Quantitative mechanical analysis of thin compressible polymer monolayers on oxide surfaces.

A clear understanding of the mechanical behavior of nanometer thick films on nanostructures, as well as developing versatile approaches to characterize their mechanical properties, are of great importance and may serve as the foundation for understanding and controlling molecular interactions at the interface of nanostructures. Here we report on the synthesis of thin, compressible polyethylene glycol (PEG) monolayers with a wet thickness of <20 nm on tin dioxide (SnO2) nanofibers through silane-based chemistries. Nanomechanical properties of such thin PEG films were extensively investigated using atomic force microscopy (AFM). In addition, tip-sample interactions were carefully studied, with different AFM tip modifications (i.e., hydrophilic and hydrophobic) and in different ionic solutions. We find that the steric forces dominate the tip-sample interactions when the polymer film is immersed in solution with salt concentrations similar to biological media (e.g., 1x phosphate buffer solution), while van der Waals and electrostatic forces have minimal contributions. A Dimitriadis thin film polymer compression model shows that the linear elastic regime is reproducible in the initial 50% indentation of these films which have tunable Young's moduli ranging from 5 MPa for the low molecular weight films to 700 kPa for the high molecular weight PEG films. Results are compared with the same PEG films deposited on silicon substrates which helped quantify the structural properties and understand the relationship between the structural and the mechanical properties of PEG films on the SnO2 fibers.

Nanofiber near-field light-matter interactions for enhanced detection of molecular level displacements and dynamics.

We experimentally demonstrate that plasmonic nanoparticles embedded in the evanescent field of subwavelength optical waveguides (WGs) are highly sensitive to distances normal to the propagation of light, showing an ~10× increase in spatial resolution compared to the optical field decay of the WG. The scattering cross-section of the Au nanoparticle is increased by the plasmon-dielectric coupling interaction when the nanoparticle is placed near the dielectric surface of the WG, and the decay of the scattering signal is enhanced, showing angstrom level distance sensitivity within 10 nm from the WG. Numerical studies with the finite-difference time-domain (FDTD) method correlate well with the experimental results. To demonstrate real-time monitoring of a single molecule stretching in the evanescent field, we linked individual single-stranded DNA molecules between the WG and plasmonic nanoparticles and pushed on the nanoparticles with fluidic forces. The simple design and ease of obtaining optical feedback on molecular displacements makes our approach ideal for new in situ force sensing devices, imaging technologies, and high-throughput molecular analysis.

Stimulus-responsive light coupling and modulation with nanofiber waveguide junctions.

We report a systematic study of light coupling at junctions of overlapping SnO(2) nanofiber waveguides (WGs) as a function of gap separation and guided wavelength. The junctions were assembled on silica substrates using micromanipulation techniques and the gap separation was controlled by depositing thin self-assembled polyelectrolyte coatings at the fiber junctions. We demonstrate that the coupling efficiency is strongly dependent on the gap separation, showing strong fluctuations (0.1 dB/nm) in the power transfer when the separation between nanofibers changes by as little as 2 nm. Experimental results correlate well with numerical simulations using three-dimensional finite-difference time-domain techniques. To demonstrate the feasibility of using coupled nanofiber WGs to modulate light, we encased the junctions in an environment-responsive matrix and exposed the junctions to gaseous vapor. The nanofiber junctions show an ~95% (or ~80%) modulation of the guided 450 nm (or 510 nm) light upon interaction with the gaseous molecules. The results reveal a unique nanofiber-based sensing scheme that does not require a change in the refractive index to detect stimuli, suggesting these structures could play important roles in localized sensing devices including force-based measurements or novel chemically induced light modulators.

Rainbow radiating single-crystal Ag nanowire nanoantenna.

