Surface nanostructuring of alkali-aluminosilicate Gorilla display glass substrates using a maskless process.

This paper reports on the formation of moth-eye nanopillar structures on surfaces of alkali-aluminosilicate Gorilla glass substrates using a self-masking plasma etching method. Surface and cross-section chemical compositions studies were carried out to study the formation of the nanostructures. CFxinduced polymers were shown to be the self-masking material during plasma etching. The nanostructures enhance transmission at wavelengths over 525 nm may be utilized for fluid-induced switchable haze. Additional functionalities associated with nanostructures may be realized such as self-cleaning, anti-fogging, and stain-resistance.

Fabrication of nanostructure on Au nano-film by nanosecond laser coupled with cantilevered scanning near-field optical microscopy probe.

Diffraction limit has been the constraint of the nanostructure fabrication. Because the scanning near-field optical microscopy (SNOM) can work in the evanescent near-field region, its application in nano-processing has received extensive attention from researchers globally. In this paper, we combined nanosecond laser with cantilevered SNOM probe. Utilizing the high precision of the confinement and enhancement effect of probe tip and the high instantaneous energy of the laser, we realized nanostructure fabrication andin situdetection on Au nano-film. Feature sizes down to 47 nm full width at half maximum were fabricated. We investigated the laser propagation through the SNOM tip aperture and the light field intensity distribution on the surface of substrate theoretically. The calculation results demonstrate that the laser is highly restricted within the SNOM aperture and enhanced on the exit plane at the rim of aperture. After the transmission, the light field intensity distribution on the surface of the Au nano-film was enhanced due to the localized surface plasmon resonance. The thermal distribution on the surface of Au nano-film indicates that the peak of the temperature distribution appeared at the surface right underneath the center of the aperture. It is proved that the simulation results are consistent with the experimental results.

Femtosecond-Pulsed Laser Written and Etched Fiber Bragg Gratings for Fiber-Optical Biosensing.

We present the development of a label-free, highly sensitive fiber-optical biosensor for online detection and quantification of biomolecules. Here, the advantages of etched fiber Bragg gratings (eFBG) were used, since they induce a narrowband Bragg wavelength peak in the reflection operation mode. The gratings were fabricated point-by-point via a nonlinear absorption process of a highly focused femtosecond-pulsed laser, without the need of prior coating removal or specific fiber doping. The sensitivity of the Bragg wavelength peak to the surrounding refractive index (SRI), as needed for biochemical sensing, was realized by fiber cladding removal using hydrofluoric acid etching. For evaluation of biosensing capabilities, eFBG fibers were biofunctionalized with a single-stranded DNA aptamer specific for binding the C-reactive protein (CRP). Thus, the CRP-sensitive eFBG fiber-optical biosensor showed a very low limit of detection of 0.82 pg/L, with a dynamic range of CRP detection from approximately 0.8 pg/L to 1.2 µg/L. The biosensor showed a high specificity to CRP even in the presence of interfering substances. These results suggest that the proposed biosensor is capable for quantification of CRP from trace amounts of clinical samples. In addition, the adaption of this eFBG fiber-optical biosensor for detection of other relevant analytes can be easily realized.

Highly-Adaptable Optothermal Nanotweezers for Trapping, Sorting, and Assembling across Diverse Nanoparticles.

Optical manipulation of various kinds of nanoparticles is vital in biomedical engineering. However, classical optical approaches demand higher laser power and are constrained by diffraction limits, necessitating tailored trapping schemes for specific nanoparticles. They lack a universal and biocompatible tool to manipulate nanoparticles of diverse sizes, charges, and materials. Through precise modulation of diffusiophoresis and thermo-osmotic flows in the boundary layer of an optothermal-responsive gold film, highly adaptable optothermal nanotweezers (HAONTs) capable of manipulating a single nanoparticle as small as sub-10 nm are designed. Additionally, a novel optothermal doughnut-shaped vortex (DSV) trapping strategy is introduced, enabling a new mode of physical interaction between cells and nanoparticles. Furthermore, this versatile approach allows for the manipulation of nanoparticles in organic, inorganic, and biological forms. It also offers versatile function modes such as trapping, sorting, and assembling of nanoparticles. It is believed that this approach holds the potential to be a valuable tool in fields such as synthetic biology, optofluidics, nanophotonics, and colloidal science.

