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Large-Scale Plasmonic Hybrid Framework with Built-In Nanohole Array as Multifunctional Optical Sensing Platforms

Light coupling with patterned subwavelength hole arrays induces enhanced transmission supported by the strong surface plasmon mode. In this work, a nanostructured plasmonic framework with vertically built-in nanohole arrays at deep-subwavelength scale (6 nm) is demonstrated using a two-step fabrication method. The nanohole arrays are formed first by the growth of a high-quality two-phase (i.e., Au–TiN) vertically aligned nanocomposite template, followed by selective wet-etching of the metal (Au). Such a plasmonic nanohole film owns high epitaxial quality with large surface coverage and the structure can be tailored as either fully etched or half-way etched nanoholes via careful control of the etching process. The chemically inert and plasmonic TiN plays a role in maintaining sharp hole boundary and preventing lattice distortion. Optical properties such as enhanced transmittance and anisotropic dielectric function in the visible regime are demonstrated. Numerical simulation suggests an extended surface plasmon mode and strong field enhancement at the hole edges. Furthermore, two demonstrations, including the enhanced and modulated photoluminescence by surface coupling with 2D perovskite nanoplates and the refractive index sensing by infiltrating immersion liquids, suggest the great potential of such plasmonic nanohole array for reusable surface plasmon-enhanced sensing applications.

42 ENGINEERING↗

Estimation of Aerosol Columnar Size Distribution from Spectral Extinction Data in Coastal and Maritime Environment

Aerosol columnar size distributions (SDs) are commonly provided by aerosol inversions based on measurements of both spectral extinction and sky radiance. These inversions developed for a fully clear sky offer few SDs for areas with abundant clouds. Here, we estimate SDs from spectral extinction data alone for cloudy coastal and maritime regions using aerosol refractive index (RI) obtained from chemical composition data. Our estimation involves finding volume and mean radius of lognormally distributed modes of an assumed bimodal size distribution through fitting of the spectral extinction data. We demonstrate that vertically integrated SDs obtained from aircraft measurements over a coastal site have distinct seasonal changes, and these changes are captured reasonably well by the estimated columnar SDs. We also demonstrate that similar seasonal changes occur at a maritime site, and columnar SDs retrieved from the combined extinction and sky radiance measurements are approximated quite well by their extinction only counterparts (correlation exceeds 0.9) during a 7-year period (2013–2019). The level of agreement between the estimated and retrieved SDs depends weakly on wavelength selection within a given spectral interval (roughly 0.4–1 µm). Since the extinction-based estimations can be performed frequently for partly cloudy skies, the number of periods where SDs can be found is greatly increased.

54 ENVIRONMENTAL SCIENCES↗

OLEDs on planarized light outcoupling-enhancing structures in plastic

Light extraction from OLEDs remains a challenge. While consumer demand for OLEDs in display technology continues to grow as prices decline, commercial use of OLEDs in solid state lighting (SSL) applications is lagging due to low light extraction, which results in low efficiency. Previous studies have been directed toward increasing the light extraction factor η out , but cost effective approaches that will enable high throughput and potential upscaling, as well as elucidation of the extraction process, are still lagging. One promising approach is the use of buried light extraction enhancing patterns that are planarized with a high refractive index (RI) layer. When adding substrate mode extracting means, the highest external quantum efficiencies (EQEs) were achieved using a complex approach of planarized vacuum nano holes. Here we present η out -enhancing planarized extraction structures (PES) in plastic. While plastic substrates currently present long-term stability issues and other drawbacks, as we show, they provide a tool for simple, inexpensive, and rapid generation of various enhancing structures that importantly can be transferred to the preferred rigid and flexible glass substrates. Moreover, plastic substrates are attractive for biomedical applications. The successful structures we present are easily scalable periodic corrugations, e.g., with pitch a ~ 4.25 µm and pitch/depth ratio a/h ~2.4 planarized by a layer of RI ~1.9, resulting in maximal EQEs exceeding 60% for a green OLED and 48.5% for a white OLED. Comparable increased EQEs were achieved for structures with a ~ 15 and 16 µm, and a/h ~ 2.1 and 4, respectively. Enhanced extraction was also observed with a very simply fabricated quasiperiodic nanohole array, and surprisingly, with a random shallow design. The latter is at variance with simulations based on diffraction only. Results are discussed in terms of a, h, and structural parameters together with scattering matrix simulations to assess the effect of various PES parameters and the nanoparticle-embedded planarizing layer on η out . The experiments and simulations indicate contributions of diffraction, reflection, and scattering to EQE enhancement.

