We numerically design and experimentally test a SERS-active substrate for enhancing the SERS signal of a monolayer of graphene in water. The monolayer is placed on top of an array of silver-covered nanoholes in a polymer and is covered with water. Here we report a large enhancement of up to 200000 in the SERS signal of the graphene monolayer on the patterned plasmonic nanostructure for a 532 nm excitation laser wavelength. Our numerical calculations of both the excitation field and the emission rate enhancements support the experimental results. We also propose a highly compact structure for near total light absorption in a monolayer of graphene in the visible. The structure consists of a grating slab covered with the graphene monolayer. The grating slab is separated from a metallic back reflector by a dielectric spacer. The proposed structure could find applications in the design of efficient nanoscale visible-light photodetectors and modulators.
Second-harmonic generation (SHG) microscopy is a label-free imaging technique to study collagenous materials in extracellular matrix environment with high resolution and contrast. However, like many other microscopy techniques, the actual spatial resolution achievable by SHG microscopy is reduced by out-of-focus blur and optical aberrations that degrade particularly the amplitude of the detectable higher spatial frequencies. Being a two-photon scattering process, it is challenging to define a point spread function (PSF) for the SHG imaging modality. As a result, in comparison with other two-photon imaging systems like two-photon fluorescence, it is difficult to apply any PSF-engineering techniques to enhance the experimental spatial resolution closer to the diffraction limit. Here, we present a method to improve the spatial resolution in SHG microscopy using an advanced maximum likelihood estimation (AdvMLE) algorithm to recover the otherwise degraded higher spatial frequencies in an SHG image. Through adaptation and iteration, the AdvMLE algorithm calculates an improved PSF for an SHG image and enhances the spatial resolution by decreasing the full-width-at-halfmaximum (FWHM) by ~20%. Similar results are consistently observed for biological tissues with varying SHG sources, such as gold nanoparticles and collagen in porcine feet tendons. By obtaining an experimental transverse spatial resolution of ~400 nm, we show that the AdvMLE algorithm brings the practical spatial resolution closer to the theoretical diffraction limit. Our approach is suitable for adaptation in micro-nano CT and MRI imaging, which has the potential to impact diagnosis and treatment of human diseases.
It has been shown that surface enhanced Raman spectroscopy (SERS) has many promising applications in ultrasensitive detection of Raman signal of substances. However, optimizing the enhancement in SERS signal for different applications typically requires several levels of fabrication of active plasmonic SERS substrates. In this paper, we report the enhancement of SERS signal of a single layer of graphene located on a plasmonic nano-Lycurgus cup array after placing water droplets on it. The experimental data shows that addition of water droplets can enhance the SERS signal of the single layer of graphene about 10 times without requiring any modifications to the nano-Lycurgus cup array. Using fullwave electromagnetic simulations, we show that addition of water droplets enhances the local electric field at the graphene layer, resulting in stronger light-graphene interaction at the excitation pump laser wavelength. We also show that the addition of water droplets on the graphene layer enables us to modify the band diagram of the structure, in order to enhance the local density of optical states at the Raman emission wavelengths of the graphene layer. Numerical calculations of both the excitation field enhancement at the location of the graphene layer, and the emission enhancement due to enhanced local density of optical states, support the experimental results. Our results demonstrate an approach to boost the SERS signal of a target material by controlling the band diagram of the active nanostructured SERS substrate through the use of fluidic dielectrics. These results could find potential applications in biomedical and environmental technologies.
