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At least 55 records · Page 3

Temporal and spatial tuning of optical constants in praseodymium doped ceria by electrochemical means

Abstract Temporal and spatial tuning of the refractive index of optical thin films is desired for flat optics applications. The redistribution of mobile ions in mixed ionic-electronic conductors (MIEC) has been demonstrated to serve as a viable means for achieving optical tuning down to the nanoscale. Here we studied the dynamic range of the optical tuning achievable in the refractive index, in the MIEC oxide – Pr x Ce 1− x O 2− δ (PCO), for x = 0.1, 0.2 and 0.4, at 500 °C, by in-situ spectrophotometry. Significant increases in the modulation of both the imaginary and real optical constants in the visible and the adjacent spectra were obtained for increased doping levels. Device employing an electrochemical titration method was implemented to modulate the oxygen concentration, and thereby the optical transmission of PCO. Incorporation of a patterned top electrode allowed for the demonstration of spatial control of PCO thin film properties by in-situ video imaging of the optical switching process. The electrochemically induced optical state is shown to remain non-volatile upon quenching the device to room temperature under applied bias.

36 MATERIALS SCIENCE↗

Testing and Characterization to Develop a Mechanistic Explanation for Unsaturated Drift of Fiber Optic Sensors during High-Dose Irradiation

The primary limitation for any optical fiber-based sensor for nuclear reactor applications is radiation-induced attenuation (RIA) of the transmitted and/or reflected signals. Based on several recent studies, RIA is tolerable for some fused silica optical fibers with the proper choice of sensing wavelength and fiber dopants. For extreme temperature applications (> 1000°C), sapphire optical fibers have been proposed; however, recent optical transmission measurements performed on bulk sapphire samples showed prohibitively large RIA. For some sensors, radiation-induced dimensional changes in the fiber materials can also cause significant drift. Moreover, the drift that was observed in numerous experiments performed in the High Flux Isotope Reactor (HFIR), the Advanced Test Reactor, the Massachusetts Institute of Technology Reactor, and other international facilities far exceeded what would be expected based on compaction of fused silica glass. Clearly, additional work is needed to better understand the origins of both RIA and radiation-induced drift in both silica and sapphire optical fiber-based sensors before these sensors can be reliably deployed for nuclear applications. This work evaluated the underlying mechanisms that may be responsible for RIA and drift in silica and sapphire materials. First, detailed characterization was performed on bulk fused silica glass samples that were previously irradiated to different neutron fluences at different temperatures to better understand the structural changes that drive radiation-induced drift in the absence of coating effects that are discussed later. Results show that the non-monotonic compaction that occurs with increasing neutron fluence continues up to fast neutron fluences approaching 10 22 n/cm 2 , which has important implications for physics-based models that may be used to compensate for the sensor drift. Initial Raman spectroscopy and synchrotron x-ray diffraction provide insights into the nature of the structural changes. Next, detailed characterizations were performed on silica fibers with various coatings that were subjected to several different thermal treatments. The hypothesis is that the coatings convert to carbon-rich materials that compact under irradiation, putting a large compressive strain on the fiber. Out-of-pile testing confirms that both polyimide and acrylate fiber coatings convert to glassy carbon (GC) materials when heated under inert conditions, and the degree of order (i.e., graphitization) increases with increasing temperature. The results provide increasingly strong evidence that the combination of polymeric coatings and inert (or vacuum) conditions render fiber optic sensors susceptible to significant radiation-induced drift that would not otherwise exist in uncoated fibers. Finally, transmission electron microscopy was performed on bulk sapphire samples that were irradiated to two neutron fluences at different temperatures to gain insights into the potential mechanisms driving the prohibitive RIA at higher neutron fluences and temperatures. Contrary to previous hypotheses, results show that scattering from radiation-induced voids cannot explain the observed RIA. Similarly, models for scattering losses from dislocation loops also do not agree with the experimental results. Instead, fitting to the experimental data shows that increased absorption from aluminum vacancy centers is the most likely explanation for the the prohibitively large RIA that was observed at high irradiation temperature and dose. In addition, the voids that formed in these single-crystal samples were found to align along the basal plane (a-axis) as opposed to that seen in previous observations of c-axis alignment in polycrystalline samples, which could have important implications for anisotropic swelling and other phenomena that could affect sensor performance at high neutron fluence.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Testing and Characterization to Develop a Mechanistic Explanation for Unsaturated Drift of Fiber Optic Sensors during High-Dose Irradiation

