Self-powered, wide spectral UV response out-of-plane photodetector based on ZnO/porous silicon heterostructure.

The photoresponse of the ZnO/porous silicon (p-Si) heterojunction is studied in an out-of-plane contact configuration. p-Si substrate is fabricated by anodic etching followed by the electrochemical deposition of ZnO NR film, forming ZnO/p-Si heterojunction. XRD study is done to understand the effect of the substrate on ZnO film growth in terms of strain and crystal size. UV-vis absorbance spectrum shows a broad absorption for wavelengths from 230 to 380 nm. The PL emission shows two narrow and prominent electron transition peaks at 263 and 383 nm and a peak of ∼550 nm corresponding to defects. The 263 nm wavelength responsivity of the photodetector from UV-vis and PL data suggests the presence of a defective SiOxas an intermediate layer between ZnO and p-Si. The photodetector is measured for its spectral selectivity and responsivity for both 266 and 370 nm. Under self-powered conditions, the device shows a low dark current of a few nA and enhancement of ∼100 nA and ∼1.37µA for both wavelengths. A responsivity of 527 mA W-1and 10.5µA W-1and detectivity of 2.5 × 1010and 2.9 × 107Jones at 1 V bias under 266 and 370 nm UV illumination are observed. The fast rise/decay time of 67/65 ms and 29/18 ms is observed for the self-powered condition of the device under both wavelengths respectively. The photoresponse of the modified ZnO/SiOx/p-Si heterojunction for both wavelengths is analyzed for the electron transfer mechanism using the heterojunction band bending model. The short circuit current and open circuit voltage of the photodetector is estimated to be 293 nA, 56.33 mV, and 13.63µA, 124.8 mV for 266 and 370 nm, respectively. It is concluded that the 266 nm responsivity comes from the defects in SiOxintermediate layer, and the photocurrent generated in the device is due to tunneling across the junction.

Symmetrical Ligand's Fabricated Porous Silicon Surface Based Photoluminescence Sensor for Metal Detection and Entrapment.

This study was based on the development of surface-based photoluminescence sensor for metal detection, quantification, and sample purification employing the solid sensory chip having the capability of metal entrapment. The Co(II), Cu(II) and Hg(II) sensitive fluorescence sensor (TP) was first synthesized and characterized its sensing abilities towards tested metal ions by using fluorescence spectral investigation while the synthesis and complexation of the receptor was confirmed by the chromogenic, optical, spectroscopic and spectrometric analysis. Under optical investigation, the ligand solution exhibited substantial chromogenic changes as well as spectral variations upon reacting with copper, cobalt, and mercuric ions, while these behaviors were not seen for the rest of tested metallic ions i.e., Na+, Ag+, Ni2+, Mn2+, Pd2+, Pb2+, Cd2+, Zn2+, Sn2+, Fe2+, Fe3+, Cr3+, and Al3+. These colorimetric alterations and spectral shifting could potentially be employed to detect and quantify these specific metal ions. After the establishment of the ligand's selective complexation ability towards selected metals, it was fabricated over the substituted porous silicon surface (FPS) keeping in view of the development of surface-based photoluminescence sensor (TP-FPS) for the selected metal sensation and entrapment to purify the sample just be putting off the metal entrapped sensory solid chip. Surface characterization and ligand fabrication was inspected by plan and cross sectional electron microscopic investigations, vibrational and electronic spectral analysis. The sensitivity of the ligand (TP) in the solution phase metal discrimination was determined by employing the fluorescence titration analysis of the ligand solution after progressive induction of Co2+, Cu2+, and Hg2+, which afford the detection limit values of 2.14 × 10- 8, 3.47 × 10- 8 and 3.13 × 10- 3, respectively. Concurrently, photoluminescence titration of the surface fabricated sensor (TP-FPS) revealed detection limit values of 3.14 × 10- 9, 7.43 × 10- 9, and 8.21 × 10- 4, respectively, for the selected metal ions.