Advanced Fabrication of 3D Micro/Nanostructures of Gallium Oxide with a Tuned Band Gap and Optical Properties.

Gallium oxide (Ga2O3) is a promising material for high-power semiconductor applications due to its wide band gap and high breakdown voltage. However, the current methods for fabricating Ga2O3 nanostructures have several disadvantages, including their complex manufacturing processes and high costs. In this study, we report a novel approach for synthesizing ß-Ga2O3 nanostructures on gallium phosphide (GaP) using ultra-short laser pulses for in situ nanostructure generation (ULPING). We varied the process parameters to optimize the nanostructure formation, finding that the ULPING method produces high-quality ß-Ga2O3 nanostructures with a simpler and more cost-effective process when compared with existing methods. Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) were used to characterize the samples, which indicated the presence of phosphorous. X-ray photoelectron spectroscopy (XPS) confirmed the formation of gallium oxide, along with a minor amount of phosphorus-containing compounds. Structural analysis using X-ray diffraction (XRD) revealed the formation of a monoclinic ß-polymorph of Ga2O3. We also measured the band gap of the materials using reflection electron energy loss spectroscopy (REELS), and found that the band gap increased with higher nanostructure formation, reaching 6.2 eV for the optimized sample. Furthermore, we observed a change in the heterojunction alignment, which we attribute to the change in the oxidation of the samples. Our results demonstrate the potential of ULPING as a novel, simple, and cost-effective method for fabricating Ga2O3 nanostructures with tunable optical properties. The ULPING method offers a green alternative to existing fabrication methods, making it a promising technology for future research in the field of Ga2O3 nanostructure fabrication.

Design Strategy and Application of Deep Eutectic Solvents for Green Synthesis of Nanomaterials.

The first report of deep eutectic solvents (DESs) was released in 2003 and was identified as a new member of ionic liquid (IL), involving innovative chemical and physical characteristics. Using green solvent technology concerning economical, practical, and environmental aspects, DESs open the window for sustainable development of nanomaterial fabrication. The DESs assist in different fabrication processes and design nanostructures with specific morphology and properties by tunable reaction conditions. Using DESs in synthesis reactions can reduce the required high temperature and pressure conditions for decreasing energy consumption and the risk of environmental contamination. This review paper provides the recent applications and advances in the design strategy of DESs for the green synthesis of nanomaterials. The strategy and application of DESs in wet-chemical processes, nanosize reticular material fabrication, electrodeposition/electrochemical synthesis of nanostructures, electroless deposition, DESs based nano-catalytic and nanofluidic systems are discussed and highlighted in this review.

The Atomic Drill Bit: Precision Controlled Atomic Fabrication of 2D Materials.

The ability to deterministically fabricate nanoscale architectures with atomic precision is the central goal of nanotechnology, whereby highly localized changes in the atomic structure can be exploited to control device properties at their fundamental physical limit. Here, an automated, feedback-controlled atomic fabrication method is reported and the formation of 1D-2D heterostructures in MoS2 is demonstrated through selective transformations along specific crystallographic orientations. The atomic-scale probe of an aberration-corrected scanning transmission electron microscope (STEM) is used, and the shape and symmetry of the scan pathway relative to the sample orientation are controlled. The focused and shaped electron beam is used to reliably create Mo6 S6 nanowire (MoS-NW) terminated metallic-semiconductor 1D-2D edge structures within a pristine MoS2 monolayer with atomic precision. From these results, it is found that a triangular beam path aligned along the zig-zag sulfur terminated (ZZS) direction forms stable MoS-NW edge structures with the highest degree of fidelity without resulting in disordering of the surrounding MoS2 monolayer. Density functional theory (DFT) calculations and ab initio molecular dynamic simulations (AIMD) are used to calculate the energetic barriers for the most stable atomic edge structures and atomic transformation pathways. These discoveries provide an automated method to improve understanding of atomic-scale transformations while opening a pathway toward more precise atomic-scale engineering of materials.

Charged Particle-Induced Surface Reactions of Organometallic Complexes as a Guide to Precursor Design for Electron- and Ion-Induced Deposition of Nanostructures.

