Surface-Enhanced Raman Spectroscopy of Ammonium Nitrate Using Al Structures, Fabricated by Laser Processing of AlN Ceramic.

This work presents results on laser-induced surface structuring of AlN ceramic and its application in Surface-Enhanced Raman Spectroscopy (SERS). The laser processing is performed by nanosecond pulses in air and vacuum. Depending on the processing conditions, different surface morphology can be obtained. The ablation process is realized by ceramic decomposition as the formation of an aluminium layer is detected. The efficiency of the fabricated structures as active substrates in SERS is estimated by the ability of the detection of ammonium nitrate (NH4NO3). It is conducted for Raman spectrometer systems that operate at wavelengths of 514 and 785 nm where the most common commercial systems work. The obtained structures contribute to enhancement of the Raman signal at both wavelengths, as the efficiency is higher for excitation at 514 nm. The limit of detection (LOD) of ammonium nitrate is estimated to be below the maximum allowed value in drinking water. The analysis of the obtained results was based on the calculations of the near field enhancement at different conditions based on Finite Difference Time Domain simulation and the extinction spectra calculations based on Generalized Mie scattering theory. The structures considered in these simulations were taken from the SEM images of the real samples. The oxidation issue of the ablated surface was studied by X-ray photoelectron spectroscopy. The presented results indicated that laser structuring of AlN ceramics is a way for fabrication of Al structures with specific near-field properties that can be used for the detection of substances with high social impact.

Formation and characterization of Group IV semiconductor nanowires.

To enable the application to next-generation devices of semiconductor nanowires (NWs), it is important to control their formation and tune their functionality by doping and the use of heterojunctions. In this paper, we introduce formation and the characterization methods of nanowires, focusing on our research results. We describe a top-down method of controlling the size and alignment of nanowires that shows advantages over bottom-up growth methods. The latter technique causes damage to the nanowire surfaces, requiring defect removal after the NW formation process. We show various methods of evaluating the bonding state and electrical activity of impurities in NWs. If an impurity is doped in a NW, mobility decreases due to the scattering that it causes. As a strategy for solving this problem, we describe research into core-shell nanowires, in which Si and Ge heterojunctions are formed in the diameter direction inside the NW. This structure can separate the impurity-doped region from the carrier transport region, promising as a channel for the new ultimate high-mobility transistor.

Binder-free boron-doped Si nanowires toward the enhancement of lithium-ion capacitor.

Lithium-ion capacitors (LICs) are next-generation electrochemical storage devices that combine the benefits of both supercapacitors and lithium-ion batteries. Silicon materials have attracted attention for the development of high-performance LICs owing to their high theoretical capacity and low delithiation potential (∼0.5 V versus Li/Li+). However, sluggish ion diffusion has severely restricted the development of LICs. Herein, a binder-free anode of boron-doped silicon nanowires (B-doped SiNWs) on a copper substrate was reported as an anode for LICs. B-doping could significantly improve the conductivity of the SiNW anode, which could enhance electron/ion transfer in LICs. As expected, the B-doped SiNWs//Li half-cell delivered a higher initial discharge capacity of 454 mAh g-1with excellent cycle stability (capacity retention of 96% after 100 cycles). Furthermore, the near-lithium reaction plateau of Si endows the LICs with a high voltage window (1.5-4.2 V), and the as-fabricated B-doped SiNWs//AC LIC possesses the maximum energy density value of 155.8 Wh kg-1at a battery-inaccessible power density of 275 W kg-1. This study provides a new strategy for using Si-based composites to develop high-performance LIC.

Value of apparent diffusion coefficient on MRI for prediction of histopathological type in anal fistula cancer.

The main histopathological types of anal fistula cancers are mucinous adenocarcinoma and tubular adenocarcinoma. The purpose of this study was to investigate the utility of the apparent diffusion coefficient (ADC) value in magnetic resonance imaging (MRI) to determine the histopathological type of an anal fistula cancer, and to investigate the relationship between ADC values and histopathological type (mucinous type or tubular carcinoma), clinical information, and surgical findings. We retrospectively identified 69 patients diagnosed with anal fistula cancer at our hospital from January 2013 to December 2021. Among them, we selected the patients diagnosed using the same 1.5-T MRI machine, underwent surgery, and a pathological sample was obtained during the operation. Finally, these 25 patients were selected for the analysis since they underwent the imaging scan using the same MRI machine. The ADC value was compared between mucinous and tubular adenocarcinomas, and between tumors at the Tis-T1-T2 and T3-T4 stages. Finally, 25 patients were selected. The mean age of the 25 patients included in the analysis was 60.8 ± 13.3 years and all were males. The median ADC of anal fistula cancers was 1.97 × 10-3 mm2/s for mucinous adenocarcinomas and 1.36 × 10-3 mm2/s for tubular adenocarcinomas; this difference was statistically significant (P < .01). Furthermore, the median ADC was 1.62 × 10-3 mm2/s for tumors in Tis-T1-T2 stages and 2.01 × 10-3 mm2/s for T3-T4 tumors (P = .02). The ADC value in MR images may predict the histopathological type and depth of anal fistula cancers. Also, the different ADC values between Tis-T1-T2 and T3-T4 tumors could help predict the classification of progression.