Detection of water pollutants using super-hydrophobic porous silicon-based SERS substrates.

Super hydrophobic porous silicon surface is prepared using a wet chemical synthesis route. Scanning electron microscopic investigation confirms a correlation between pore size and reaction time. SERS substrates are prepared by silver nanoparticle deposition on porous silicon surface. They exhibit excellent characteristics in terms of sensitivity, reproducibility, stability, and uniformity. They could detect rhodamine 6G in femtomolar range with SERS enhancement factor of ~ 6.1 × 1012, which is best ever reported for these substrates. Molecule-specific sensing of water pollutants such as methylene blue, glyphosate, and chlorpyrifos, is demonstrated for concentrations well below their permissible limits along with excellent enhancement factors. Porous silicon substrate functionalized with Ag nanoparticles demonstrates to be a promising candidate for low-cost, long-life, reliable sensors for environmental conservation applications.

Optical Biosensor Based on Porous Silicon and Tamm Plasmon Polariton for Detection of CagA Antigen of Helicobacter pylori.

Helicobacter pylori (H. pylori) is a common pathogen with a high prevalence of infection in human populations. The diagnosis of H. pylori infection is critical for its treatment, eradication, and prognosis. Biosensors have been demonstrated to be powerful for the rapid onsite detection of pathogens, particularly for point-of-care test (POCT) scenarios. In this work, we propose a novel optical biosensor, based on nanomaterial porous silicon (PSi) and photonic surface state Tamm Plasmon Polariton (TPP), for the detection of cytotoxin-associated antigen A (CagA) of H. pylori bacterium. We fabricated the PSi TPP biosensor, analyzed its optical characteristics, and demonstrated through experiments, with the sensing of the CagA antigen, that the TPP biosensor has a sensitivity of 100 pm/(ng/mL), a limit of detection of 0.05 ng/mL, and specificity in terms of positive-to-negative ratio that is greater than six. From these performance factors, it can be concluded that the TPP biosensor can serve as an effective tool for the diagnosis of H. pylori infection, either in analytical labs or in POCT applications.

The Pattern of Granuloma Formation in the Liver of Rats as a Reflection of the Mechanism of Internalization of Submicron Silicon Particles.

A morphological analysis of the liver of Wistar rats was performed 2 months after a single intravenous injection of porous silicon particles of different sizes (60-80, 250-300, and 500-600 nm; 2 mg/ml, 1 ml). Histological, immunohistochemical, and electron microscopic methods showed the development of CD68+ granulomas in all experimental groups. Injection of 60-80-nm porous silicon particles led to the formation of single large granulomas (>2000 µm2), while 500-600-nm nanoparticles caused the formation of numerous smaller granulomas. The mechanism of involution of granulomas by apoptosis of Kupffer cells and the absence of subsequent connective tissue remodeling of the organ tissue is shown.

Morphological and Optical Transformation of Gas Assisted Direct Laser Written Porous Silicon Films.

Direct laser writing (DLW) of mesoporous porous silicon (PS) films is shown to selectively create spatially separated nitridized and carbonized features on a single film. Nitridized or carbonized features are formed during DLW at 405 nm in an ambient of nitrogen and propane gas, respectively. The range of laser fluence required to create varying feature sizes while avoiding damage to the PS film is identified. At high enough fluence, nitridation using DLW has been shown as an effective method for laterally isolating regions on the PS films. The efficacy in preventing oxidation once passivated is investigated via energy dispersive X-ray spectroscopy. Changes in composition and optical properties of the DL written films are investigated using spectroscopic analysis. Results show carbonized DLW regions have a much higher absorption than as-fabricated PS, attributed to pyrolytic carbon or transpolyacetylene deposits in the pores. Nitridized regions exhibit optical loss similar to previously published thermally nitridized PS films. This work presents methods to engineer PS films for a variety of potential device applications, including the application of carbonized PS to selectively engineer thermal conductivity and electrical resistivity and of nitridized PS to micromachining and selective modification of refractive index for optical applications.