The primary limitation for any optical fiber-based sensor for nuclear reactor applications is radiation-induced attenuation (RIA) of the transmitted and/or reflected signals. Based on several recent studies, RIA is tolerable for some fused silica optical fibers with the proper choice of sensing wavelength and fiber dopants. For extreme temperature applications (> 1000°C), sapphire optical fibers have been proposed; however, recent optical transmission measurements performed on bulk sapphire samples showed prohibitively large RIA. For some sensors, radiation-induced dimensional changes in the fiber materials can also cause significant drift. Moreover, the drift that was observed in numerous experiments performed in the High Flux Isotope Reactor (HFIR), the Advanced Test Reactor, the Massachusetts Institute of Technology Reactor, and other international facilities far exceeded what would be expected based on compaction of fused silica glass. Clearly, additional work is needed to better understand the origins of both RIA and radiation-induced drift in both silica and sapphire optical fiber-based sensors before these sensors can be reliably deployed for nuclear applications. This work evaluated the underlying mechanisms that may be responsible for RIA and drift in silica and sapphire materials. First, detailed characterization was performed on bulk fused silica glass samples that were previously irradiated to different neutron fluences at different temperatures to better understand the structural changes that drive radiation-induced drift in the absence of coating effects that are discussed later. Results show that the non-monotonic compaction that occurs with increasing neutron fluence continues up to fast neutron fluences approaching 10 22 n/cm 2 , which has important implications for physics-based models that may be used to compensate for the sensor drift. Initial Raman spectroscopy and synchrotron x-ray diffraction provide insights into the nature of the structural changes. Next, detailed characterizations were performed on silica fibers with various coatings that were subjected to several different thermal treatments. The hypothesis is that the coatings convert to carbon-rich materials that compact under irradiation, putting a large compressive strain on the fiber. Out-of-pile testing confirms that both polyimide and acrylate fiber coatings convert to glassy carbon (GC) materials when heated under inert conditions, and the degree of order (i.e., graphitization) increases with increasing temperature. The results provide increasingly strong evidence that the combination of polymeric coatings and inert (or vacuum) conditions render fiber optic sensors susceptible to significant radiation-induced drift that would not otherwise exist in uncoated fibers. Finally, transmission electron microscopy was performed on bulk sapphire samples that were irradiated to two neutron fluences at different temperatures to gain insights into the potential mechanisms driving the prohibitive RIA at higher neutron fluences and temperatures. Contrary to previous hypotheses, results show that scattering from radiation-induced voids cannot explain the observed RIA. Similarly, models for scattering losses from dislocation loops also do not agree with the experimental results. Instead, fitting to the experimental data shows that increased absorption from aluminum vacancy centers is the most likely explanation for the the prohibitively large RIA that was observed at high irradiation temperature and dose. In addition, the voids that formed in these single-crystal samples were found to align along the basal plane (a-axis) as opposed to that seen in previous observations of c-axis alignment in polycrystalline samples, which could have important implications for anisotropic swelling and other phenomena that could affect sensor performance at high neutron fluence.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Conceptual design and performance predictions for 2D beam emission spectroscopy turbulence measurements at Wendelstein 7-X

A conceptual design for a 2D beam emission spectroscopy diagnostic system to measure ion gyro-scale plasma turbulence at Wendeslstein 7-X is described. The conceptual design identifies field-aligned viewing geometries and ports for cross-field turbulence measurements in the neutral beam volume. A 2D sightline grid covers the outer plasma region, and the grid configuration provides sufficient k-space coverage in radial and poloidal directions for ion temperature gradient and trapped-electron mode turbulence measurements. Emission intensity estimates, optical transmission losses, and detector noise levels indicate that the measurements will be sensitive to plasma density fluctuations as small as δn/n ≈ 0.5% with a bandwidth of 1 MHz. Implementation challenges include a small beam emission Doppler shift due to nearly radial heating beams and reduced optical throughput due to collection aperture limitations.