Atomically Dispersed Nickel Anchored on a Nitrogen-Doped Carbon/TiO2 Composite for Efficient and Selective Photocatalytic CH4 Oxidation to Oxygenates.

Direct photocatalytic oxidation of methane to liquid oxygenated products is a sustainable strategy for methane valorization at room temperature. However, in this reaction, noble metals are generally needed to function as cocatalysts for obtaining adequate activity and selectivity. Here, we report atomically dispersed nickel anchored on a nitrogen-doped carbon/TiO2 composite (Ni-NC/TiO2 ) as a highly active and selective catalyst for photooxidation of CH4 to C1 oxygenates with O2 as the only oxidant. Ni-NC/TiO2 exhibits a yield of C1 oxygenates of 198 µmol for 4 h with a selectivity of 93 %, exceeding that of most reported high-performance photocatalysts. Experimental and theoretical investigations suggest that the single-atom Ni-NC sites not only enhance the transfer of photogenerated electrons from TiO2 to isolated Ni atoms but also dominantly facilitate the activation of O2 to form the key intermediate ⋅OOH radicals, which synergistically lead to a substantial enhancement in both activity and selectivity.

Improving the efficiency of n-Si/PEDOT:PSS hybrid solar cells by incorporating AuNP-decorated graphene oxide as a nanoadditive for conductive polymers.

A gold nanoparticle-decorated graphene oxide (GO-AuNP) hybrid material was prepared by using the chemical reduction method. The obtained results showed that the AuNPs of about of 15 nm are well bound on the surface of GO. The GO-AuNP hybrid material was used for transparent conductive film (TCF) and organic/inorganic hybrid solar cells. The TCF based on poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) containing GO-AuNPs was fabricated at room temperature. The obtained results show that the TCF containing 0.5 wt% GO-AuNPs has a high transmittance of 69.7% at 550 nm, a low sheet resistance of 50.5 Ω â–¡-1 and a conductivity that increased to 3960 S cm-1, which is three times higher than those of the PEDOT:PSS and PEDOT:PSS/GO film. The power conversion efficiency (PCE) of the n-Si/PEDOT:PSS hybrid solar cell containing GO-AuNPs was 8.39% and is higher than pristine PEDOT:PSS (5.81%) and PEDOT:PSS/GO (7.58%). This is a result of the increased electrical conductivity and localized surface plasmon resonance of the PEDOT:PSS coating layer containing the GO-AuNP hybrid material.

MOF-derived nanocrystalline ZnO with controlled orientation and photocatalytic activity.

We show here that MOF-5, a sample Zn-based MOF, can uniquely transform into distinct zinc oxide nanostructures. Inspired by the interconversion synthesis of zeolites, we converted MOF-5 into nanocrystalline ZnO. We found the conversion of MOF-5 into ZnO to be tunable and straightforward simply by controlling the treatment temperature and choosing an appropriate structure-directing agent (SDA). Refined X-ray diffraction (XRD) patterns showed that a synthesis temperature of 180 °C (sample ZnO-180) was optimal for achieving high crystallinity. We examined ZnO-180 with high-resolution transmission electron microscopy (HRTEM), which confirmed that the samples were made of individual crystallites grown along the c-axis, or the (001) direction, thus exposing lower energy surfaces and corroborating the XRD pattern and the molecular dynamics calculations. Further investigations revealed that the obtained ZnO at 180 °C has a superior photocatalytic activity in degrading methylene blue to other ZnO nanostructures obtained at lower temperatures.

Photosensitizer Encryption with Aggregation Enhanced Singlet Oxygen Production.