Wafer-Scale Fabrication of Hierarchically Porous Silicon and Silica by Active Nanoparticle-Assisted Chemical Etching and Pseudomorphic Thermal Oxidation.

Many biological materials exhibit a multiscale porosity with small, mostly nanoscale pores as well as large, macroscopic capillaries to simultaneously achieve optimized mass transport capabilities and lightweight structures with large inner surfaces. Realizing such a hierarchical porosity in artificial materials necessitates often sophisticated and expensive top-down processing that limits scalability. Here, an approach that combines self-organized porosity based on metal-assisted chemical etching (MACE) with photolithographically induced macroporosity for the synthesis of single-crystalline silicon with a bimodal pore-size distribution is presented, i.e., hexagonally arranged cylindrical macropores with 1 µm diameter separated by walls that are traversed by pores 60 nm across. The MACE process is mainly guided by a metal-catalyzed reduction-oxidation reaction, where silver nanoparticles (AgNPs) serve as the catalyst. In this process, the AgNPs act as self-propelled particles that are constantly removing silicon along their trajectories. High-resolution X-ray imaging and electron tomography reveal a resulting large open porosity and inner surface for potential applications in high-performance energy storage, harvesting and conversion or for on-chip sensorics and actuorics. Finally, the hierarchically porous silicon membranes can be transformed structure-conserving by thermal oxidation into hierarchically porous amorphous silica, a material that could be of particular interest for opto-fluidic and (bio-)photonic applications due to its multiscale artificial vascularization.

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.

A Multifunctional Porous Silicon Nanocarrier for Glioblastoma Treatment.

Clinical treatment of glioblastoma (GBM) remains a major challenge because of the blood-brain barrier, chemotherapeutic resistance, and aggressive tumor metastasis. The development of advanced nanoplatforms that can efficiently deliver drugs and gene therapies across the BBB to the brain tumors is urgently needed. The protein "downregulated in renal cell carcinoma" (DRR) is one of the key drivers of GBM invasion. Here, we engineered porous silicon nanoparticles (pSiNPs) with antisense oligonucleotide (AON) for DRR gene knockdown as a targeted gene and drug delivery platform for GBM treatment. These AON-modified pSiNPs (AON@pSiNPs) were selectively internalized by GBM and human cerebral microvascular endothelial cells (hCMEC/D3) cells expressing Class A scavenger receptors (SR-A). AON was released from AON@pSiNPs, knocked down DRR and inhibited GBM cell migration. Additionally, a penetration study in a microfluidic-based BBB model and a biodistribution study in a glioma mice model showed that AON@pSiNPs could specifically cross the BBB and enter the brain. We further demonstrated that AON@pSiNPs could carry a large payload of the chemotherapy drug temozolomide (TMZ, 1.3 mg of TMZ per mg of NPs) and induce a significant cytotoxicity in GBM cells. On the basis of these results, the nanocarrier and its multifunctional strategy provide a strong potential for clinical treatment of GBM and research for targeted drug and gene delivery.

Antibacterial Effect of Acoustic Cavitation Promoted by Mesoporous Silicon Nanoparticles.

As-prepared mesoporous silicon nanoparticles, which were synthesized by electrochemical etching of crystalline silicon wafers followed by high-energy milling in water, were explored as a sonosensitizer in aqueous media under irradiation with low-intensity ultrasound at 0.88 MHz. Due to the mixed oxide-hydride coating of the nanoparticles' surfaces, they showed both acceptable colloidal stability and sonosensitization of the acoustic cavitation. The latter was directly measured and quantified as a cavitation energy index, i.e., time integral of the magnitude of ultrasound subharmonics. The index turned out to be several times greater for nanoparticle suspensions as compared to pure water, and it depended nonmonotonically on nanoparticle concentration. In vitro tests with Lactobacillus casei revealed a dramatic drop of the bacterial viability and damage of the cells after ultrasonic irradiation with intensity of about 1 W/cm2 in the presence of nanoparticles, which themselves are almost non-toxic at the studied concentrations of about 1 mg/mL. The experimental results prove that nanoparticle-sensitized cavitation bubbles nearby bacteria can cause bacterial lysis and death. The sonosensitizing properties of freshly prepared mesoporous silicon nanoparticles are beneficial for their application in mild antibacterial therapy and treatment of liquid media.