36 MATERIALS SCIENCE↗

Understanding the Solution Dynamics and Binding of a PVDF Binder with Silicon, Graphite, and NMC Materials and the Influence on Cycling Performance

The impact of the binding, solution structure, and solution dynamics of poly(vinylidene fluoride) (PVDF) with silicon on its performance as compared to traditional graphite and Li 1.05 Ni 0.33 Mn 0.33 Co 0.33 O 2 (NMC) electrode materials was explored. Through refractive index (RI) measurements, the concentration of the binder adsorbed on the surface of electrode materials during electrode processing was determined to be less than half of the potentially available material resulting in excessive free binder in solution. Using ultrasmall-angle neutron scattering (USANS) and small-angle neutron scattering (SANS), it was found that PVDF forms a conformal coating over the entirety of the silicon particle. This is in direct contrast to graphite–PVDF and NMC–PVDF slurries, where PVDF only covers part of the graphite surface, and the PVDF chains make a network-like graphite–PVDF structure. Conversely, a thick layer of PVDF covers NMC particles, but the coating is porous, allowing for ion and electronic transport. The homogeneous coating of silicon breaks up percolation pathways, resulting in poor cycling performance of silicon materials as widely reported. These results indicate that the Si–PVDF interactions could be modified from a binder to a dispersant.

25 ENERGY STORAGE↗

Sequential infiltration of two-photon polymerized 3D photonic crystals for mid-IR spectroscopic applications

Photonic crystals (PhCs) are spatially organized structures with lattice parameters equivalent to the operational wavelength of light. PhCs have been subject to extensive research efforts in the last two decades and are known for controlling light propagation with applications in sensing and time-delayed communication due to the slow-light phenomenon. Despite their exceptional properties, PhCs are difficult to fabricate using planar micromachining techniques due to their periodic structures. Techniques like two-photon stereolithography have been discussed for PhC fabrication in the literature, but the inherent disadvantage of poor refractive index (RI) contrast results in limited application. In this work, we present sequential infiltration synthesis performed on two-photon stereolithographically printed 3D PhCs for infiltration with zinc oxide to increase the RI of 3D PhCs. Further, finite element analysis was performed over a range of RI contrast values to study the change in photonic bandgap (PBG) with RI contrast. The transmission spectra were recorded on 3D PhCs before and after infiltration to demonstrate the change experimentally. An increase in the PBG width and absorbance is seen postinfiltration due to enhanced RI. This work presents the first, to our knowledge, sequentially infiltrated enhanced 3D PhC fabricated with two-photon stereolithography.

3D printing↗

MatLab Package for Whispering Gallery Mode Data

Dye-doped whispering gallery mode resonator (WGMR) microspheres yield highly structured emission spectra that are extremely sensitive to their environment and are of intense interest for use in a variety of sensing applications. Efforts to leverage the unique sensitivities of WGMRs have relied on stringent experimental requirements to correlate specific spectral shifts/changes to an analyte/stimulus such as 1) precise positional knowledge, 2) reference spectra for each microsphere, and 3) high mechanical stability. Consequently, these can hinder adequate mixing or incorporation of analytes and creates challenges for remote sensing. The MATLAB codes provided here are to be used in conjunction with a continuous flow technique for measuring WGM spectra of dye-doped microspheres suspended in solution. One MATLAB script, smooths the data, automatically baseline corrects it to isolate the whispering gallery modes (WGM) from the unwanted bulk emission, and assesses the similarity of each spectrum to aid in selecting a set of unique WGM spectra for further analysis. The next script is designed to analyze WGM spectra to determine the size of the resonator and the refractive index (RI) of its local environment without a priori knowledge of the individual microsphere. The final script allows the user to cluster spheres based on the product of their RI and radius and the contrast ratio of the RI of the sphere material and that of its environment by using a shared nearest neighbor spectral clustering algorithm.

Lilley, Laura↗

Real-time measurement of parametric influences on the refractive index and length changes in silica optical fibers

In this paper, we present a simple cascaded Fabry-Perot interferometer (FPI) that can be used to measure in real-time the refractive index (RI) and length variation in silica optical fibers caused due to external physical parameters, such as temperature, strain, and radiation. As a proof-of-concept, we experimentally demonstrate real-time monitoring of temperature effects on the RI and length and measure the thermo-optic coefficient (TOC) and thermal expansion coefficient (TEC) by using the cascaded FPI within a temperature range of 21–486°C. The experimental results provide a TEC of 5.53 × 10 −7 /°C and TOC of 4.28 × 10 −6 /°C within the specified temperature range. Such a simple cascaded FPI structure will enable the design of optical sensors to correct for measurement errors by understanding the change in RI and length of optical fiber caused by environment parameters.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Enhanced Light Outcoupling from OLEDs Fabricated on Novel Low-Cost Patterned Plastic Substrates of Varying Periodicity

