Metal-enhanced fluorescence through conventional Ag-polyethylene glycol nanoparticles for cellular imaging.

A novel application of conventional Ag nanoparticles (NPs) for metal-enhanced fluorescence (MEF) in cellular imaging is proposed. Different molecular weights of polyethylene glycol (PEG) were tested to determine a suitable spacer on Ag NPs for MEF, and NPs comprising Ag with PEG with a molecular weight of 6000 g (Ag-PEG6k), when present in fluorescein solution, were discovered to cause a 2-fold quantum yield enhancement. For fluorescence imaging of mesenchymal stem cells stained by Alexa Fluor 488, the enhancement factor increased with the Ag-PEG6k NP concentration but decreased with the Alexa Fluor 488 concentration. At 243 parts per billion Ag-PEG6k NPs and 625 parts per million Alexa Fluor 488, the enhancement factor reached its greatest value of over 4.

Effect of synthesis time on plasmonic properties of Ag dendritic nanoforests.

The effects of synthesis time on the plasmonic properties of Ag dendritic nanoforests on Si substrate (Ag-DNF/Si) samples synthesized through the fluoride-assisted galvanic replacement reaction were investigated. The Ag-DNF/Si samples were characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy, reflection spectroscopy, X-ray diffraction and surface-enhanced Raman spectroscopy (SERS). The prolonged reaction time led to the growth of an Ag-DNF layer and etched Si hole array. SEM images and variations in the fractal dimension index indicated that complex-structure, feather-like leaves became coral-like branches between 30 and 60 min of synthesis. The morphological variation during the growth of the Ag DNFs resulted in different optical responses to light illumination, especially those of light harvest and energy transformation. The sample achieved the most desirable light-to-heat conversion efficiency and SERS response with a 30 min growth time. A longer synthesis time or thicker Ag-DNF layer on the Si substrate did not have superior plasmonic properties.

Au@Ag Dendritic Nanoforests for Surface-Enhanced Raman Scattering Sensing.

The effects of Au cores in Ag shells in enhancing surface-enhanced Raman scattering (SERS) were evaluated with samples of various Au/Ag ratios. High-density Ag shell/Au core dendritic nanoforests (Au@Ag-DNFs) on silicon (Au@Ag-DNFs/Si) were synthesized using the fluoride-assisted Galvanic replacement reaction method. The synthesized Au@Ag-DNFs/Si samples were characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy, reflection spectroscopy, X-ray diffraction, and Raman spectroscopy. The ultraviolet-visible extinction spectrum exhibited increased extinction induced by the addition of Ag when creating the metal DNFs layer. The pure Ag DNFs exhibited high optical extinction of visible light, but low SERS response compared with Au@Ag DNFs. The Au core (with high refractive index real part) in Au@Ag DNFs maintained a long-leaf structure that focused the illumination light, resulting in the apparent SERS enhancement of the Ag coverage.

Dendritic Forest-Like Ag Nanostructures Prepared Using Fluoride-Assisted Galvanic Replacement Reaction for SERS Applications.

Dendritic forest-like Ag nanostructures were deposited on a silicon wafer through fluoride-assisted galvanic replacement reaction (FAGRR) in aqueous AgNO3 and buffered oxide etchant. The prepared nanostructures were characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma-optical emission spectroscopy, a surface profiler (alpha step), and X-ray diffraction. Additionally, the dendritic forest-like Ag nanostructures were characterized using surface-enhanced Raman scattering (SERS) when a 4-mercaptobenzoic acid (4-MBA) monolayer was adsorbed on the Ag surface. The Ag nanostructures exhibited intense SERS signal from 4-MBA because of their rough surface, and this intense signal led to an intense local electromagnetic field upon electromagnetic excitation. The enhancement factor for 4-MBA molecules adsorbed on the Ag nanostructures was calculated to be 9.18 × 108. Furthermore, common Raman reporters such as rhodamine 6G, 4-aminothiolphenol, 5,5'-dithiobis-2-nitrobenzoic acid, and carboxyfluorescein (FAM) were characterized on these dendritic forest-like Ag nanostructures, leading to the development of an ultrasensitive SERS-based DNA sensor with a limit of detection of 33.5 nM of 15-mer oligonucleotide.