Porous silicon pillar structures/photosynthetic reaction centre protein hybrid for bioelectronic applications.

Photosynthetic biomaterials have attracted considerable attention at different levels of the biological organisation, from molecules to the biosphere, due to a variety of artificial application possibilities. During photosynthesis, the first steps of the conversion of light energy into chemical energy take place in a pigment-protein complex, called reaction centre (RC). In our experiments photosynthetic reaction centre protein, purified from Rhodobacter sphaeroides R-26 purple bacteria, was bound to porous silicon pillars (PSiP) after the electropolymerisation of aniline onto the surface. This new type of biohybrid material showed remarkable photoactivity in terms of measured photocurrent under light excitation in an electrochemical cell. The photocurrent was found to increase considerably after the addition of ubiquinone (UQ-0), an e--acceptor mediator of the RC. The photoactivity of the complex was found to decrease by the addition of terbutryn, the chemical which inhibits the e--transport on the acceptor side of the RC. In addition to the generation of sizeable light-induced photocurrents, using the PSiP/RC photoactive hybrid nanocomposite material, the system was found to be sensitive towards RC inhibitors and herbicides. This highly ordered patterned 3D structure opens new solution for designing low-power (bio-)optoelectronic, biophotonic and biosensing devices.

Detection of ß-Lactoglobulin by a Porous Silicon Microcavity Biosensor Based on the Angle Spectrum.

In this paper, carbon quantum dot-labelled ß-lactoglobulin antibodies were used for refractive index magnification, and ß-lactoglobulin was detected by angle spectroscopy. In this method, the detection light is provided by a He-Ne laser whose central wavelength is the same as that of the porous silicon microcavity device, and the light source was changed to a parallel beam to illuminate the porous silicon microcavity' surface by collimating beam expansion, and the reflected light was received on the porous silicon microcavity' surface by a detector. The angle corresponding to the smallest luminous intensity before and after the onset of immune response was measured by a detector for different concentrations of ß-lactoglobulin antigen and carbon quantum dot-labelled ß-lactoglobulin antibodies, and the relationship between the variation in angle before and after the immune response was obtained for different concentrations of the ß-lactoglobulin antigen. The results of the experiment present that the angle variations changed linearly with increasing ß-lactoglobulin antigen concentration before and after the immune response. The limit of detection of ß-lactoglobulin by this method was 0.73 µg/L, indicating that the method can be used to detect ß-lactoglobulin quickly and conveniently at low cost.

Denoising of Fluorescence Image on the Surface of Quantum Dot/Nanoporous Silicon Biosensors.

In the process of biological detection of porous silicon photonic crystals based on quantum dots, the concentration of target organisms can be indirectly measured via the change in the gray value of the fluorescence emitted from the quantum dots in the porous silicon pores before and after the biological reaction on the surface of the device. However, due to the disordered nanostructures in porous silicon and the roughness of the surface, the fluorescence images on the surface contain noise. This paper analyzes the type of noise and its influence on the gray value of fluorescent images. The change in the gray value caused by noise greatly reduces the detection sensitivity. To reduce the influence of noise on the gray value of quantum dot fluorescence images, this paper proposes a denoising method based on gray compression and nonlocal anisotropic diffusion filtering. We used the proposed method to denoise the quantum dot fluorescence image after DNA hybridization in a Bragg structure porous silicon device. The experimental results show that the sensitivity of digital image detection improved significantly after denoising.