47 OTHER INSTRUMENTATION↗

Observation of interacting polaronic gas behavior in Ta-doped TiO 2 thin films via terahertz time-domain spectroscopy

Transparent conductive oxides (TCOs)—materials that have the twin desirable features of high optical transmission and electrical conductivity—play an increasingly significant role in the fields of photovoltaics and information technology. As an excellent TCO, Ta-doped anatase TiO 2 shows great promise for a wide range of applications. Here, terahertz time-domain spectroscopy is used to study the complex optical conductivity $\tilde{σ}$ (ω) of the TCO—heavily Ta-doped TiO 2 thin films with different Ta-doping concentrations, in the frequency range of 0.3–2.7 THz and the temperature range of 10–300 K. Fitting the complex optical conductivity to a Drude-like behavior allows us to extract the temperature dependence of the effective mass, which suggests the existence of many-body large polarons. Moreover, the carrier scattering rate of Ta-doped TiO 2 with different carrier concentrations agrees with the interacting polaron gas theory. Our results suggest that with increasing electron density in TiO 2 , the interaction between polarons is larger and electron–phonon coupling is smaller, which is beneficial for achieving high mobility and conductivity in TiO 2 .

36 MATERIALS SCIENCE↗

Second-harmonic and linear spectroscopy of $\textit{α}$-In 2 Se 3

We report spectroscopic measurements of optical transmission, ellipsometry, and second-harmonic generation (SHG) from as-grown vapor-deposited $\textit{α}$-In 2 Se 3 nanoflakes ranging in thickness from a single quintuple layer (QL) to bulk material. In this work, we compare these measurements with ab initio calculations of structural and optical properties. Linear optical measurements yield thickness-dependent band gaps and dielectric functions, while SHG diagnoses microscopic film structure and ferroelectric polarization. The rotational anisotropy of SHG for s-polarized incident photons of energy 1.4 eV reveals crystalline symmetry and orientation of individual QLs. Peak SHG intensity increases from one to three QLs, then decreases for larger numbers, tracking thickness-dependent trends in the second-order susceptibility components $χ^{xxx}$ and $χ^{zxx}$. Comparison of measured and calculated SHG spectra for s-polarized photons of energies between 1.2 and 1.7 eV incident upon two QL samples discriminates among candidate stacking arrangements, and favors an arrangement with electric polarization vectors of the two QLs pointing outward in opposite directions.

36 MATERIALS SCIENCE↗

Ex situ calibration of the scattered-light time-history diagnostic on the National Ignition Facility

The scattered-light time-history diagnostic (SLTD) suite measures time-resolved scattered light in three wavelength bands: stimulated Brillouin scattering (350–352 nm), stimulated Raman scattering (430–760 nm), and plasma emission at half the laser frequency (695–735 nm), at 15 locations around the National Ignition Facility (NIF) target chamber. The SLTD, along with the full-aperture backscatter station (FABS), collects scattered light from direct- and indirect-drive inertial confinement fusion experiments. The SLTD calibration was revisited after a discrepancy between FABS and SLTD measurements was observed on NIF polar direct-drive experiments. An integrated calibration of the SLTD was performed for the first time, and individual components were also calibrated for the wavelengths of 351, 527, and 532 nm. The optical transmission of the instrument was measured to be (1.12 ± 0.04) × 10 –7 and (1.96 ± 0.11) × 10 –7 for the wavelengths of 351 and 532 nm, respectively. The revised calibration at 351 nm brings the SLTD measured scattered energy in agreement with the FABS measured scattered energy after additionally accounting for the degradation of an optical element in FABS. Furthermore, this decreased the inferred absorption by 7% for a representative experiment. However, discrepancies remain between FABS and SLTD measurements in the SRS band (532 nm).

