Investigations on Optical Absorption and the Pyro-phototronic Effect with Selectively Patterned Black Silicon for Advanced Photodetection.

A novel property existing in the stain-etching technique that eliminates the need for expensive etchant masks in the texturization process of silicon wafers was identified. Through the combination of grayscale lithography and stain-etching methodologies, selective patterning of silicon with AR-P 3510 T, a positive-photoresist mask, was carried out. The etch area ratio was varied in nine different patterns of various feature sizes ranging from 400 to 1500 µm. The optical characteristics of the patterned substrates were determined from diffuse reflectance spectroscopy analysis, and the results were supported with finite-difference time-domain simulations. Complimenting the improvement in optical properties, the electrical losses in microwell-patterned photodetector devices have been reduced with an electro-optic optimum value of the surface enhancement factor, γ. The photodetecting efficiency of a selectively patterned microwell photodetector device exceeded the planar and black silicon photodetector devices with a considerable improvement in the pyro-phototronic effect. This work suggests an alternative for black silicon optoelectronic devices providing a new route to fabricate selectively patterned substrates with an achieved detectivity 16- and 20-fold higher than black and planar silicon photodetector devices, respectively.

Development and Analytical Evaluation of a Point-of-Care Electrochemical Biosensor for Rapid and Accurate SARS-CoV-2 Detection.

The COVID-19 pandemic has underscored the critical need for rapid and accurate screening and diagnostic methods for potential respiratory viruses. Existing COVID-19 diagnostic approaches face limitations either in terms of turnaround time or accuracy. In this study, we present an electrochemical biosensor that offers nearly instantaneous and precise SARS-CoV-2 detection, suitable for point-of-care and environmental monitoring applications. The biosensor employs a stapled hACE-2 N-terminal alpha helix peptide to functionalize an in situ grown polypyrrole conductive polymer on a nitrocellulose membrane backbone through a chemical process. We assessed the biosensor's analytical performance using heat-inactivated omicron and delta variants of the SARS-CoV-2 virus in artificial saliva (AS) and nasal swab (NS) samples diluted in a strong ionic solution, as well as clinical specimens with known Ct values. Virus identification was achieved through electrochemical impedance spectroscopy (EIS) and frequency analyses. The assay demonstrated a limit of detection (LoD) of 40 TCID50/mL, with 95% sensitivity and 100% specificity. Notably, the biosensor exhibited no cross-reactivity when tested against the influenza virus. The entire testing process using the biosensor takes less than a minute. In summary, our biosensor exhibits promising potential in the battle against pandemic respiratory viruses, offering a platform for the development of rapid, compact, portable, and point-of-care devices capable of multiplexing various viruses. The biosensor has the capacity to significantly bolster our readiness and response to future viral outbreaks.

Reversible Light-Responsive Solventless-Liquid Switch: Polarization-Induced Dynamic Surface Ordering-Disordering in Liquid-Like Carbon Quantum Dots.

Naturally stimulated dynamic ordering-disordering of biomolecules via noncovalent interactions is a commonly occurring phenomenon in biological systems. Herein, we report the effect of induced polarization on the charge carrier dynamics of carbon-quantum-dot-based nano ionic materials (CQD-NIMs) under simulated solar radiation. The solventless liquid-like CQD-NIMs is composed of polystyrenesulfonate (PSS)-passivated CQD as the core-corona system with a polyetheramine (Jeffamine) forming the canopy. The material was observed to behave as a dielectric when placed between two electrodes. Dynamic ordering-disordering of the corona around the CQD surface under induced polarization allowed excess current flow through the solventless material when exposed to simulated solar radiation. Such reversible molecular-assembly-induced photoconducting behavior of the CQDs was characterized with impedance spectroscopy and steady state fluorescence spectroscopy. The concept depicted in the present manuscript may be further developed to design smart light-sensitive molecular switching devices.