Impedance Spectroscopy of Hierarchical Porous Nanomaterials Based on por-Si, por-Si Incorporated by Ni and Metal Oxides for Gas Sensors.

Approaches are being developed to create composite materials with a fractal-percolation structure based on intercalated porous matrices to increase the sensitivity of adsorption gas sensors. Porous silicon, nickel-containing porous silicon, and zinc oxide have been synthesized as materials for such structures. Using the impedance spectroscopy method, it has been shown that the obtained materials demonstrate high sensitivity to organic solvent vapors and can be used in gas sensors. A model is proposed that explains the high sensitivity and inductive nature of the impedance at low frequencies, considering the structural features and fractal-percolation properties of the obtained oxide materials.

Spectral-Free Double Light Detection of DNA Based on a Porous Silicon Bragg Mirror.

To improve the detection sensitivity of a porous silicon optical biosensor in the real-time detection of biomolecules, a non-spectral porous silicon optical biosensor technology, based on dual-signal light detection, is proposed. Double-light detection is a combination of refractive index change detection and fluorescence change detection. It uses quantum dots to label probe molecules to detect target molecules. In the double-signal-light detection method, the first detection-signal light is the detection light that is reflected from the surface of the porous silicon Bragg mirror. The wavelength of the detection light is the same as the wavelength of the photonic band gap edge of the porous silicon Bragg mirror. CdSe/ZnS quantum dots are used to label the probe DNA and hybridize it with the target DNA molecules in the pores of porous silicon to improve its effective refractive index and enhance the detection-reflection light. The second detection-signal light is fluorescence, which is generated by the quantum dots in the reactant that are excited by light of a certain wavelength. The Bragg mirror structure further enhances the fluorescence signal. A digital microscope is used to simultaneously receive the digital image of two kinds of signal light superimposed on the surface of porous silicon, and the corresponding algorithm is used to calculate the change in the average grey value before and after the hybridization reaction to calculate the concentration of the DNA molecules. The detection limit of the DNA molecules was 0.42 pM. This method can not only detect target DNA by hybridization, but also detect antigen by immune reaction or parallel biochip detection for a porous silicon biosensor.

High-Temperature Magnesiothermic Reduction Enables HF-Free Synthesis of Porous Silicon with Enhanced Performance as Lithium-Ion Battery Anode.

Porous silicon-based anode materials have gained much interest because the porous structure can effectively accommodate volume changes and release mechanical stress, leading to improved cycling performance. Magnesiothermic reduction has emerged as an effective way to convert silica into porous silicon with a good electrochemical performance. However, corrosive HF etching is normally a mandatory step to improve the electrochemical performance of the as-synthesized silicon, which significantly increases the safety risk. This has become one of the major issues that impedes practical application of the magnesiothermic reduction synthesis of the porous silicon anode. Here, a facile HF-free method is reported to synthesize macro-/mesoporous silicon with good cyclic and rate performance by simply increasing the reduction temperature from 700 °C to 800 °C and 900 °C. The mechanism for the structure change resulting from the increased temperature is elaborated. A finite element simulation indicated that the 3D continuous structure formed by the magnesiothermic reduction at 800 °C and 900 °C could undertake the mechanical stress effectively and was responsible for an improved cyclic stability compared to the silicon synthesized at 700 °C.

6-Phenylhexyl silane derivatized, sputtered silicon solid phase microextraction fiber for the parts-per-trillion detection of polyaromatic hydrocarbons in water and baby formula.