47 OTHER INSTRUMENTATION↗

Raman Wavelength Conversion in Ionic Liquids

Here, we explore the use of room-temperature ionic liquids (ILs) as Raman wavelength converters. ILs provide an engineerable framework to design suitable liquids for wavelength conversion over a broad spectral range, through careful selection of the molecular structures of the IL anions and cations so that specific characteristics can be obtained, such as a desirable Raman shift, low Brillouin scattering, and good optical transmission in the pump and Stokes wavelengths. Applying such criteria, we demonstrate that 1-ethyl-3-methylimidazolium dicyanamide (EMIM DCA) is an effective medium for conversion of 532-nm pulses from a Q-switched Nd :YAG laser to 603 nm. This corresponds to an approximate 2200 cm –1 shift, which can be used to generate mid-infrared radiation through subsequent difference frequency generation for optical pumping of CO 2 lasers. Threefold-higher Raman conversion efficiency is obtained in EMIM DCA compared with water under identical conditions in a proof-of-principle single-pass conversion setup, resulting in an efficient generation of multimillijoule, <6 ns duration, high-quality orange laser pulses in a wavelength region that is difficult to access at high energies. Consequently, we examine ILs representing two other classes of Raman-active functional groups and obtain conversion up to the fifth-order Stokes shift and first anti-Stokes shift. Through the tunable selection of their components and their useful dynamical properties, ILs provide a platform for efficient, simple, and alignment-tolerant high-energy Raman shifting with numerous industrial and technological applications.

74 ATOMIC AND MOLECULAR PHYSICS↗

Active Tuning of Optical Constants in the Visible–UV: Praseodymium-Doped Ceria—a Model Mixed Ionic–Electronic Conductor

Mixed ionic-electronic conductors offer chemical and electrical means for active tuning of their optical constants, e.g. with variations in oxygen non-stoichiometry in Pr 0.1 Ce 0.9 O 2-δ , enabling implementation of adaptive thin film optical devices. Here, we demonstrate in-situ chemo-tuning of the extinction coefficient in Pr 0.1 Ce 0.9 O 2-δ at elevated temperatures and provide a tuning model that treats the interdependence of mobile oxygen vacancies and small polarons coupled to variations in optically active praseodymium ions. Further, a new means for electro-tuning of the optical constants of mixed ionic-electronic conductors was demonstrated experimentally and modeled for Pr 0.1 Ce 0.9 O 2-δ thin films deposited on grid-like electrode structures. Modeling of non-steady state optical transmittance modulations in the latter allows for estimation of oxygen vacancy mobility that determines the switching speed of the device. Quenched-in values of nr and k to room temperature become nonvolatile, providing a modulation range in the extinction coefficient of Δk ~0.1 (change of ~800%) and in the refractive index of Δn r ~0.1 (relative to initial n r of ~2.35). Key figures of merit including, transmission optical modulation of ~0.04 per 1 mV nm -1 , switching energy per area of 670 pJ μm -2 and switching times of seconds, were demonstrated, with further improvements possible.

36 MATERIALS SCIENCE↗

Magnetic and Optical Properties of Au–Co Solid Solution and Phase-Separated Thin Films and Nanoparticles