Silicon-Based Ag Dendritic Nanoforests for Light-Assisted Bacterial Inhibition.

Silver dendritic nanoforests (Ag-DNFs) on silicon (Ag-DNFs/Si) were synthesized through the fluoride-assisted Galvanic replacement reaction (FAGRR) method. The synthesized Ag-DNFs/Si were characterized by scanning electron microscopy, energy-dispersive X-ray spectrometry, inductively coupled plasma mass spectrometry (ICP-MS), reflection absorbance spectrometry, surface-enhanced Raman scattering spectrometry, and X-ray diffractometry. The Ag+ concentration in ICP-MS measurements indicated 1.033 mg/cm2 of deposited Ag synthesized for 200 min on Si substrate. The optical absorbance spectra indicated the induced surface plasmon resonance of Ag DNFs increased with the thickness of the Ag DNFs layer. Surface-enhanced Raman scattering measurement and a light-to-heat energy conversion test presented the superior plasmonic response of Ag-DNFs/Si for advanced applications. The Ag-DNFs/Si substrate exhibited high antibacterial activity against Escherichia coli and Staphylococcus aureus. The large surface area of the dense crystal Ag DNFs layer resulted in high antibacterial efficiency. The plasmonic response in the metal-crystal Ag DNFs under external light illumination can supply energy to enhance bacterial inhibition. High-efficiency plasmonic heating by the dense Ag DNFs can lead to localized bacterial inhibition. Thus, the Ag-DNFs/Si substrate has excellent potential for antibacterial applications.

Characterization of silicon oxynitride films deposited by a high-power impulse magnetron sputtering deposition technique.

In this research, silicon oxynitride films were prepared by high-power impulse magnetron sputtering with 45/955 pulse on/off time. The extinction coefficient was smaller than 1×10-3 from 250 to 700 nm after introducing 2.2 sccm O2 gas at room temperature. A three-layer of AlF3/SiOxNy AR coating was designed and fabricated on double-sided quartz, and a high transmittance of 99.2% was attained at 248 nm. The silicon oxynitride films deposited at 350°C had the better mechanical and optical properties in the visible range. The hardness of all deposited films was greater than 19 GPa, and the greatest hardness could reach to 29.8 GPa. A film structure of six-layer transparent hard coating/glass/four-layer AR coating was designed and deposited. Its average transmittance was 96.0% in the visible range, while its hardness was 21 GPa and its surface roughness was 0.23 nm.

Light Energy Conversion Surface with Gold Dendritic Nanoforests/Si Chip for Plasmonic Polymerase Chain Reaction.

Surfaces with gold dendritic nanoforests (Au DNFs) on Si chips demonstrate broadband-light absorption. This study is the first to utilize localized surface plasmons of Au DNFs/Si chips for polymerase chain reaction (PCR) applications. A convenient halogen lamp was used as the heating source to illuminate the Au DNFs/Si chip for PCR. A detection target of Salmonella spp. DNA fragments was reproduced in this plasmonic PCR chip system. By semi-quantitation in gel electrophoresis analysis, the plasmonic PCR with 30 cycles and a largely reduced processing time provided results comparable with those of a commercial PCR thermal cycler with 40 cycles in more than 1 h. In the presence of an Au DNFs/Si chip, the plasmonic PCR provides superior results in a short processing time.

Growth of Gold Dendritic Nanoforests on Titanium Nitride-coated Silicon Substrates.