Focused electron beam-induced deposition (FEBID) and focused ion beam-induced deposition (FIBID) are direct-write fabrication techniques that use focused beams of charged particles (electrons or ions) to create 3D metal-containing nanostructures by decomposing organometallic precursors onto substrates in a low-pressure environment. For many applications, it is important to minimize contamination of these nanostructures by impurities from incomplete ligand dissociation and desorption. This spotlight on applications describes the use of ultra high vacuum surface science studies to obtain mechanistic information on electron- and ion-induced processes in organometallic precursor candidates. The results are used for the mechanism-based design of custom precursors for FEBID and FIBID.

Controlled fabrication of nanoscale wrinkle structure by fluorocarbon plasma for highly transparent triboelectric nanogenerator.

In this paper, we report a novel nanoscale wrinkle-structure fabrication process using fluorocarbon plasma on poly(dimethylsiloxane) (PDMS) and Solaris membranes. Wrinkles with wavelengths of hundreds of nanometers were obtained on these two materials, showing that the fabrication process was universally applicable. By varying the plasma-treating time, the wavelength of the wrinkle structure could be controlled. Highly transparent membranes with wrinkle patterns were obtained when the plasma-treating time was <125 s. The transmittances of these membranes were >90% in the visible region, making it difficult to distinguish them from a flat membrane. The deposited fluorocarbon polymer also dramatically reduced the surface energy, which allowed us to replicate the wrinkle pattern with high precision onto other membranes without any surfactant coating. The combined advantages of high electron affinity and high transparency enabled the fabricated membrane to improve the performance of a triboelectric nanogenerator. This nanoscale, single-step, and universal wrinkle-pattern fabrication process, with the functionality of high transparency and ultra-low surface energy, shows an attractive potential for future applications in micro- and nanodevices, especially in transparent energy harvesters.

Diphenylalanine in tetrahydrofuran: a highly potent candidate for the development of novel nanomaterials.

The peptide di-L-phenylalanine (FF) has emerged as a highly potent candidate for the development of novel nanomaterials. The unprotected peptide was dissolved in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) mixed with tetrahydrofuran (THF) and single crystals of the THF monosolvate, C18H20N2O3·C4H8O, were grown by slow evaporation in a `vial-in-closed-bottle' system. THF is a molecule that can only act as a hydrogen-bond acceptor. Thus, the hydrogen-bond patterns observed in the crystal structures at 100 and 299 K are different compared to that of crystals grown from water and methanol [Mason et al. (2014). ACS Nano. 8, 1243-1253].

Synthesis of Electrical Conductive Silica Nanofiber/Gold Nanoparticle Composite by Laser Pulses and Sputtering Technique.

Biocompatible-sensing materials hold an important role in biomedical applications where there is a need to translate biological responses into electrical signals. Increasing the biocompatibility of these sensing devices generally causes a reduction in the overall conductivity due to the processing techniques. Silicon is becoming a more feasible and available option for use in these applications due to its semiconductor properties and availability. When processed to be porous, it has shown promising biocompatibility; however, a reduction in its conductivity is caused by its oxidization. To overcome this, gold embedding through sputtering techniques are proposed in this research as a means of controlling and further imparting electrical properties to laser induced silicon oxide nanofibers. Single crystalline silicon wafers were laser processed using an Nd:YAG pulsed nanosecond laser system at different laser parameters before undergoing gold sputtering. Controlling the scanning parameters (e.g., smaller line spacings) was found to induce the formation of nanofibrous structures, whose diameters grew with increasing overlaps (number of laser beam scanning through the same path). At larger line spacings, nano and microparticle formation was observed. Overlap (OL) increases led to higher light absorbance's by the wafers. The gold sputtered samples resulted in greater conductivities at higher gold concentrations, especially in samples with smaller fiber sizes. Overall, these findings show promising results for the future of silicon as a semiconductor and a biocompatible material for its use and development in the improvement of sensing applications.

Plasmonic Structures, Materials and Lenses for Optical Lithography beyond the Diffraction Limit: A Review.

