of 10 and 20 µm (namely, over 10 times the operation wavelength) featuring ultra-high-order PBGs in the near-infrared region (namely, up to 50th at 1.1 µm). Fabrication of high-order 1D-PhCs was carried out by electrochemical micromachining (ECM) of silicon, which allowed both surface roughness and deviation from vertical of etched structures to be controlled below 5 nm and 0.1%, respectively. Optical characterization of ECM-fabricated 1D-PhCs, which was performed by acquiring reflectivity spectra over the wavelength range 1-1.7 µm, highlighted the presence of ultra-high-order PBGs with minor optical losses (i.e., <1 dB in reflectivity) separated by deep reflectivity notches with high Q-factors (i.e., >6000), in good agreement with theoretical calculations. Remarkably, the use of high-order 1D-PhCs as refractometric transducers for the quantitative detection of traces of water in water-ethanol mixtures, allowed high sensitivity (namely, either 1000 nm/RIU or ∼0.4 nm/% of water), good detection limit (namely, 5 × 10-3 RIU or ∼10% water), and excellent resolution (namely, either 6 × 10-4 RIU or 1.6% of water) to be reliably achieved on a detection volume of about 168 fL.

High Anodic-Voltage Focusing of Charge Carriers in Silicon Enables the Etching of Regularly-Arranged Submicrometer Pores at High Density and High Aspect-Ratio.

The anodic dissolution of silicon in acidic electrolytes is a well-known technology enabling the silicon machining to be accurately controlled down to the micrometer scale in low-doped n-type silicon electrodes. Attempts to scale down this technology to the submicrometer scale has shown to be challenging, though it premises to enable the fabrication of meso and nano structures/systems that would greatly impact the fields of biosensors and nanomedicine. In this work, we report on the electrochemical etching at high anodic voltages (up to 40 V) of two-dimensional regular arrays of millions pores per square centimeter (up to 30 × 106 cm-2) with sub-micrometric diameter (down to ~860 nm), high depth (up to ~40 µm), and high aspect-ratio (up to ~45) using low-doped n-type silicon electrodes (resistivity 3-8 Ω cm). The use of high anodic voltages, which are over one order of magnitude higher than that commonly used in electrochemical etching of silicon, tremendously improves hole focusing at the pore tips during the etching and enables, in turn, the control of electrochemical etching of submicrometer-sized pores when spatial period reduces below 2 µm. A theoretical model allows experimental results to be interpreted in terms of an electric-field-enhanced focusing of holes at the tip apex of the pores at high anodic voltages, with respect to the pore base, which leads to a smaller curvature radius of the tip apex and enables, in turn, the etching of pore tips to be preferentially sustained over time and space.