OLEDs continue to make strides in display applications, but their commercial utilization in solid-state lighting (SSL) is lagging. An ongoing challenge, in particular for manufacturing, is the need for enhanced efficiency and hence the necessity to increase in an inexpensive approach the extraction of the light generated inside the OLED into the forward (viewing) hemisphere. In conventional OLEDs fabricated on a transparent flat anode coated on glass, the external quantum efficiency (EQE) is only ~20%. About 50% of the light is lost to internal waveguiding in the high refractive index (RI) organic + ITO anode layers and to surface plasmon polaritons (SPPs) at the organic/metal cathode interface. Another ~30% of the light is externally waveguided in the substrate to its edges. While extraction of the externally waveguided light is commonly addressed by adding a microlens array (MLA) or a scattering layer at the substrate’s air-side, light outcoupling increases by only ~1.6-1.7x (vs up to 2.5x in improving from ~20% to ~50%). The use of a hemispherical lens or an index matching fluid (IMF) at the substrate/photodetector (PD) interface increases the outcoupling by at least 2x; these approaches however, are not viable industrially, and even a MLA is sometimes undesirable due to its non-planar, scattering structure. In multi-stack tandem OLEDs, where the metal cathode is far from the emitting zone(s), the impact of photons loss to SPPs decreases. Our project addressed the ~50% loss to the internally waveguided light and SPPs. We evaluated OLEDs fabricated on patterned or planarized plastic substrates manufactured in a cost-effective approach compatible with a roll-to-roll (R2R) process. The OLEDs were either (i) patterned to various degrees depending on the pitch a and height or depth h of the pattern features or (ii) planar, with a pattern buried under a flat high RI planarization layer. We demonstrated that the outcoupling from green patterned OLEDs reaches ~50% by mitigating plasmon–related loss and internal waveguiding, even without the addition of a MLA, a hemispherical lens, or IMF. Simulations conducted in parallel with the experimental effort demonstrated how diffraction by conformally corrugated OLEDs increases the outcoupling to >60%. Structures with varying pitch values were also simulated indicating that combining domains of varying pitch could increase outcoupling to 55-60%. Experimentally, we additionally assessed the role a and h in determining not only the OLED efficiencies, but also their structural properties, i.e., the uniformity and conformality throughout the OLED stack. As planar OLEDs are preferred over corrugated devices, we studied different patterns in plastic substrates that were planarized by a high RI formulation. Planar green OLEDs on such structures showed enhanced efficiencies with EQEs larger than 60% with the addition of an IMF (to extract the substrate mode) at the substrate/Si PD interface. White OLEDs showed EQEs of 45.5%. Plastic substrates are currently less attractive than glass substrates due to drawbacks such as permeability to water vapor and oxygen, and in some cases thermal instability. Plastic substrates however, are flexible and easy to handle unlike thin flexible glass, and once transparent thin barrier films are available, they will become more attractive; they are already of interest in medical applications. Importantly, as it is easy to generate various patterns in different plastic materials, they provide excellent means for assessing and optimizing enhancing extracting structures. Such structures can also be transferred to glass substrates with some process modifications. The technical effectiveness and economic feasibility of the project lie in the patterning of the extracting plastic substrates in an approach that is scalable to R2R manufacturing. R2R processes are of drastically lower-cost than batch or single-unit fabrication. The patterned plastic can be a part of an integrated substrate either plastic or glass, which includes also a MLA or a planar layer with embedded scattering particles, as well as a conductive metal mesh/electrode design. SSL is environmentally-friendly and as OLED SSL becomes more efficient it will reduce electricity consumption, and hence lighting cost, as well as produce less expensive attractive lighting fixtures. Our university-industry collaboration is hence of major benefit to the public as it demonstrates the feasibility of manufacturing optimized extracting substrates for highly efficient OLEDs for SSL in a future R2R process, which would drastically reduce the manufacturing cost and increase production in the USA. Moreover, newly developed methods by our team allow low-cost roll manufactured substrates to be transferred to flexible or rigid glass substrates, which solves the plastic substrate barrier issues, and when combined with device encapsulation will increase the OLEDs’ environmental stability.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Computational Determination of the Refractive Index of TATB, LLM-105, β-HMX, & α-RDX

In this study, we use Materials Studio CASTEP, an ab initio quantum mechanical (QM) program employing density functional theory (DFT), to compute the refractive index (RI) of solid energetic materials, specifically, PETN (tetragonal phase), TATB, LLM-105, β-HMX, and α-RDX. The use of quantum mechanical DFT methods affords the investigation of the optical mate rial properties of a system without the need for any experimental input. The RI values of PETN and TATB have been experimentally determined previously and are compared here to the QM derived RI values as validation of the theoretical approach in determining material optical proper ties. To date, experimental measurements to determine the RI values for LLM-105 have yet to be determined. This fact obviates the need to determine LLM-105 RI values using quantum mechanical means.