The chemical composition and morphology of Au x Co 1–x thin films and nanoparticles are controlled via a combination of cosputtering, pulsed laser-induced dewetting (PLiD), and annealing, leading to tunable magnetic and optical properties. Regardless of chemical composition, the as-deposited thin films and as-PLiD nanoparticles are found to possess a face-centered cubic (FCC) Au x Co 1–x solid-solution crystal structure. Annealing results in large phase-separated grains of Au and Co in both the thin films and nanostructures for all chemical compositions. The magnetic and optical properties are characterized via vibrating sample magnetometry (VSM), ellipsometry, optical transmission spectroscopy, and electron energy loss spectroscopy (EELS). Despite the exceptionally high magnetic anisotropy inherent to Co, the presence of sufficient Au (72 atom %) in the Au x Co 1–x solid solution results in superparamagnetic thin films. Among the as-PLiD nanoparticle samples, an increased Co composition leads to a departure from traditional ferromagnetism in favor of wasp-waisted hysteresis caused by magnetic vortices. Phase separation resulting from annealing leads to ferromagnetism for all compositions in both the thin films and nanoparticles. The optical properties of Au x Co 1–x nanostructures are also largely influenced by the chemical morphology, where the Au x Co 1–x intermixed solid solution has significantly damped plasmonic performance relative to pure Au and comparable to pure Co. Phase separation greatly enhances the quality factor, optical absorption, and electron energy loss spectroscopy (EELS) signatures. The enhancement of the localized surface plasmon resonances (LSPRs) scales with the reduction in Co composition, despite EELS evidence that excitation of the Co portions of a nanoparticle can provide a similar, and in some instances enhanced, LSPR resonance compared to Au. This behavior, however, is seemingly limited to the LSPR dipole mode, while higher-order modes are greatly damped by a Co aloof position. As a result, this observed magneto-plasmonic functionality and tunability could be applicable in biomedicine, namely, cancer therapeutics.

annealing (metallurgy)↗

A transmissive concentrator photovoltaic module with cells directly cooled by silicone oil for solar cogeneration systems

Hybrid concentrator photovoltaic-thermal systems can cogenerate electricity and heat by beam-splitting incoming concentrated light onto photovoltaic cells and a thermal receiver to increase total conversion efficiency and potentially reduce system cost. To demonstrate this, we have designed and prototyped a transmissive spectrum-splitting concentrator photovoltaic module that maximizes solar energy conversion by utilizing the entire solar spectrum. Visible light is collected using infrared-transmissive triple-junction photovoltaic cells to achieve an in-band module efficiency of 43.3% for light of wavelength λ < 873 nm, while 44.2% of out-of-band light with λ > 873 nm is transmitted through for collection by a thermal receiver. During testing on a dual-axis tracked parabolic concentrator dish at up to 166 suns, cell temperatures were maintained at 119 °C or below via a novel active cooling method. This cooling system strictly flows silicone oil directly across both sides of the cells, without inhibiting optical transmission, as verified through experimentation and simulation. The module was validated outdoors for 572 sun·hrs, and achieved a maximum thermal receiver temperature of 180 °C. 86.1% of incident solar power is collected at 166 suns average concentration collectively among the electrical, cooling, and thermal receiver subsystems. The remaining 13.9% is lost to mirror reflectivity, dish shadowing, receiver reflection, and thermal losses. The ability to directly cool the cells with an inert silicone oil offers the potential for reduced system cost relative to previous transmissive hybrid concentrator photovoltaic-thermal systems, including microfluidic-cooled designs. This solar cogeneration capability is valuable in a wide range of commercial and industrial applications.

14 SOLAR ENERGY↗

Integrating fiber optic sensors into metallic components for sensing in harsh environments

The integration of fiber optic sensors into high-temperature materials is critical for real-time monitoring and autonomous operation of engineering systems. This study demonstrated a spark plasma sintering (SPS)-assisted embedding process for integrating sapphire fiber optic sensors into stainless steel components during part fabrication. Optical fibers were encapsulated in stainless steel 316L powders which were sintered at different fabrication conditions using SPS to investigate the effects of sintering parameters on the embedment. Measurements of optical transmittance, combined with microstructural analysis (X-ray computed tomography and scanning electron microscopy) and mechanical testing (tensile and microhardness), were conducted to examine the fiber functionality, fiber–matrix bonding quality, and properties of the sintered materials. Here, the results show that under suitable fabrication conditions, intact optical fibers can be encapsulated in highly-densified (>98 % relative density) stainless steel components. These conditions also led to a good bond at the fiber–matrix interface with micron-sized material interdiffusion across the interface. The sintering parameters were observed to affect fiber optical attenuation, where high temperature, pressure, and hold time during SPS enhanced fiber–matrix bonding and adversely affected optical transmission. Tensile testing confirmed the superior tensile strength and ductility of the matrix fabricated by SPS. Furthermore, the materials exhibited limited strength reduction (~70 MPa) upon the integration of fibers. This study demonstrates the effectiveness of SPS for fiber-material integration for high-temperature applications.