We report the fabrication of 6-phenylhexylsilane derivatized, sputtered silicon, solid phase microextraction fibers that show parts per trillion detection limits for polyaromatic hydrocarbons, and negligible carry over and phase bleed. Their fabrication involves sputtering silicon on silica fibers under various conditions. Six different fibers were evaluated by generating three different thicknesses of sputtered silicon at two different throw distances, which altered the morphologies of the silicon surfaces. All of the fibers were coated with similar thicknesses of 6-phenylhexylsilane (ca. 2 nm). These fibers were characterized with multiple analytical techniques. The optimum fiber configuration was then used to analyze polyaromatic hydrocarbons via direct immersion, gas chromatography mass spectrometry. Our best fiber for the extraction of low molecular weight polyaromatic hydrocarbons in water had similar performance to that of a commercial fiber. However, our fiber demonstrated ca. 3 times the extraction efficiency for higher molecular weight polyaromatic hydrocarbons. In addition, it outperformed the commercial fiber by showing better linearity, repeatability, and detection limits. A method for analyzing polyaromatic hydrocarbons in baby formula was developed, which showed very good linearity (0.5-125 ppb), repeatability (2-26%), detection limits (0.12-0.81 ppb), and recoveries (103-135%). In addition, our fiber showed much less (negligible) carry over and phase bleed than the commercially available fibers.

3D-printed microfluidics integrated with optical nanostructured porous aptasensors for protein detection.

Microfluidic integration of biosensors enables improved biosensing performance and sophisticated lab-on-a-chip platform design for numerous applications. While soft lithography and polydimethylsiloxane (PDMS)-based microfluidics are still considered the gold standard, 3D-printing has emerged as a promising fabrication alternative for microfluidic systems. Herein, a 3D-printed polyacrylate-based microfluidic platform is integrated for the first time with a label-free porous silicon (PSi)-based optical aptasensor via a facile bonding method. The latter utilizes a UV-curable adhesive as an intermediate layer, while preserving the delicate nanostructure of the porous regions within the microchannels. As a proof-of-concept, a generic model aptasensor for label-free detection of his-tagged proteins is constructed, characterized, and compared to non-microfluidic and PDMS-based microfluidic setups. Detection of the target protein is carried out by real-time monitoring reflectivity changes of the PSi, induced by the target binding to the immobilized aptamers within the porous nanostructure. The microfluidic integrated aptasensor has been successfully used for detection of a model target protein, in the range 0.25 to 18 µM, with a good selectivity and an improved limit of detection, when compared to a non-microfluidic biosensing platform (0.04 µM vs. 2.7 µM, respectively). Furthermore, a superior performance of the 3D-printed microfluidic aptasensor is obtained, compared to a conventional PDMS-based microfluidic platform with similar dimensions.

Peptide-Based Capture of Chikungunya Virus E2 Protein Using Porous Silicon Biosensor.

The detection of pathogens presents specific challenges in ensuring that biosensors remain operable despite exposure to elevated temperatures or other extreme conditions. The most vulnerable component of a biosensor is typically the bioreceptor. Accordingly, the robustness of peptides as bioreceptors offers improved stability and reliability toward harsh environments compared to monoclonal antibodies that may lose their ability to bind target molecules after such exposures. Here, we demonstrate peptide-based capture of the Chikungunya virus E2 protein in a porous silicon microcavity biosensor at room temperature and after exposure of the peptide-functionalized biosensor to high temperature. Contact angle measurements, attenuated total reflectance-Fourier transform infrared spectra, and optical reflectance measurements confirm peptide functionalization and selective E2 protein capture. This work opens the door for other pathogenic biomarker detection using peptide-based capture agents on porous silicon and other surface-based sensor platforms.

Porous Silicon Optical Devices: Recent Advances in Biosensing Applications.

This review summarizes the leading advancements in porous silicon (PSi) optical-biosensors, achieved over the past five years. The cost-effective fabrication process, the high internal surface area, the tunable pore size, and the photonic properties made the PSi an appealing transducing substrate for biosensing purposes, with applications in different research fields. Different optical PSi biosensors are reviewed and classified into four classes, based on the different biorecognition elements immobilized on the surface of the transducing material. The PL signal modulation and the effective refractive index changes of the porous matrix are the main optical transduction mechanisms discussed herein. The approaches that are commonly employed to chemically stabilize and functionalize the PSi surface are described.