Novel synthesis of Cu2CoSnS4-carbon quantum dots nano-composites potential light absorber for hybrid photovoltaics.

A novel and simple synthesis of the absorber layer is indispensable in order to reduce the cost and processing of quantum solar cells. In this work, we developed novel Cu2CoSnS4-carbon quantum dot (CCTS:CQD) nano-composite as an absorbing material for solar cell applications. CCTS:CQD nano-composites were prepared by direct pyrolysis of CCTS precursors and citric acid. The proportions of citric acid precursor to CCTS were varied from 0.1 to 0.7. The properties of the synthesized nano-composite were studied using a UV-vis spectrophotometer in the wavelength range of 300-900 nm. CCTS:CQD has a property of dynamic photoluminescence that depends on the excitation wavelength. The results of the x-ray diffraction revealed that the CCTS:CQD nano-composites were predominantly polycrystalline in nature. The formation of CCTS:CQD was confirmed by a high-resolution transmission electron microscope (HRTEM), which exhibits the size ∼3 nm. The thin films of CCTS:CQD nano-composites were deposited on glass/ITO substrates by spray pyrolysis technique at 170 °C. Current-voltage (I-V) measurements carried out in dark and light conditions revealed CCTS: CQD thin films with good photo-response. The purpose of the present study is to develop CCTS: CQD nano-composite p-type absorber layer suitable for thin film solar cells.

Synthesis and photovoltaic application of NIR-emitting perylene-monoimide dyes with large Stokes-shift.

An efficient Sonogashira coupling protocol is developed for tetra-alkynylation at the bay and peri-positions of the perylene-monoimide (PMI) dye in its PMI(Br)4 form. The absorption band for these PMI dyes covered from the visible to Near-infrared (NIR) region and PMI(NMe2)4 is found to exhibit a record-breaking Stokes-shifted NIR emission with good photovoltaic properties.

Synthesis of highly-soluble push-pull perylenemonoimide derivatives by regioselective peri-functionalization for switchable memory applications.

A regioselective synthetic protocol is developed via tetrabromination of perylenemonoimide (PMI) which leads to a series of PMI derivatives. The push-pull characteristics of these derivatives are established by spectroscopic and theoretical investigations. Finally, the semiconducting properties of the PMI dyes are utilized for the development of a switchable memory device.

Solvent Directed Morphogenesis and Electrical Properties of a Peptide-Perylenediimide Conjugate.

Molecular organization of electron-deficient aromatic systems like perylenediimides (PDI) is extremely appealing, as they are potential candidates for organic electronics. The performance of these molecules in such applications primarily depends on the self-organization of the molecules. However, any correlation between the morphology of these self-assembled semiconducting molecules and their electrical performances has not yet been formulated. Herein, for the first time, we have made an effort to find such a correlation by studying the self-assembly, morphology, and their conducting properties for a peptide-PDI conjugate. The PDI conjugate formed fiber-like morphology in relatively nonpolar solvents (THF and CHCl3) while in more polar solvents (HFIP, MeOH, ACN, and acetone), spherical morphology could be found. Interestingly, the self-assembly and the morphologies showed a clear dependence on the solvent polarity. In polar solvents, the conjugate aggregates more efficiently than in the nonpolar solvents, and with decrease in solvent polarity, the dimension of the nanostructures increased. However, in all the tested solvents, irrespective of their polarity, the PDI-peptide conjugate adopts a right-handed helicity. To find a correlation between the morphologies with the conducting property, detailed electrical characterization of these nanostructures was carried out. While no significant change could be observed for the dc conductivities of these nanostructures, the ac conductivities show prominent difference at the low-frequency region. A dispersion of conductivity was observed for the nanospheres due to the polarization effect. A critical correlation between the nanostructures and the activation energy was observed as with decrease in radii of curvature of the aggregates the activation energy increases with an exception in the case of MeOH. The observed results suggest that the long-range transport of charge carriers is less favorable when the aggregates are small and closely packed.