36 MATERIALS SCIENCE↗

High-Temperature 2D Optical Relaxation Visualizes Enhanced Oxygen Exchange Kinetics at Metal-Mixed Conducting Oxide Interfaces

Solid-state heterointerfaces are of interest for emergent local behavior that is distinct from either bulk parent compound. One technologically relevant example is the case of mixed ionic/electronic conductor (MIEC)–metal interfaces, which play an important role in electrochemistry. Metal–MIEC composite electrodes can demonstrate improved catalytic activity vs single-phase MIECs, improving fuel cell efficiency. Similarly, MIEC surface reaction kinetics are often evaluated using techniques that place metal current collectors in contact with the surface under evaluation, potentially altering the response vs the native surface. Here, techniques enabling direct and local in situ observation of the behavior at and around such heterointerfaces are needed. Here, we develop a spatially resolved optical transmission relaxation (2D-OTR) method providing continuous evaluation of local, high-temperature, controlled atmosphere defect kinetics across a ~1 cm2 sample area simultaneously in a contact-free manner. We apply it to observe the spatial variance of oxygen incorporation and evolution rates at ~525–620 °C, in response to step changes in oxygen partial pressure, on MIEC SrTi 0.65 Fe 0.35 O 3–x films as a function of distance from porous Pt and Au layers. Using this model geometry, we find significant enhancements in kinetics adjacent to the metals that decay over a few millimeter distance. To extract kinetic parameters, we fit the short-term optical data (initial portion of relaxations) with an exponential decay function appropriate for surface-exchange-limited kinetics, yielding apparent surface exchange coefficients (k chem ) with spatial resolution, decreasing with distance from the metal. To understand the kinetic processes governing the complete (long-term) optical relaxations, we performed COMSOL simulations, which demonstrated that a combination of laterally varying k chem and in-plane diffusion controls the observed kinetics over the full time range. Further support for spatially varying kchem comes from demonstrations of changing surface and bulk chemistry vs distance from the metal–MIEC interface, by X-ray photoelectron and optical absorption spectroscopies, respectively. Although microporous Pt and Au are not excellent electrodes in isolation, both metals exert a synergistic effect on the oxygen surface exchange rate in the presence of the mixed conducting film.

36 MATERIALS SCIENCE↗

Engineering the temporal dynamics of all-optical switching with fast and slow materials

Abstract All-optical switches control the amplitude, phase, and polarization of light using optical control pulses. They can operate at ultrafast timescales – essential for technology-driven applications like optical computing, and fundamental studies like time-reflection. Conventional all-optical switches have a fixed switching time, but this work demonstrates that the response-time can be controlled by selectively controlling the light-matter-interaction in so-called fast and slow materials. The bi-material switch has a nanosecond response when the probe interacts strongly with titanium nitride near its epsilon-near-zero (ENZ) wavelength. The response-time speeds up over two orders of magnitude with increasing probe-wavelength, as light’s interaction with the faster Aluminum-doped zinc oxide (AZO) increases, eventually reaching the picosecond-scale near AZO’s ENZ-regime. This scheme provides several additional degrees of freedom for switching time control, such as probe-polarization and incident angle, and the pump-wavelength. This approach could lead to new functionalities within key applications in multiband transmission, optical computing, and nonlinear optics.