Colorimetric detection is cost-effective and user-friendly when used for sensing target analytes without a need of bulky and expensive equipment. The extraordinary transmission phenomena through plasmonic periodic nanocup arrays achieve colorimetric sensing by detecting color changes of transmitted light associated with the refractive index variation. The application of the nanocup arrays, however, is relatively restricted due to a limited sensitivity for monolayered target analyte detections on the surface. In order to improve the sensitivity bounded by the underlying nanostructures, hybrid nanoparticle (NP) – nanocup array substrates are developed for enhancing the sensitivity to the refractive index change. The three dimensionally assembled Au NPs in circle along the sidewall of each nanocup increases the density of hot spots by the heterogeneous plasmonic coupling between the NP and the edge of the nanocup; thus a small refractive index change at the hot spot becomes easily detected than bare nanocup arrays. In addition to the bulk refractive index sensing, an ultrasensitive spectroscopic detection of the antigen-antibody binding is achieved by this three-dimensional self-assembly of Au NPs on the Au nanocup arrays.
To improve light absorption, previously various antireflection material layers were created on solar wafer surface including multilayer dielectric film, nanoparticle sludges, microtextures, noble metal plasmonic nanoparticles and 3D silicon nanostructure arrays. All of these approaches involve nanoscale prepatterning, surface-area-sensitive assembly processes or extreme fabrication conditions; therefore, they are often limited by the associated high cost and low yield as well as the consequent industry incompatibility. In comparison, our nanomanufacturing, an unique synchronized and simultaneous top-down and bottom-up nanofabrication approach called simultaneous plasma enhanced reactive ion synthesis and etching (SPERISE), offers a better antireflection solution along with the potential to increase p-n junction surface area. High density and high aspect ratio anechoic nanocone arrays are repeatedly and reliably created on the entire surface of single and poly crystalline silicon wafers as well as amorphous silicon thin films within 5 minutes under room temperature. The nanocone surface had lower than 5% reflection over the entire solar spectrum and a desirable omnidirectional absorption property. Using the nanotextured solar wafer, a 156mm × 156mm 18.1%-efficient black silicon solar cell was fabricated, which was an 18.3% enhancement over the cell fabricated by standard industrial processes. This process also reduces silicon loss during the texturing step and enables tighter process control by creating more uniform surface structures. Considering all the above advantages, the demonstrated nanomanufacturing process can be readily translated into current industrial silicon solar cell fabrication lines to replace the costly and ineffective wet chemical texturing and antireflective coatings.
The interaction of biomolecules and solid-state nanomaterials at the nano-bio interfaces is a long-lasting research topic in nanotechnology. Historically, fundamental problems, such as the electron transfer, energy transfer, and plasmonic interaction at the bio-nano interfaces, have been intensively studied, and revolutionary technologies, such as molecular electronics, peptide chips, nanoplasmonic sensors, have been created. With the combined effort of molecular dynamics simulation and surface-enhanced Raman spectroscopy, we studied the external electric field-induced conformation changes of dodecapeptide probes tethered to a nanostructured metallic surface. Through this study, we demonstrated a reversible manipulation of the biomolecule conformations as well as an in situ eletro-optical detection of the subnanometer conformational changes at the bio-nano interfaces. Based on the proof-of-concept established in this study, we further propose a novel nanophotonic peptide phosphorylation sensor for high-sensitive peptide kinase profiling. We have also demonstrated the same SERS nano-bio-chip can be used for environmental monitoring applications, such as detection of contaminants in drinking water at ultralow concentrates. The fabrication of this nanosensor is based on a single step, lithography-less nanomanufacturing process, which can produce hundreds of these chips in several minutes with nearly 100% yield and uniformity. Therefore, the demonstrated research can be readily translated into industrial mass productions.
In this paper, we fabricated gold particle array substrate by thermal dewetting technique. The fabrication process is
simple, reliable, cost efficient with comparing to other techniques. From optical characteristic it shows light trapping
ability to reduce reflectance around 75%. Combining light trapping and its localized plasmonic properties, this substrate
has significant advantages on plasmonic based sensing methods such as surface enhanced Raman scattering (SERS).
SERS measurement has been performed and the enhancement factor is 2.58×105. Further more, after silver thin film
deposition the enhancement can be increased up to 2 orders and the enhancement factor is 3.66×107.