36 MATERIALS SCIENCE↗

Numerical Analysis of Radiation Effects on Fiber Optic Sensors

Optical fiber sensors (OFS) are a potential candidate for monitoring physical parameters in nuclear environments. However, under an irradiation field the optical response of the OFS is modified via three primary mechanisms: (i) radiation-induced attenuation (RIA), (ii) radiation-induced emission (RIE), and (iii) radiation-induced compaction (RIC). For resonance-based sensors, RIC plays a significant role in modifying their performance characteristics. In this paper, we numerically investigate independently the effects of RIC and RIA on three types of OFS widely considered for radiation environments: fiber Bragg grating (FBG), long-period grating (LPG), and Fabry-Perot (F-P) sensors. In our RIC modeling, experimentally calculated refractive index (RI) changes due to low-dose radiation are extrapolated using a power law to calculate density changes at high doses. The changes in RI and length are subsequently calculated using the Lorentz–Lorenz relation and an established empirical equation, respectively. The effects of both the change in the RI and length contraction on OFS are modeled for both low and high doses using FIMMWAVE, a commercially available vectorial mode solver. An in-depth understanding of how radiation affects OFS may reveal various potential OFS applications in several types of radiation environments, such as nuclear reactors or in space.

42 ENGINEERING↗

Active Compensation of Radiation Effects on Optical Fibers for Sensing Applications

Neutron and gamma irradiation is known to compact silica, resulting in macroscopic changes in refractive index (RI) and geometric structure. The change in RI and linear compaction in a radiation environment is caused by three well-known mechanisms: (i) radiation-induced attenuation (RIA), (ii) radiation-induced compaction (RIC), and (iii) radiation-induced emission (RIE). These macroscopic changes induce errors in monitoring physical parameters such as temperature, pressure, and strain in optical fiber-based sensors, which limit their application in radiation environments. We present a cascaded Fabry–Perot interferometer (FPI) technique to measure macroscopic properties, such as radiation-induced change in RI and length compaction in real time to actively account for sensor drift. The proposed cascaded FPI consists of two cavities: the first cavity is an air cavity, and the second is a silica cavity. The length compaction from the air cavity is used to deduce the RI change within the silica cavity. We utilize fast Fourier transform (FFT) algorithm and two bandpass filters for the signal extraction of each cavity. Inclusion of such a simple cascaded FPI structure will enable accurate determination of physical parameters under the test.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Molecular Weight Distribution Analysis of Pyrolysis Oils by Gel Permeation Chromatography

Comprehensive analysis of the molecular weight distribution of raw and catalytic fast pyrolysis oils derived from biomass remains a key technical hurdle to understanding oil quality as it relates to downstream use and multiple methods may be necessary to accurately represent all components present. Here, we report the molecular weight distribution metrics of fast pyrolysis (FP) and catalytic fast pyrolysis (CFP) oils as determined by gel permeation chromatography (GPC) combined with UV-diode array (UV), differential refractive index (RI), and multi-angle laser light scattering (MALS) detection. The measured molar mass distributions revealed that FP oil consisted of a higher proportion of larger products relative to the low molecular weight products contained in the CFP oil. GPC/RI and UV methods showed FP oil to have higher weight-average molecular weight (Mw) and number-average molecular weight (Mn) than CFP oil based on elution time. However, GPC/MALS, determined the two oils to have similar overall molecular weight distribution metrics (Mw and Mn) and yielded values significantly higher than those determined by RI and UV detectors relative to external standards. Overall, the use of a multiple detection GPC method could enable a more accurate comparison and determination of true molecular weight metrics of bio-oils.

BIOMASS FUELS↗

High Refractive Index Adhesives for Laser Glass Cladding Applications (ABBREVIATED Report)

To eliminate parasitic light oscillations (amplified spontaneous emission (ASE)), high energy laser systems often utilize polymeric materials to adhere optically absorptive cladding materials to laser gain media (glass or crystal). Most of these polymeric optical adhesives are index matched to lower index gain media, and there was no capability to achieve refractive indices (RI) greater than 1.60 with low color, while also maintaining mechanical compliance to serve as adhesives for cladding applications. The completion of LDRD 23-FS-043 shows we can chemically develop novel suitable adhesive candidates with refractive indices above 1.64 at 532 nm while also exhibiting Shore A hardness between 50-90, with high optical clarity, low color, and minimal haze for films ~1-2 mm thick (84 %Transmission at 532 nm). This will enable us to begin mapping a process space to allow future customizable adhesive formulations for building a variety of laser systems with tunable refractive index matching for various gain and cladding media.

36 MATERIALS SCIENCE↗