42 ENGINEERING↗

Uncovering surface plasmon optical resonances in nanohole arrays through interferometric photoemission electron microscopy

In this work, the role of surface plasmon polaritons (SPPs) in nanohole array optical extinction spectra is explored using a time-resolved technique capable of isolating the air/metal interfacial SPP contribution to the typical Fano profile in optical transmission curves. A pair of interferometrically locked broad-band femtosecond pulses is used to launch SPPs from lithographically patterned plasmonic nanohole arrays. SPPs launched in the co- and counter-propagating directions are probed using a third probe pulse in a photoemission electron microscope. Using this approach, we record interferometric SPP–SPP linear autocorrelations that selectively report on the resonances of SPPs launched from arrays of varying pitches and hole diameters. Aside from advancing an approach to selective SPP spectroscopy, we illustrate that resonant coupling in the counter-propagating direction may be exploited to control the spatial, temporal, and spectral characteristics of SPPs. For the counter-propagating direction, we show that tuning the array pitch near the fundamental plasmon resonance generates color-tuned (~770–820 nm), narrow bandwidth SPPs, and the bandwidth may be controlled by changing the ratio of pitch to hole diameter. The SPP resonances we recover through Fourier transforms of the interferometric autocorrelations shed light on the classical problem of Fano interference in nanohole array extinction spectra.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

On-chip frequency-bin quantum photonics

Abstract Frequency-bin encoding furnishes a compelling pathway for quantum information processing systems compatible with established lightwave infrastructures based on fiber-optic transmission and wavelength-division multiplexing. Yet although significant progress has been realized in proof-of-principle tabletop demonstrations, ranging from arbitrary single-qubit gates to controllable multiphoton interference, challenges in scaling frequency-bin processors to larger systems remain. In this Perspective, we highlight recent advances at the intersection of frequency-bin encoding and integrated photonics that are fundamentally transforming the outlook for scalable frequency-based quantum information. Focusing specifically on results on sources, state manipulation, and hyperentanglement, we envision a possible future in which on-chip frequency-bin circuits fulfill critical roles in quantum information processing, particularly in communications and networking.

electro-optic modulators↗

Direct Evidence of Graphene-Induced Molecular Reorientation in Polymer Films

For the first time, direct evidence of graphene-induced molecular reorientation in polymer films using polarization modulated infrared reflection absorption spectroscopy (PMIRRAS) are presented. By creating favorable electrostatic interactions, graphene-polymer interfaces can be controlled by varying polymer and solvent composition. After trans of unmodified graphene from copper onto a polymer substrate, polymer chain rearrangement relative to the orientation at the polymer-copper interface is observed using PM-IRRAS. Transfer success is characterized using both optical transmission measurements and Raman spectroscopy to quantify the transfer fidelity, i.e. graphene coverage fraction. Taken together, oxygencontaining poly(ethylene-co-vinyl acetate) shows more polymer chain rearrangement and better graphene coverage compared to oxygen-free polyethylene. Polymer composition seems to dominate graphene-polymer interactions while solvent choice has a smaller effect on transfer quality. These results are the first direct measurement of this effect and point towards the possibility of engineering graphene-polymer interactions for specific applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hyper-Raman spectroscopy of CeO 2

Cerium dioxide (CeO 2 ) belongs to the fluorite structure group (Oh 5 point group) resulting in one Raman active T 2g mode and two IR active T 1u TO and LO modes. The T 2g Raman band in CeO 2 has been used to probe the symmetric Ce-O vibrational mode of different sized nanoparticulates. Far infrared studies of the Ce-O interactions are difficult to conduct due to low optical transmission, efficiency of the detector and water absorption bands interfering with the measurements. The selection rules of hyper-Raman spectroscopy (HRS) allow the study of IR bands in the far infrared spectral region, such as the motion of the Ce atoms. For the first time, HRS was used to investigate the T 1u TO and LO IR modes in CeO 2 . The position and full-width half-maximum (FWHM) of the TO and LO bands in the HRS spectrum were used to investigate the spectral response in relation to particle size (i.e., phonon confinement). The investigation of CeO2 with HRS provides a research platform for future work in the study of ThO 2 , UO 2 and PuO 2 IR modes.

74 ATOMIC AND MOLECULAR PHYSICS↗