Optical antennas interface an object with optical radiation and boost the absorption and emission of light by the objects through the antenna modes. It has been much desired to enhance both excitation and emission processes of the quantum emitters as well as to interface multiwavelength channels for many nano-optical applications. Here we report the experimental implementation of an optical antenna operating in the full visible range via surface plasmon currents induced in a defect-free single-crystalline Ag nanowire (NW). With its atomically flat surface, the long Ag NW reliably establishes multiple plasmonic resonances and produces a unique rainbow antenna radiation in the Fresnel region. Detailed antenna radiation properties, such as radiating near-field patterns and polarization states, were experimentally examined and precisely analyzed by numerical simulations and antenna theory. The multiresonant Ag NW nanoantenna will find superb applications in nano-optical spectroscopy, high-resolution nanoimaging, photovoltaics, and nonlinear signal conversion.

Dual-Functional Solar-to-Steam Generation and SERS Detection Substrate Based on Plasmonic Nanostructure.

Solar-to-steam (STS) generation based on plasmonic materials has attracted significant attention as a green method for producing fresh water. Herein, a simple in situ method is introduced to fabricate Au nanoparticles (AuNPs) on cellulose filter papers as dual-functional substrates for STS generation and surface-enhanced Raman spectroscopy (SERS) sensing. The substrates exhibit 90% of broadband solar absorption between 350 and 1800 nm and achieve an evaporation rate of 0.96 kg·m-2·h-1 under 1-sun illumination, room temperature of 20 °C, and relative humidity of 40%. The STS generation of the substrate is stable during 30 h continuous operation. Enriched SERS hotspots between AuNPs endow the substrates with the ability to detect chemical contamination in water with ppb limits of detection for rhodamine 6G dye and melamine. To demonstrate dual-functional properties, the contaminated water was analyzed with SERS and purified by STS. The purified water was then analyzed with SERS to confirm its purity. The developed substrate can be an improved and suitable candidate for fresh water production and qualification.

Surface Modification of ZrO2 Nanoparticles with TEOS to Prepare Transparent ZrO2@SiO2-PDMS Nanocomposite Films with Adjustable Refractive Indices.

Here, highly transparent nanocomposite films with an adjustable refractive index were fabricated through stable dispersion of ZrO2 (n = 2.16) nanoparticles (NPs) subjected to surface modification with SiO2 (n = 1.46) in polydimethylsiloxane (PDMS) (n = 1.42) using the Stöber method. ZrO2 NPs (13.7 nm) were synthesized using conventional hydrothermal synthesis, and their surface modification with SiO2 (ZrO2@SiO2 NPs) was controlled by varying the reaction time (3-54 h). The surface modification of the NPs was characterized using Fourier-transform infrared spectroscopy, dynamic light scattering, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and ellipsometry. The surface modification was monitored, and the effective layer thickness of SiO2 varied from 0.1 nm to 4.2 nm. The effective refractive index of the ZrO2@SiO2 NPs at λ = 633 nm was gradually reduced from 2.16 to 1.63. The 100 nm nanocomposite film was prepared by spin-coating the dispersion of ZrO2@SiO2 NPs in PDMS on the coverslip. The nanocomposite film prepared using ZrO2@SiO2 NPs with a reaction time of 18 h (ZrO2@SiO2-18h-PDMS) exhibited excellent optical transparency (Taverage = 91.1%), close to the transparency of the coverslip (Taverage = 91.4%) in the visible range, and an adjustable refractive index (n = 1.42-1.60) as the NP content in the film increased from 0 to 50.0 wt%.

Polymorph-tuned synthesis of α- and ß-Bi2O3 nanowires and determination of their growth direction from polarized Raman single nanowire microscopy.

We report polymorph-tuned synthesis of α- and ß-Bi(2)O(3) nanowires and their single nanowire micro-Raman study. The single crystalline Bi(2)O(3) nanowires in different phases (α and ß) were selectively synthesized by adjusting the heating temperature of Bi precursor in a vapor transport process. No catalyst was employed. Furthermore, at an identical precursor evaporation temperature, α- and ß- phase Bi(2)O(3) nanowires were simultaneously synthesized along the temperature gradient at a substrate. The growth direction of α-Bi(2)O(3) nanowires was revealed by polarized Raman single nanowire spectra. For thin ß-Bi(2)O(3) nanowires with a very small diameter, the polarized Raman single nanowire spectrum was strongly influenced by the shape effect.