KEYWORDS: Etching, Silicon, Nanolithography, Nanostructures, Reflection, Aluminum, Photomasks, Deep reactive ion etching, Reactive ion etching, Scanning electron microscopy
We have fabricated nanotextured Si substrates that exhibit controllable optical reflection intensities and colors. Si
Nanopore, which has photon-trapping nanostructure but has abrupt changes in the index of refraction displaying a
darkened specular reflection. Aluminum is evaporated on the surface of N-type Si by e-beam evaporation. Nanopore
structure is formed by a two-step AAO formation in oxalyic acid. Diameter size from 30 to 80 nm is achieved,
depending on the condition of anodization and etch. Deep reactive ionic etch (DRIE) is done, with AAO as the mask
layer. The nanopore AAO template allows etching depth of up to 1600 nm. By tuning the nanoscale silicon structure, the
optical reflection peak wavelength and intensity are changed, making the surface to have different reflectivity and
apparent colors. Parameters that affect the fabrication are evaluated. Optical properties of various pore depths are
discussed. The relation between the surface optical properties with the spatial features of the photon trapping
nanostructures is examined. The tunable photon trapping silicon structures have potential applications in enhancing the
performance of semiconductor photoelectric devices.ope>
Improvement of energy conversion efficiency of solar cells has led to innovative approaches, in particular the
introduction of nanopillar photovoltaics [1]. Previous work on nanopillar Si photovoltaic has shown broadband reduction
in optical reflection and enhancement of absorption [2]. Radial or axial PN junctions [3, 4] have been of high interest for
improved photovoltaic devices. However, with the PN junction incorporated as part of the pillar, the discreteness of
individual pillar requires additional conductive layer that would electrically short the top of each pillar for efficient
carrier extraction. The fragile structure of the surface pillars would also require a protection layer for possible
mechanical scratch to prevent pillars from breaking. Any additional layer that is applied, either for electrical contact or
for mechanical properties may introduce additional recombination sites and also reduce the actual light absorption by the
photovoltaic material. In this paper, nanopore Si photovoltaics that not only provides the advantages but also addresses
the challenges of nanopillers is demonstrated. PN junction substrate of 250 nm thick N-type polycrystalline Si on P-type
Si wafer is prepared. The nanopore structure is formed by using anodized aluminum oxide (AAO) as an etching mask
against deep reactive ionic etching (DRIE). The device consists of semi-ordered pores of ~70 nm diameter.
With the goal of improving photo-absorption of photovoltaic device and for plasmonic application we have fabricated
nanopillar black silicon devices through etching-passivation technique which does not require any photomask and whole
wafer scale uniformity is achieved at room temperature in a short time. We have carried out thorough optical
characterization for nanopillar black silicon devices to be used for solar cell and plasmonic applications.
Cathodoluminescence (CL), current dependent CL spectroscopy, photoluminescence (at room temperature and 77 K),
Raman spectroscopy, reflectance and absorption measurement have been performed on the device. A thin layer of Ag is
deposited to render with plasmonic property and the plasmonic effect is probed using surface plasmon enhanced
fluorescence, angle dependent reflectance measurements, high resolution cathodoluminescence (CL), surface enhanced
Raman spectroscopy (SERS) measurement and Fluorescence Lifetime Imaging Microscopy (FLIM) experiment. We
obtained reduction in optical reflection of ~ 12 times on b-Si substrate from UV to NIR range, the nanostructured
fluorescence enhancement of ~40 times and the Raman scattering enhancement factor of 6.4×107.
In this paper, a unique nanoscrew Si structure is presented. The nanoscrew surface is made by anodized aluminum oxide
(AAO) mask formation followed by extended deep reactive ionic etching (DRIE). Dense random zig-zag pillar
structures that represent screw shapes are formed, with 1 um in height and the bottom base width ranging from 100 nm
to 250 nm. The tip of the nanoscrews have radius of curvature even lower than 10 nm. The apparent naked-eye view of
the nanoscrew surface, which only consists of nanopatterned N-type single crystalline Si is diffusively green. The optical
properties of nanoscrew Si with and without metal deposition is presented as discussion in applications for SERS.