Chromophores that generate singlet oxygen (1O2) in water are essential to developing noninvasive disease treatments using photodynamic therapy (PDT). A facile approach for formation of stable colloidal nanoparticles of 1O2 photosensitizers, which exhibit aggregation enhanced 1O2 generation in water toward applications as PDT agents, is reported. Chromophore encryption within a fuchsonarene macrocyclic scaffold insulates the photosensitizer from aggregation induced deactivation pathways, enabling a higher chromophore density than typical 1O2 generating nanoparticles. Aggregation enhanced 1O2 generation in water is observed, and variation in molecular structure allows for regulation of the physical properties of the nanoparticles which ultimately affects the 1O2 generation. In vitro activity and the ability of the particles to pass through the cell membrane into the cytoplasm is demonstrated using confocal fluorescence microscopy with HeLa cells. Photosensitizer encryption in rigid macrocycles, such as fuchsonarenes, offers new prospects for the production of biocompatible nanoarchitectures for applications involving 1O2 generation.

ZnO/Ge core-shell nanowires and Ge nanotubes fabricated by chemical vapor deposition and wet etching.

One-dimensional germanium (Ge)-related nanostructures including core-shell nanowires and nanotubes with high specific surface area show enhanced performance in energy storage and electronic devices, and their structural control is important for further improving their performance and stability. In this work, we fabricated vertically formed ZnO/Ge core-shell nanowires with different shell thicknesses. The dependence of morphology, crystallinity, and internal stress of the nanowires on the shell growth time and temperature was investigated. By applying the wet-etching method to the ZnO/Ge core-shell heterojunction nanowires, we demonstrated the Ge nanotube fabrication and stress relaxation in Ge after ZnO core removal.

Enhanced power conversion efficiency of an n-Si/PEDOT:PSS hybrid solar cell using nanostructured silicon and gold nanoparticles.

Herein, the effect of nanostructured silicon and gold nanoparticles (AuNPs) on the power conversion efficiency (PCE) of an n-type silicon/poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (n-Si/PEDOT:PSS) hybrid solar cell was investigated. The Si surface modified with different nanostructures including Si nanopyramids (SiNPs), Si nanoholes (SiNHs) and Si nanowires (SiNWs) was utilized to improve light trapping and photo-carrier collection. The highest power conversion efficiency (PCE) of 8.15% was obtained with the hybrid solar cell employing SiNWs, which is about 8%, 20% and 40% higher compared to the devices using SiNHs, SiNPs and planar Si, respectively. The enhancement is attributed to the low reflectance of the SiNW structures and large PEDOT:PSS/Si interfacial area. In addition, the influence of AuNPs on the hybrid solar cell's performance was examined. The PCE of the SiNW/PEDOT:PSS hybrid solar cell with 0.5 wt% AuNP is 8.89%, which is ca. 9% higher than that of the device without AuNPs (8.15%). This is attributed to the increase in the electrical conductivity and localized surface plasmon resonance of the AuNP-incorporated PEDOT:PSS coating layer.

Study of Structural and Optical Properties of Electrodeposited Silicon Films on Graphite Substrates.

Silicon (Si) films were deposited on low-cost graphite substrates by the electrochemical reduction of silicon dioxide nanoparticles (nano-SiO2) in calcium chloride (CaCl2), melted at 855 °C. Cyclic voltammetry (CV) was used to analyze the electrochemical reduction mechanism of SiO2 to form Si deposits on the graphite substrate. X-ray diffraction (XRD) along with Raman and photoluminescence (PL) results show that the crystallinity of the electrodeposited Si-films was improved with an increase of the applied reduction potential during the electrochemical process. Scanning electron microscopy (SEM) reveals that the size, shape, and morphology of the Si-layers can be controlled from Si nanowires to the microcrystalline Si particles by controlling the reduction potentials. In addition, the morphology of the obtained Si-layers seems to be correlated with both the substrate materials and particle size of the feed materials. Thus, the difference in the electron transfer rate at substrate/nano-SiO2 interface due to different applied reduction potentials along with the dissolution rate of SiO2 particles during the electrochemical reduction process were found to be crucial in determining the microstructural properties of the Si-films.

Defect control and Si/Ge core-shell heterojunction formation on silicon nanowire surfaces formed using the top-down method.

Control of surface defects and impurity doping are important keys to realizing devices that use semiconductor nanowires (NWs). As a structure capable of suppressing impurity scattering, p-Si/i (intrinsic)-Ge core-shell NWs with radial heterojunctions inside the NWs were formed. When forming NWs using a top-down method, the positions of the NWs can be controlled, but their surface is damaged. When heat treatment for repairing surface damage is performed, the surface roughness of the NWs closely depends on the kind of atmospheric gas. Oxidation and chemical etching prior to shell formation removes the surface damaged layer on p-SiNWs and simultaneously achieves a reduction in the diameter of the NWs. Finally, hole gas accumulation, which is important for suppressing impurity scattering, can be observed in the i-Ge layers of p-Si/i-Ge core-shell NWs.