Au nanowire-on-film SERRS sensor for ultrasensitive Hg2+ detection.

We report an ultrasensitive and selective single nanowire-on-film (SNOF) surface-enhanced resonance Raman scattering (SERRS) sensor for Hg(2+) detection based on structure-switching double stranded DNAs (dsDNAs). Binding of Hg(2+) induces conformational changes of the dsDNAs and let a Raman reporter get close to the SNOF structure, thereby turning on SERRS signal. The well-defined SNOF structure provides a detection limit of 100 pM with improved accuracy in Hg(2+) detection. This sensor is stable over a considerable amount of time and reusable after simple treatment. Since this SNOF sensor is composed of a single Au NW on a film, development of a multiplex sensor would be possible by employing NWs modified by multiple kinds of aptamers.

Patterned multiplex pathogen DNA detection by Au particle-on-wire SERS sensor.

A Au particle-on-wire system that can be used as a specific, sensitive, and multiplex DNA sensor is developed. A pattern formed by multiple Au nanowire sensors provides positional address and identification for each sensor. By using this system, multiplex sensing of target DNAs was possible in a quantitative manner with a detection limit of 10 pM. Target DNAs from reference bacteria and clinical isolates were successfully identified by this sensor system, enabling diagnostics for infectious diseases.

Au@ZIF-8 SERS paper for food spoilage detection.

Putrescine and cadaverine are important volatile indicators for the evaluation of food spoilage. In this study, a metal-organic framework (MOF)-coated surface-enhanced Raman scattering (SERS) paper platform for the detection of putrescine and cadaverine is developed. Au@ zeolite imidazolate framework-8 (ZIF-8) SERS paper is fabricated by the coating of ZIF-8 layer on a Au nanoparticle-impregnated paper that is prepared by dry plasma reduction. The Au@ZIF-8 SERS paper is characterized by scanning electron microscope, energy-dispersive X-ray spectroscopy, X-ray diffraction, and N2 sorption isotherm. The ZIF-8 layer enables the accumulation of gaseous molecules and also provides enhancement of SERS signals. The fluorescence, SERS, and simulation results prove the improved detection ability of the Au@ZIF-8 platform for the volatile molecules. For the selective detection of putrescine and cadaverine, the Au@ZIF-8 SERS paper is functionalized with 4-mercatobenzaldehyde (4-MBA). The 4-MBA molecule acts as a Raman reporter and also a specific receptor for the volatile amine molecules. Using the intensity ratiometric detection of 4-MBA-functionalized Au@ZIF-8 SERS paper, putrescine and cadaverine are quantitatively detected with detection limits of 76.99 and 115.88 parts per billion, respectively. Furthermore, the detection of volatile amine molecules released from spoiled salmon, chicken, beef, and pork samples is demonstrated. It is anticipated that the MOF-coated SERS paper platforms will be applicable not only in food safety but other applications including disease diagnosis and environmental monitoring.

Au nanowire-Au nanoparticles conjugated system which provides micrometer size molecular sensors.

We report a new type of molecular sensor using a Au nanowire (NW)-Au nanoparticles (NPs) conjugated system. The Au NW-NPs structure is fabricated by the self-assembly of biotinylated Au NPs on a biotinylated Au NW through avidin; this creates hot spots between NW and NPs that strongly enhance the Raman signal. The number of the Au NPs attached to the NW is reproducibly proportional to the concentration of the avidin, and is also proportional to the measured surface-enhanced Raman scattering (SERS) signals. Since this well-defined NW-NPs conjugated sensor is only a few micrometer long, we expect that development of multiplex nanobiosensor of a few tens micrometer size would become feasible by combining individually modified multiple Au NWs together on one substrate.

Newly Developed Broadband Antireflective Nanostructures by Coating a Low-Index MgF2 Film onto a SiO2 Moth-Eye Nanopattern.