KEYWORDS: Luminescence, Nanoplasmonics, Silver, Confocal microscopy, Metals, Resonance enhancement, 3D image processing, Near field optics, 3D image enhancement, Surface plasmons
We have created an enhanced cell-imaging platform for 3D confocal fluorescence cell imaging where fluorescence
sensitivity is amplified for more than 100 folds especially for cell membrane and cytoplasm. The observed
unprecedented three-dimensional fluorescence intensity enhancement on the entire cell microstructure including cell
membrane 10 μm above the substrate surface is attributed to a novel far field enhancement mechanism, nanoplasmon
coupled optical resonance excitation (CORE) mechanism which permits enhanced surface plasmon on the substrate
being evanescently coupled to Whispering Gallery mode optical resonance inside the spheroidal cell membrane
microcavity. Theoretical model of the hypothesis is explained using coupled mode theory. In addition, preliminary result
has been provided for the observation of early stage of transfection in a cancer cell.
We demonstrate surface plasmon-induced enhancements in optical imaging and spectroscopy on silver coated silicon
nanocones which we call black silver substrate. The black silver substrate with dense and homogeneous nanocone forest
structure is fabricated on wafer level with a mass producible nanomanufacturing method. The black silver substrate is
able to efficiently trap and convert incident photons into localized plasmons in a broad wavelength range, which permits
the enhancement in optical absorption from UV to NIR range by 12 times, the visible fluorescence enhancement of ~30
times and the NIR Raman scattering enhancement factor up to ~108. We show a considerable potential of the black silver
substrate in high sensitivity and broadband optical sensing and imaging of chemical and biological molecules.one)
We demonstrate that the optical response of a single Au bowtie nano-antenna (BNA) can be favorably modified
to increase the local intensity by a factor of 103 in the feed gap region when a periodic array of BNAs are used.
We use the periodicity of the arrays as an additional degree of freedom in manipulating the optical response and
investigate the behavior of the resultant nonlinear emission, which include second harmonic generation (SHG),
two-photon photoluminescence (TPPL), and an additional photoluminescence that cannot be attributed to a
single multiphoton process. We discuss the effects of the array with respect to the nonlinear emission and also find
that the considerable field enhancement of our antenna system leads to a broadband continuum whose spectral
response is highly controllable. Resonantly excited arrays of BNAs were seen to exhibit a remarkably uniform
emission over 250 nm of the visible spectrum. In addition, our analysis suggests that high field enhancements,
as well as resonance matching, may not be the only preconditions for enhanced nonlinear emission. To our
knowledge, this is the first report of implementing optical antennas in an array to favorably augment its optical
response.
We demonstrated gold-coated polymer surface enhanced Raman scattering (SERS) substrates with a pair of complementary structures-positive and inverted pyramid array structures fabricated by a multiple-step molding and replication process. The uniform SERS enhancement factors over the entire device surface were measured as 7.2×104 for positive pyramid substrates while 1.6×106 for inverted pyramid substrates with Rhodamine 6G as the target analyte. Based on the optical reflection measurement and finite difference time domain simulation result, the enhancement factor difference is attributable to plasmon resonance matching and to SERS "hot spots" distribution. With this simple, fast, and versatile complementary molding process, we can produce polymer SERS substrates with extremely low cost, high throughput, and high repeatability.
Nano plasmonic resonance energy transfer (PRET) spectroscopy is a new sensing technique to study the electronic
energy transfer between plasmonic nanoparticles and adsorbed biological/chemical molecules. PRET spectroscopy has
been used to detect complex biomolecular activities including conformational change, electron transfer and protein
interactions with ultrahigh sensitivity and specificity. Here we demonstrate in vitro and intracellular imaging of pH
values using PRET spectroscopy. Potentially submicron spatial resolution and decimal pH sensitivity can be achieved in
PRET pH imaging.