The rapid development of nanotechnologies and sciences has led to the great demand for novel lithography methods allowing large area, low cost and high resolution nano fabrications. Characterized by unique sub-diffraction optical features like propagation with an ultra-short wavelength and great field enhancement in subwavelength regions, surface plasmon polaritons (SPPs), including surface plasmon waves, bulk plasmon polaritons (BPPs) and localized surface plasmons (LSPs), have become potentially promising candidates for nano lithography. In this paper, investigations into plasmonic lithography in the manner of point-to-point writing, interference and imaging were reviewed in detail. Theoretical simulations and experiments have demonstrated plasmonic lithography resolution far beyond the conventional diffraction limit, even with ultraviolet light sources and single exposure performances. Half-pitch resolution as high as 22 nm (~1/17 light wavelength) was observed in plasmonic lens imaging lithography. Moreover, not only the overview of state-of-the-art results, but also the physics behind them and future research suggestions are discussed as well.

Doxorubicin loaded nanodiamond-silk spheres for fluorescence tracking and controlled drug release.

Nanoparticle (NP) based technologies have proved to be considerably beneficial for advances in biomedicine especially in the areas of disease detection, drug delivery and bioimaging. Over the last few decades, NPs have garnered interest for their exemplary impacts on the detection, treatment, and prevention of cancer. The full potential of these technologies are yet to be employed for clinical use. The ongoing research and development in this field demands single multifunctional composite materials that can be employed simultaneously for drug delivery and biomedical imaging. In this manuscript, a unique combination of silk fibroin (SF) and nanodiamonds (NDs) in the form of nanospheres are fabricated and investigated. The spheres were loaded with the anthracyline Doxorubicin (DoX) and the drug release kinetics for these ND-SF-DoX (NDSX) spheres were studied. NDs provided the fluorescence modality for imaging while the degradable SF spheres stabilized and released the drug in a controlled manner. The emission and structural properties of the spheres were characterized during drug release. The degradability of SF and the subsequent release of DoX from the spheres were monitored through fluorescence of NDs inside the spheres. This research demonstrates the enormous potential of the ND-SF nanocomposite platforms for diagnostic and therapeutic purposes, which are both important for pharmaceutical research and clinical settings.

Tailored surface-enhanced Raman nanopillar arrays fabricated by laser-assisted replication for biomolecular detection using organic semiconductor lasers.

Organic semiconductor distributed feedback (DFB) lasers are of interest as external or chip-integrated excitation sources in the visible spectral range for miniaturized Raman-on-chip biomolecular detection systems. However, the inherently limited excitation power of such lasers as well as oftentimes low analyte concentrations requires efficient Raman detection schemes. We present an approach using surface-enhanced Raman scattering (SERS) substrates, which has the potential to significantly improve the sensitivity of on-chip Raman detection systems. Instead of lithographically fabricated Au/Ag-coated periodic nanostructures on Si/SiO2 wafers, which can provide large SERS enhancements but are expensive and time-consuming to fabricate, we use low-cost and large-area SERS substrates made via laser-assisted nanoreplication. These substrates comprise gold-coated cyclic olefin copolymer (COC) nanopillar arrays, which show an estimated SERS enhancement factor of up to ∼ 10(7). The effect of the nanopillar diameter (60-260 nm) and interpillar spacing (10-190 nm) on the local electromagnetic field enhancement is studied by finite-difference-time-domain (FDTD) modeling. The favorable SERS detection capability of this setup is verified by using rhodamine 6G and adenosine as analytes and an organic semiconductor DFB laser with an emission wavelength of 631.4 nm as the external fiber-coupled excitation source.

Handheld imaging photonic crystal biosensor for multiplexed, label-free protein detection.

We present a handheld biosensor system for the label-free and specific multiplexed detection of several biomarkers employing a spectrometer-free imaging measurement system. A photonic crystal surface functionalized with multiple specific ligands forms the optical transducer. The photonic crystal slab is fabricated on a glass substrate by replicating a periodic grating master stamp with a period of 370 nm into a photoresist via nanoimprint lithography and deposition of a 70-nm titanium dioxide layer. Capture molecules are coupled covalently and drop-wise to the photonic crystal surface. With a simple camera and imaging optics the surface-normal transmission is detected. In the transmission spectrum guided-mode resonances are observed that shift due to protein binding. This shift is observed as an intensity change in the green color channel of the camera. Non-functionalized image sections are used for continuous elimination of background drift. In a first experiment we demonstrate the specific and time-resolved detection of 90.0 nm CD40 ligand antibody, 90.0 nM EGF antibody, and 500 nM streptavidin in parallel on one sensor chip. In a second experiment, aptamers with two different spacer lengths are used as receptor. The binding kinetics with association and dissociation of 250 nM thrombin and regeneration of the sensor surface with acidic tris-HCl-buffer (pH 5.0) is presented for two measurement cycles.