In this study, a high-power impulse magnetron sputtering system is used to coat a flat and firm titanium nitride (TiN) film on silicon (Si) wafers, and a fluoride-assisted galvanic replacement reaction (FAGRR) is employed for the rapid and easy deposition of gold dendritic nanoforests (Au DNFs) on the TiN/Si substrates. Scanning electron microscopy (SEM) images and energy-dispersive X-ray spectroscopy patterns of TiN/Si and Au DNFs/TiN/Si samples validate that the synthesis process is accurately controlled. Under the reaction conditions in this study, the thickness of the Au DNFs increases linearly to 5.10 ± 0.20 µm within 15 min of the reaction. Therefore, the employed synthesis procedure is a simple and rapid approach for preparing Au DNFs/TiN/Si composites.

Novel Gold Dendritic Nanoforests Combined with Titanium Nitride for Visible-Light-Enhanced Chemical Degradation.

In this study, gold dendritic nanoforests (Au DNFs)-titanium nitride (TiN) composite was firstly proposed for visible-light photodegradation of pollutants. A high-power impulse magnetron sputtering system was used to coat TiN films on silicon wafers, and a fluoride-assisted galvanic replacement reaction was applied to deposit Au DNFs on TiN/Si substrates. Scanning electron microscope images and X-ray diffraction patterns of TiN/Si, Au DNFs/Si, and Au DNFs/TiN/Si samples verified that this synthesis process was accurately controlled. The average reflectance of Au DNFs/Si and Au DNFs/TiN/Si considerably declined to approximately 10%, because the broadband localized surface plasmon resonances of Au DNFs cause broadband absorbance and low reflectance. In photocatalytic performance, 90.66 ± 1.41% 4-nitrophenol was successfully degraded in 180 min by Au DNFs/TiN/Si under visible-light irradiation. Therefore, Au DNFs/TiN/Si has the chance to be a visible-light photocatalyst for photodegradation of pollutants.

Interplay of mutual electric and magnetic couplings between three-dimensional split-ring resonators.

We experimentally and theoretically study the interplay between capacitive electric and inductive magnetic couplings in infrared metamaterials consisting of densely-packed three-dimensional (3D) meta-atoms. The meta-atom is made of metal-stress-driven assembled 3D split-ring resonators to exhibit strong bi-anisotropy, where electric and magnetic resonances occur simultaneously. By varying the spatial arrangement of the arrayed meta-atoms, the mutual coupling between meta-atoms dramatically modifies their mode profiles and resultant spectral responses. The corresponding numerical simulations evidently retrieved current densities and magnetic field strengths, as well as the transmittance, to reveal the important resonant behavior in the coupled meta-atom systems. We conclude that the mutual electric coupling between the neighboring meta-atoms plays a crucial role to the scattering behaviors of the bi-anisotropic metamaterials.

Facile Preparation of a Platinum Silicide Nanoparticle-Modified Tip Apex for Scanning Kelvin Probe Microscopy.

In this study, we propose an ultra-facile approach to prepare a platinum silicide nanoparticle-modified tip apex (PSM tip) used for scanning Kelvin probe microscopy (SKPM). We combined a localized fluoride-assisted galvanic replacement reaction (LFAGRR) and atmospheric microwave annealing (AMA) to deposit a single platinum silicide nanoparticle with a diameter of 32 nm on the apex of a bare silicon tip of atomic force microscopy (AFM). The total process was completed in an ambient environment in less than 3 min. The improved potential resolution in the SKPM measurement was verified. Moreover, the resolution of the topography is comparable to that of a bare silicon tip. In addition, the negative charges found on the PSM tips suggest the possibility of exploring the use of current PSM tips to sense electric fields more precisely. The ultra-fast and cost-effective preparation of the PSM tips provides a new direction for the preparation of functional tips for scanning probe microscopy.

A facile approach to prepare silicon-based Pt-Ag tubular dendritic nano-forests (tDNFs) for solar-light-enhanced methanol oxidation reaction.