Nanoplasmonic resonance spectroscopy enhances sensitivity and throughput of conventional SPR detection technique
while still suffers with modest molecular specificity. Here we demonstrated a new sensing technique --- nano plasmonic
resonance energy transfer (PRET) spectroscopy to detect complex biomolecular activities including conformational
change, electron transfer and protein interactions with ultrahigh sensitivity and specificity. Compared to FRET sensing
technology, PRET has much stronger optical signal to noise ratio and minimal photobleaching problems. Nano PRET
spectroscopic molecular imaging technique can be used in multiplexed label-free cancer biomarker detections and
environmental sensing applications.
We have invented a novel all-optical-logic microfluidic system which is automatically controlled only by visible or near infrared light with down to submilliwatt power. No electric power supply, no external or MEMS pump, no tubings or connectors, no microfluidic valves, nor surface patterning are required in our system. Our device only consists of a single-layer PDMS microfluidic chip and newly invented photoactive nanoparticles. Our photoactive nanoparticles are capable of converting optical energy to hydrodynamic energy in fluids. The nanoparticle themselves are biocompatible and can be biofunctionalized. Via these photoactive nanoparticles, we used only light to drive, guide, switch and mix liquid in optofluidic logic circuits with desired speeds and directions. We demonstrated the optofluidic controls in transportation of biomolecules and cells.
An electron transfer pathway between Cytochrome c (Cyt c) molecules, a 30nm Au nanoparticle and an ITO working electrode in an electrochemical cell is constituted by molecular junctions. The scattering spectrum of single Au nanoparticle is measured simultaneously with the cyclic voltammogram. The plasmon resonance wavelength and the scattering cross section of the single Au nanoparticle are affected by the redox reactions of less than 200 cyt c molecules on its surface and exhibit cyclic variations. The electron shuttling between Cyt c molecules and ITO electrode through the Au nanoparticle in the redox process as well as the conformation change of the Cyt c molecules between ferric and ferrous states are accounted the reasons for the change of the plasmon resonance wavelength and scattering cross section. The presented study of the interaction of biological electron transporter protein and photonic nanostructure provide a nano-scale system to probe the electron transfer events in the biological system. It also has the implicational importance to the development of future hybrid bio-optoelectronic devices.
A gold nanowire array that we call nanorainbow SPR sensor array can be chemically functionalized and used to capture biomolecules. The localized plasmon resonance wavelength of the gold nanowires shifts on the biomolecule binding and reaction sites. The plasmon resonance shift of the gold nanorainbow is sensitive to the biomolecule immobilization in sub-nM concentration. As an application example, label-free oligonucleotide hybridizations are detected on the nanorainbow sensor in a multiplexed microfluidic chip.
In this investigation, a polarization-based imaging system is developed and described that measures the two-dimensional effective backscattering Mueller matrix of a sample in near real-time. As is well known, a Mueller matrix can provide considerable information on the makeup and optical characteristics of a sample and also directly describes how the sample transforms an incident light beam. The ability to measure the two-dimensional Mueller matrix of a biological sample, therefore, can provide considerable information on the sample composition as well as the potential to reveal significant structural information that normally would not be visible through standard imaging techniques. Additional information can also be obtained through the application of image-processing, decomposition, and reconstruction techniques that operate directly on the 2D Mueller matrix. Using the developed system, it is shown how the induction of internal strain within the sample coupled with image reconstruction and decomposition techniques can further improve image contrast and aid in the detection of boundaries between tissues of different biomechanical and structural properties. The studies presented were performed with both rat tissue and a melanoma-based tissue culture. The results demonstrate how these techniques could provide information that may be of diagnostic value in the physical detection of malignant lesion boundaries.
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