A newly developed nanopatterned broadband antireflective (AR) coating was fabricated on the front side of a glass/indium tin oxide/perovskite solar cell (PSC) by depositing a single interference layer onto a two-dimensional (2D)-patterned moth-eye-like nanostructure. The optimized developed AR nanostructure was simulated in a finite-difference time domain analysis. To realize the simulated developed AR nanostructure, we controlled the SiO2 moth-eye structure with various diameters and heights and a MgF2 single layer with varying thicknesses by sequentially performing nanosphere lithography, reactive ion etching, and electron-beam evaporation. Optimization of the developed AR nanostructure, which has a 100 nm-thick MgF2 film coated onto the SiO2 moth-eye-like nanostructure (diameter 165 nm and height 400 nm), minimizes the reflection loss throughout the visible range. As a result, the short-circuit current density (JSC) of the newly AR-coated PSC increases by 11.80%, while the open-circuit voltage (VOC) remains nearly constant. Therefore, the power conversion efficiency of the newly developed AR-decorated PSC increases by 12.50%, from 18.21% for a control sample to 20.48% for the optimum AR-coated sample. These results indicate that the newly developed MgF2/SiO2 AR nanostructure can provide an advanced platform technology that reduces the Fresnel loss and therefore increases the possibility of the commercialization of glass-based PSCs.

Single nanowire on a film as an efficient SERS-active platform.

Fabricating well-defined and highly reproducible platforms for surface-enhanced Raman scattering (SERS) is very important in developing practical SERS sensors. We report a novel SERS platform composed of a single metallic nanowire (NW) on a metallic film. Optical excitation of this novel sandwich nanostructure provides a line of SERS hot spots (a SERS hot line) at the gap between the NW and the film. This single nanowire on a film (SNOF) architecture can be easily fabricated, and the position of hot spots can be conveniently located in situ by using an optical microscope during the SERS measurement. We show that high-quality SERS spectra from benzenethiol, brilliant cresyl blue, and single-stranded DNA can be obtained on a SNOF with reliable reproducibility, good time stability, and excellent sensitivity, and thus, SNOFs can potentially be employed as effective SERS sensors for label-free biomolecule detection. We also report detailed studies of polarization- and material-dependent SERS enhancement of the SNOF structure.

Enhanced Surface Properties of Light-Trapping Si Nanowires Using Synergetic Effects of Metal-Assisted and Anisotropic Chemical Etchings.

Metal-assisted chemical etching (MACE) has been widely explored for developing silicon (Si)-based energy and optical devices with its benefits for low-cost and large-area fabrication of Si nanostructures of high aspect ratios. Surface structures and properties of Si nanostructures fabricated through MACE are significantly affected by experimental and environmental conditions of etchings. Herein, we showed that surfaces and interfacial energy states of fabricated Si nanowires can be critically affected by oxidants of MACE etching solutions. Surfaces of fabricated Si nanowires are porous and their tips are fully covered with lots of Si nano-sized grains. Strongly increased photoluminescence (PL) intensities, compared to that of the crystalline Si substrate, are observed for MACE-fabricated Si nanowires due to interfacial energy states of Si and SiOx of Si nano-sized grains. These Si grains can be completely removed from the nanowires by an additional etching process of the anisotropic chemical etching (ACE) of Si to taper the nanowires and enhance light trapping of the nanowires. Compared with the MACE-fabricated Si nanowires, ACE-fabricated tapered Si nanowires have similar Raman and PL spectra to those of the crystalline Si substrate, indicating the successful removal of Si grains from the nanowire surfaces by the ACE process.

Enhancement of Light Absorption in Photovoltaic Devices using Textured Polydimethylsiloxane Stickers.