In this paper, a facile two-step Galvanic replacement reaction (GRR) is proposed to prepare Pt-Ag tubular dendritic nano-forests (tDNFs) in ambient condition for enhancing methanol oxidation reaction (MOR) under solar illumination. In the first GRR, a homogeneous layer of silver dendritic nano-forests (DNFs) with 10 µm in thickness was grown on Si wafer in 5 min in silver nitride (AgNO3) and buffer oxide etchant (BOE) solution. In the second GRR, we utilized chloroplatinic acid (H2PtCl6) as the precursor for platinum (Pt) deposition to further transform the prepared Ag DNFs into Pt-Ag tDNFs. The catalytic performance and solar response of the Pt-Ag tDNFs toward methanol electro-oxidation are also studied by cyclic voltammetry (CV) and chronoamperometry (CA). The methanol oxidation current was boosted by 6.4% under solar illumination on the Pt-Ag tDNFs due to the induced localized surface plasmon resonance (LSPR) on the dendritic structure. Current results provide a cost-effective and facile approach to prepare solar-driven metallic electrodes potentially applicable to photo-electro-chemical fuel cells.

The effect of inductively-coupled-plasma reactive ion etching power on the etching rate and the surface roughness of a sapphire substrate.

In this study, patterned sapphire substrates are fabricated using nanosphere lithography (NSL) and inductively-coupled-plasma reactive ion etching (ICP-RIE). Polystyrene nanospheres of approximately 600 nm diameter are self-assembled on c-plane sapphire substrates by spin-coating. The diameter of the polystyrene nanospheres is modified to adjust the etching mask pitch cycle using oxygen plasma in the ICP-RIE system. A nickel thin film mask of 100 nm thickness is deposited by electron-beam evaporation on a substrate covered with treated nanospheres. The sapphire substrate is then etched in an inductively coupled plasma system using BCl3/Ar gas, to fabricate a structure with a periodic sub-micron hole array with different sidewall intervals. The DC bias voltage, the sapphire etching rate, the surface roughness, are studied as a function of the ICP and the RF power. Different sub-micron hole arrays with spacing cycles of 89 nm, 139 nm and 167 nm are successfully fabricated on the sapphire substrate, using suitable etching parameters.

The sub-micron hole array in sapphire produced by inductively-coupled plasma reactive ion etching.

The sub-micron hole array in a sapphire substrate was fabricated by using nanosphere lithography (NSL) combined with inductively-coupled-plasma reactive ion etching (ICP-RIE) technique. Polystyrene nanospheres of about 600 nm diameter were self-assembled on c-plane sapphire substrates by the spin-coating method. The diameter of polystyrene nanosphere was modified by using oxygen plasma in ICP-RIE system. The size of nanosphere modified by oxygen plasma was varied from 550 to 450 nm with different etching times from 15 to 35 s. The chromium thin film of 100 nm thick was then deposited on the shrunk nanospheres on the substrate by electron-beam evaporation system. The honeycomb type chromium mask can be obtained on the sapphire substrate after the polystyrene nanospheres were removed. The substrate was further etched in two sets of chlorine/Argon and boron trichloride/Argon mixture gases at constant pressure of 50 mTorr in ICP-RIE processes. The 400 nm hole array in diameter can be successfully produced under suitable boron trichloride/Argon gas flow ratio.

Effects of temperature on columnar microstructure and recrystallization of TiO2 film produced by ion-assisted deposition.

Titanium oxide thin films were deposited by electron-beam evaporation with ion-beam-assisted deposition. The effect of the substrate temperature and annealing temperature on the columnar microstructure and recrystallization of titanium oxide was studied. The values of the refractive index varied from 2.26 to 2.4, indicating that the different substrate temperatures affected the film density. X-ray diffraction revealed that all films were amorphous as deposited. At annealing temperatures from 100 degrees C to 300 degrees C, only the anatase phase was formed. As the substrate temperature increased from 150 degrees C to 200 degrees C to 250 degrees C, the recrystallization temperature fell from 300 degrees C through 250 degrees C to 200 degrees C. Changing the substrate temperature resulted in the formation of various types of columnar microstructure, as determined by scanning-electron microscopy. Different columnar structures resulted in different surface morphologies, as measured by atomic-force microscopy.