Direct Detection of Free H2 Outgassing in Blisters Formed in Al2O3 Atomic Layers Deposited on Si and Methods of Its Prevention.

The phenomenon of blistering, seen in atomic layer-deposited aluminum oxide layers caused by thermal treatment, represents a serious problem in the field of device fabrication. Determining its causes and controlling them have been a major task in this field. Various groups have so far confronted the challenge, with several mechanisms having been proposed, but it is still under investigation. This paper reports how we have systematically characterized and summarized the blistering phenomenon from the viewpoints of annealing temperature and Al2O3-Si interface conditions. In this study, we have succeeded in directly detecting hydrogen gas generation from the interface between Si and Al2O3 using blister-penetrating Raman spectroscopy. The results have enabled us to propose a mechanism for blister formation using a hydrogen outgassing model. Based on our model, we also propose a method of suppressing blister formation by applying surface treatment or passivation to eliminate the Si-H bonds. These discoveries and methods will provide important insights that are applicable to a wide range of applications such as electronic devices and nanostructured solar cells.

Phenyl-Modified Carbon Nitride Quantum Nanoflakes for Ultra-Highly Selective Sensing of Formic Acid: A Combined Experimental by QCM and Density Functional Theory Study.

Formic acid (HCOOH) is an important intermediate in chemical synthesis, pharmaceuticals, the food industry, and leather tanning and is considered to be an effective hydrogen storage molecule. Direct contact with its vapor and its inhalation lead to burns, nerve injury, and dermatosis. Thus, it is critical to establish efficient sensing materials and devices for the rapid detection of HCOOH. In the present study, we introduce a chemical sensor based on a quartz crystal microbalance (QCM) sensor capable of detecting trace amounts of HCOOH. This sensor is composed of colloidal phenyl-terminated carbon nitride (Ph-g-C3N4) quantum nanoflakes prepared using a facile solid-state method involving the supramolecular preorganization technology. In contrast to other synthetic methods of modified carbon nitride materials, this approach requires no hard templates, hazardous chemicals, or hydrothermal treatments. Comprehensive characterization and density functional theory (DFT) calculations revealed that the QCM sensor designed and prepared here exhibits enhanced detection sensitivity and selectivity for volatile HCOOH, which originates from chemical and hydrogen-bonding interactions between HCOOH and the surface of Ph-g-C3N4. According to DFT results, HCOOH is located close to the cavity of the Ph-g-C3N4 unit, with bonding to graphitic carbon and pyridinic nitrogen atoms of the nanoflake. The sensitivity of the Ph-g-C3N4-nanoflake-based QCM sensor was found to be the highest (128.99 Hz ppm-1) of the substances studied, with a limit of detection (LOD) of HCOOH down to a sub-ppm level of 80 ppb. This sensing technology based on phenyl-terminated attached-g-C3N4 nanoflakes establishes a simple, low-cost solution to improve the performance of QCM sensors for the effective discrimination of HCOOH, HCHO, and CH3COOH vapors using smart electronic noses.

New Approach toward Laser-Assisted Modification of Biocompatible Polymers Relevant to Neural Interfacing Technologies.

We report on a new approach toward a laser-assisted modification of biocompatible polydimethylsiloxane (PDMS) elastomers relevant to the fabrication of stretchable multielectrode arrays (MEAs) devices for neural interfacing technologies. These applications require high-density electrode packaging to provide a high-resolution integrating system for neural stimulation and/or recording. Medical grade PDMS elastomers are highly flexible with low Young's modulus < 1 MPa, which are similar to soft tissue (nerve, brain, muscles) among the other known biopolymers, and can easily adjust to the soft tissue curvatures. This property ensures tight contact between the electrodes and tissue and promotes intensive development of PDMS-based MEAs interfacing devices in the basic neuroscience, neural prosthetics, and hybrid bionic systems, connecting the human nervous system with electronic or robotic prostheses for restoring and treating neurological diseases. By using the UV harmonics 266 and 355 nm of Nd:YAG laser medical grade PDMS elastomer is modified by ns-laser ablation in water. A new approach of processing is proposed to (i) activate the surface and to obtain tracks with (ii) symmetric U-shaped profiles and (iii) homogeneous microstructure This technology provides miniaturization of the device and successful functionalization by electroless metallization of the tracks with platinum (Pt) without preliminary sensitization by tin (Sn) and chemical activation by palladium (Pd). As a result, platinum black layers with a cauliflower-like structure with low values of sheet resistance between 1 and 8 Ω/sq are obtained.

Functionalized aluminum-catalyzed silicon nanowire formation and radial junction photovoltaic devices.