We designed and fabricated a random-size inverted-pyramid-structured polydimethylsiloxane (RSIPS-PDMS) sticker to enhance the light absorption of solar cells and thus increase their efficiency. The fabricated sticker was laminated onto bare glass and crystalline silicon (c-Si) surfaces; consequently, low solar-weighted reflectance values were obtained for these surfaces (6.88 and 17.2%, respectively). In addition, we found that incident light was refracted at the PDMS-air interface of each RSIPS, which redirected the incident power and significantly increased the optical path length in the RSIPS-PDMS sticker which was 14.7% greater than that in a flat-PDMS sticker. Moreover, we investigated power reflection and propagation through the RSIPS-PDMS sticker using a finite-difference time-domain method. By attaching an RSIPS-PDMS sticker onto both an organic solar cell (OSC) based on a glass substrate and a c-Si solar cell, the power conversion efficiency of the OSC and the c-Si solar cell were increased from 8.57 to 8.94% and from 16.2 to 17.9%, respectively. Thus, the RSIPS-PDMS sticker is expected to be universally applicable to the surfaces of solar cells to enhance their light absorption.

Nanofibre optic force transducers with sub-piconewton resolution via near-field plasmon-dielectric interactions.

Ultrasensitive nanomechanical instruments, including the atomic force microscope (AFM)1-4 and optical and magnetic tweezers5-8, have helped shed new light on the complex mechanical environments of biological processes. However, it is difficult to scale down the size of these instruments due to their feedback mechanisms9, which, if overcome, would enable high-density nanomechanical probing inside materials. A variety of molecular force probes including mechanophores10, quantum dots11, fluorescent pairs12,13 and molecular rotors14-16 have been designed to measure intracellular stresses; however, fluorescence-based techniques can have short operating times due to photo-instability and it is still challenging to quantify the forces with high spatial and mechanical resolution. Here, we develop a compact nanofibre optic force transducer (NOFT) that utilizes strong near-field plasmon-dielectric interactions to measure local forces with a sensitivity of <200 fN. The NOFT system is tested by monitoring bacterial motion and heart-cell beating as well as detecting infrasound power in solution.

Gap controlled plasmon-dielectric coupling effects investigated with single nanoparticle-terminated atomic force microscope probes.

Precise positioning of a plasmonic nanoparticle (NP) near a small dielectric surface is not only necessary for understanding gap-dependent interactions between a metal and dielectric but it is also a critical component in building ultrasensitive molecular rulers and force sensing devices. In this study we investigate the gap-dependent scattering of gold and silver NPs by controllably depositing them on an atomic force microscope (AFM) tip and monitoring their scattering within the evanescent field of a tin dioxide nanofiber waveguide. The enhanced distance-dependent scattering profiles due to plasmon-dielectric coupling effects show similar decays for both gold and silver NPs given the strong dependence of the coupling on the decaying power in the near-field. Experiments and simulations also demonstrate that the NPs attached to the AFM tips act as free NPs, eliminating optical interference typically observed from secondary dielectric substrates. With the ability to reproducibly place individual plasmonic NPs on an AFM tip, and optically monitor near-field plasmon-dielectric coupling effects, this approach allows a wide-variety of light-matter interactions studies to be carried out on other low-dimensional nanomaterials.

Profiling the evanescent field of nanofiber waveguides using self-assembled polymer coatings.

Here we demonstrate a facile method of quantifying the decaying optical field surrounding free-standing tin dioxide (SnO(2)) nanofiber waveguides. Through the use of thin self-assembled polyelectrolyte coatings and fluorescent optical transmitters we map out the optical intensity as a function of distance with nanometer resolution.

Pattern-selective epitaxial growth of twin-free Pd nanowires from supported nanocrystal seeds.

We report that twin-free single-crystalline Pd nanowire (NW) arrays grow epitaxially in a selected pattern on a substrate. Parallel aligned Pd NWs are synthesized on a SrTiO(3) (110) substrate in a very high density. On a SrTiO(3) (001) substrate, Pd NWs grow horizontally in two perpendicular directions. Vertical Pd NWs are synthesized instead of horizontal NWs when a c-cut sapphire substrate is employed. We reveal that the atomic structure of the substrate surface determines the geometry and orientation of seeds, which in turn direct the growth patterns of the NWs. The interface energy between the NW material and the substrate is also critical in determining the NW growth pattern. Polarization-dependent localized surface plasmon resonance of as-synthesized epitaxial Pd NW arrays is investigated for application as a plasmonic platform.