Solvent Assisted Tuning of Morphology of a Peptide-Perylenediimide Conjugate: Helical Fibers to Nano-Rings and their Differential Semiconductivity.

Understanding the regulatory factors of self-assembly processes is a necessity in order to modulate the nano-structures and their properties. Here, the self-assembly mechanism of a peptide-perylenediimide (P-1) conjugate in mixed solvent systems of THF/water is studied and the semiconducting properties are correlated with the morphology. In THF, right handed helical fibers are formed while in 10% THF-water, the morphology changes to nano-rings along with a switch in the helicity to left-handed orientation. Experimental results combined with DFT calculations reveal the critical role of thermodynamic and kinetic factors to control these differential self-assembly processes. In THF, P-1 forms right handed helical fibers in a kinetically controlled fashion. In case of 10% THF-water, the initial nucleation of the aggregate is controlled kinetically. Due to differential solubility of the molecule in these two solvents, elongation of the nuclei into fibers is restricted after a critical length leading to the formation of nano-rings which is governed by the thermodynamics. The helical fibers show superior semi-conducting property to the nano-rings as confirmed by conducting-AFM and conventional I-V characteristics.

Magnetic-field-assisted layer-by-layer electrostatic assembly of ferromagnetic nanoparticles.

We report that layer-by-layer (LbL) electrostatic assembly of Fe(3)O(4) nanoparticles can be supplemented by orienting magnetic domains of the nanoparticles. With the oriented domains of ionic-capped nanoparticles, both magnetic and electrostatic forces of attraction become operative during the LbL deposition process. The magnetic-field-assisted LbL adsorption process has been evidenced by increased electronic absorbance of the films. While atomic force microscopy studies rule out formation of multiple layers during a single adsorption process, magnetic force microscopy images evidence oriented domains in the LbL films. The results show a novel route for LbL deposition of ferromagnetic nanoparticles with oriented magnetic domains in the thin films.

Diode junctions between two ZnO nanoparticles: current rectification and the role of particle size (and bandgap).

We form junctions between two ZnO nanoparticles of two different dopant concentrations. A monolayer of intrinsic (n-type) and a monolayer of Al-doped (n(+)-type) ZnO nanoparticles are deposited in sequence to form the junctions. The size of the nanoparticles (and hence their bandgap) has been varied. Such junctions on a doped Si electrode have been characterized with a scanning tunneling microscope (STM) tip as the other electrode. The junctions show rectifying current-voltage characteristics. Control experiments, such as (1) symmetric characteristics from the components of the junctions and (2) inverse rectification in a junction having the monolayers in reverse sequence, rule out any effect of interfaces in the observed rectification. The results show that rectification is higher in nanodiodes with high bandgap nanoparticles. The ideality factor of the nanodiodes has been calculated.

A control over accessibility of immobilized enzymes through porous coating layer.

We report immobilization of an enzyme by layer-by-layer (LbL) film deposition technique. All the enzyme layers, including the inner ones, contributed to the activity. We put-forwarded additional coating layers to protect the enzymes. To control the accessibility of the enzymes beneath the coating layer, pores have been introduced. Our results show controlled accessibility of immobilized enzymes in solid-state matrices.

Electrical bistability in electrostatic assemblies of CdSe nanoparticles.

We report electrical bistability in electrostatic assembly of CdSe nanoparticles. We obtained thin films of the nanoparticles via layer-by-layer electrostatic assembly technique, which provided a nanoscale control to tune the thickness. Devices based on such thin films exhibit electrical bistability along with memory phenomenon. The bistability is due to charge confinement in the nanoparticles. Conduction mechanism changes from an injection-dominated to a bulk one during switching from a low- to a high-conducting state. Additionally, results from impedance spectroscopy show that the dielectric constant of the material increases during the transition. Both random-access and read-only memory applications are observed in these systems.