Vertical-oriented silicon nanowire (SiNW) arrays with shaped smooth, nanodot-, or NW-structured surfaces offer many desirable advantages for advanced device applications. In this study, these functionalized SiNW formations were simplified by ex situ preparation of an aluminum (Al) catalyst along with optimization of the substrate temperature and time during vapor-liquid-solid chemical vapor deposition as a one-step process. SiNW-based photovoltaic cells were demonstrated with minimized NW surface defects through NW surface modification, opening a new path for the development of versatile Al-catalyzed SiNWs as a material of choice for on-chip integration in future nanotechnologies.

Conversion of Amorphous Carbon on Silicon Nanostructures into Similar Shaped Semi-Crystalline Graphene Sheets.

Graphene sheets displaying partial crystallinity and nanowire structures were formed on a silicon substrate with silicon nanowires by utilizing an amorphous carbon source. The carbon source was deposited onto the silicon nanostructured substrate by breaking down a polymer precursor and was crystallized by a nickel catalyst during relatively low temperature inert gas annealing. The resulting free-standing graphene-based material can remain on the substrate surface after catalyst removal or can be removed as a separate film. The film is flexible, continuous, and closely mimics the silicon nanostructure. This follows research on similar solid carbon precursor derived semi-crystalline graphene synthesis procedures and applies it to complex silicon nanostructures. This work examined the progression of the carbon, finding that it migrates through the thin film catalyst and forms the graphene only on the other side, and that the process can successfully be used to form 3D shaped graphene films. Semi-crystalline graphene has the possible application of being flexible transparent electrodes, and the 3D shaping opens the possibility of more complex configurations and applications.

Cancer antigen 125 assessment using carbon quantum dots for optical biosensing for the early diagnosis of ovarian cancer.

Fluorometric quantification of biological molecules is a key feature used in many biosensing studies. Fluorescence resonance energy transfer (FRET) using highly fluorescent quantum dots offers highly sensitive detection of the in-proximity wide variety of analyst molecules. In this contribution, we report the use of carbon quantum dots (CDs) for the ultrasensitive optical biosensing of cancer antigen 125 (CA-125) in the early malignant stage. This approach is based on monitoring the quenching of CDs luminescence at 535 nm by CA-125 after excitation at 425 nm and pH 10. The calibration of this method was performed in the concentration range of CA-125 from 0.01 to 129 U ml-1 (R 2 = 0.99) with a detection limit of 0.66 U ml-1, which matches remarkably with the standard chemiluminometric method in control and real patient samples. The sensing mechanism for cancer antigen 125 assessment was discussed on the basis of fluorescence quenching of CDs and time-resolved photoluminescence spectroscopy. The current method is easy, sensitive, cost-effective and provides a wide range of validity, which helps in overcoming the limitations of high cost and time consumption exhibited by many other traditional clinical assays for CA-125 quantification.

Silicon Nanotubes Fabricated by Wet Chemical Etching of ZnO/Si Core-Shell Nanowires.

Silicon nanotubes (SiNTs) have garnered a great deal of interest for both their synthesis and their potential for application to high-capacity energy storage, biosensors, and selective transport. In this study, we report a convenient and low-cost route to the fabrication of vertically aligned SiNTs via a wet-etching process that enables the control of the wall thickness of SiNTs by varying the gas flux and growth temperature. Transmission electron microscopy (TEM) characterization showed the resultant SiNTs to have an amorphous nature and a hexagonal hollow core. These SiNTs can be crystallized by thermal annealing.

Solar Cell Based on Hybrid Structural SiNW/Poly(3,4 ethylenedioxythiophene): Poly(styrenesulfonate)/Graphene.

Solar energy is considered as a potential alternative energy source. The solar cell is classified into three main types: i) solar cells based on bulk silicon materials (monocrystalline, polycrystalline), ii) thin-film solar cells (CIGS, CdTe, DSSC, etc.), and iii) solar cells based on nanostructures and nanomaterials. Nowadays, commercial solar cells are usually made by bulk silicon material, which requires not only high fabrication costs but also limited performance. In this study, the fabrication of high-performance solar cells based on hybrid structure of silicon nanowires/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/graphene (SiNW/PEDOT:PSS/Gr) is focused upon. SiNWs with different lengths of 125, 400, 800 nm, and 2 µm are fabricated by a metal-assisted chemical etching method, and their influence on the performance of the hybrid solar cells is studied and investigated. The experimental results indicate that the suitable SiNW length for the fabrication of the hybrid solar cells is about 400 nm and the best power conversion efficiency obtained is about 9.05%, which is about 2.1 times higher than that of the planar Si solar cell.