Self-bridging of vertical silicon nanowires and a universal capacitive force model for spontaneous attraction in nanostructures.

Spontaneous attractions between free-standing nanostructures have often caused adhesion or stiction that affects a wide range of nanoscale devices, particularly nano/microelectromechanical systems. Previous understandings of the attraction mechanisms have included capillary force, van der Waals/Casimir forces, and surface polar charges. However, none of these mechanisms universally applies to simple semiconductor structures such as silicon nanowire arrays that often exhibit bunching or adhesions. Here we propose a simple capacitive force model to quantitatively study the universal spontaneous attraction that often causes stiction among semiconductor or metallic nanostructures such as vertical nanowire arrays with inevitably nonuniform size variations due to fabrication. When nanostructures are uniform in size, they share the same substrate potential. The presence of slight size differences will break the symmetry in the capacitive network formed between the nanowires, substrate, and their environment, giving rise to electrostatic attraction forces due to the relative potential difference between neighboring wires. Our model is experimentally verified using arrays of vertical silicon nanowire pairs with varied spacing, diameter, and size differences. Threshold nanowire spacing, diameter, or size difference between the nearest neighbors has been identified beyond which the nanowires start to exhibit spontaneous attraction that leads to bridging when electrostatic forces overcome elastic restoration forces. This work illustrates a universal understanding of spontaneous attraction that will impact the design, fabrication, and reliable operation of nanoscale devices and systems.

Self-assembled hierarchical nanostructures for high-efficiency porous photonic crystals.

The nanoscale modulation of material properties such as porosity and morphology is used in the natural world to mold the flow of light and to obtain structural colors. The ability to mimic these strategies while adding technological functionality has the potential to open up a broad array of applications. Porous photonic crystals are one such technological candidate, but have typically underachieved in terms of available materials, structural and optical quality, compatibility with different substrates (e.g., silicon, flexible organics), and scalability. We report here an alternative fabrication method based on the bottom-up self-assembly of elementary building blocks from the gas phase into high surface area photonic hierarchical nanostructures at room temperature. Periodic refractive index modulation is achieved by stacking layers with different nanoarchitectures. High-efficiency porous Bragg reflectors are successfully fabricated with sub-micrometer thick films on glass, silicon, and flexible substrates. High diffraction efficiency broadband mirrors (R≈1), opto-fluidic switches, and arrays of photonic crystal pixels with size<10 µm are demonstrated. Possible applications in filtering, sensing, electro-optical modulation, solar cells, and photocatalysis are envisioned.

Terahertz Dipole Nanoantenna Arrays: Resonance Characteristics.

Resonant dipole nanoantennas promise to considerably improve the capabilities of terahertz spectroscopy, offering the possibility of increasing its sensitivity through local field enhancement, while in principle allowing unprecedented spatial resolutions, well below the diffraction limit. Here, we investigate the resonance properties of ordered arrays of terahertz dipole nanoantennas, both experimentally and through numerical simulations. We demonstrate the tunability of this type of structures, in a range (∼1-2 THz) that is particularly interesting and accessible by means of standard zinc telluride sources. We additionally study the near-field resonance properties of the arrays, finding that the resonance shift observed between near-field and far-field spectra is predominantly ascribable to ohmic damping.

A reflection-based localized surface plasmon resonance fiber-optic probe for biochemical sensing.

We report the fabrication and characterization of an optical fiber biochemical sensing probe based on localized surface plasmon resonance (LSPR) and spectra reflection. Ordered array of gold nanodots was fabricated on the optical fiber end facet using electron-beam lithography (EBL). We experimentally demonstrated for the first time the blue shift of the LSPR scattering spectrum with respected to the LSPR extinction spectrum, which had been predicted theoretically. High sensitivity [195.72 nm/refractive index unit (RIU)] of this sensor for detecting changes in the bulk refractive indices has been demonstrated. The label-free affinity bio-molecules sensing capability has also been demonstrated using biotin and streptavidin as the receptor and the analyte.