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Thermal conductivity of (Ge2Sb2Te5)1–xCx phase change films

Journal of Applied Physics

Scott, Ethan A.; Ziade, Elbara Z.; Saltonstall, Christopher B.; McDonald, Anthony E.; Rodriguez, Mark A.; Hopkins, Patrick E.; Beechem, Thomas E.; Adams, David P.

Germanium–antimony–telluride has emerged as a nonvolatile phase change memory material due to the large resistivity contrast between amorphous and crystalline states, rapid crystallization, and cyclic endurance. Improving thermal phase stability, however, has necessitated further alloying with optional addition of a quaternary species (e.g., C). In this work, the thermal transport implications of this additional species are investigated using frequency-domain thermoreflectance in combination with structural characterization derived from x-ray diffraction and Raman spectroscopy. Specifically, the room temperature thermal conductivity and heat capacity of (Ge2Sb2Te5)1–xCx are reported as a function of carbon concentration (x ≤ 0:12) and anneal temperature (T ≤ 350 °C) with results assessed in reference to the measured phase, structure, and electronic resistivity. Phase stability imparted by the carbon comes with comparatively low thermal penalty as materials exhibiting similar levels of crystallinity have comparable thermal conductivity despite the addition of carbon. The additional thermal stability provided by the carbon does, however, necessitate higher anneal temperatures to achieve similar levels of structural order.

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Enhancing graphene plasmonic device performance via its dielectric environment

Physical Review Applied

Jarzembski, Amun J.; Goldflam, Michael G.; Siddiqui, Aleem M.; Ruiz, Isaac R.; Beechem, Thomas E.

Graphene plasmons provide a compelling avenue toward chip-scale dynamic tuning of infrared light. Dynamic tunability emerges through controlled alterations in the optical properties of the system defining graphene's plasmonic dispersion. Typically, electrostatic induced alterations of the carrier concentration in graphene working in conjunction with mobility have been considered the primary factors dictating plasmonic tunability. We find here that the surrounding dielectric environment also plays a primary role, dictating not just the energy of the graphene plasmon but so too the magnitude of its tuning and spectral width. To arrive at this conclusion, poles in the imaginary component of the reflection coefficient are used to efficiently survey the effect of the surrounding dielectric on the tuning of the graphene plasmon. By investigating several common polar materials, optical phonons (i.e., the Reststrahlen band) of the dielectric substrate are shown to appreciably affect not only the plasmon's spectral location but its tunability, and its resonance shape as well. In particular, tunability is maximized when the resonances are spectrally distant from the Reststrahlen band, whereas sharp resonances (i.e., high-Q) are achievable at the band's edge. These observations both underscore the necessity of viewing the dielectric environment in aggregate when considering the plasmonic response derived from two-dimensional materials and provide heuristics to design dynamically tunable graphene-based infrared devices.

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Nanoantenna-Enhanced Resonant Detectors for Improved Infrared Detector Performance

Goldflam, Michael G.; Anderson, Evan M.; Fortune, Torben R.; Klem, John F.; Hawkins, Samuel D.; Davids, Paul D.; Campione, Salvatore; Pung, Aaron J.; Webster, Preston T.; Weiner, Phillip H.; Finnegan, Patrick S.; Wendt, Joel R.; Wood, Michael G.; Haines, Chris H.; Coon, Wesley T.; Olesberg, Jonathon T.; Shaner, Eric A.; Kadlec, Clark N.; Beechem, Thomas E.; Sinclair, Michael B.; Tauke-Pedretti, Anna; Kim, Jin K.; Peters, D.W.

Abstract not provided.

Complexion dictated thermal resistance with interface density in reactive metal multilayers

Physical Review B

Saltonstall, Christopher B.; McClure, Zachary D.; Abere, Michael J.; Guzman, David; Reeve, Samuel T.; Strachan, Alejandro; Kotula, Paul G.; Adams, David P.; Beechem, Thomas E.

Multilayers composed of aluminum (Al) and platinum (Pt) exhibit a nonmonotonic trend in thermal resistance with bilayer thickness as measured by time domain thermoreflectance. The thermal resistance initially increases with reduced bilayer thickness only to reach a maximum and then decrease with further shrinking of the multilayer period. These observations are attributed to the evolving impact of an intermixed amorphous complexion approximately 10 nm in thickness, which forms at each boundary between Al- and Pt-rich layers. Scanning transmission electron microscopy combined with energy dispersive x-ray spectroscopy find that the elemental composition of the complexion varies based on bilayer periodicity as does the fraction of the multilayer composed of this interlayer. These variations in complexion mitigate boundary scattering within the multilayers as shown by electronic transport calculations employing density-functional theory and nonequilibrium Green's functions on amorphous structures obtained via finite temperature molecular dynamics. The lessening of boundary scattering reduces the total resistance to thermal transport leading to the observed nonmonotonic trend thereby highlighting the central role of complexion on thermal transport within reactive metal multilayers.

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Monolithically fabricated tunable long-wave infrared detectors based on dynamic graphene metasurfaces

Applied Physics Letters

Goldflam, Michael G.; Ruiz, Isaac R.; Howell, S.W.; Tauke-Pedretti, Anna; Anderson, Evan M.; Wendt, J.R.; Finnegan, P.; Hawkins, Samuel D.; Coon, W.; Fortune, Torben R.; Shaner, Eric A.; Kadlec, Clark N.; Olesberg, Jonathon T.; Klem, John F.; Webster, Preston T.; Sinclair, Michael B.; Kim, Jin K.; Peters, D.W.; Beechem, Thomas E.

Here, the design, fabrication, and characterization of an actively tunable long-wave infrared detector, made possible through direct integration of a graphene-enabled metasurface with a conventional type-II superlattice infrared detector, are reported. This structure allows for post-fabrication tuning of the detector spectral response through voltage-induced modification of the carrier density within graphene and, therefore, its plasmonic response. These changes modify the transmittance through the metasurface, which is fabricated monolithically atop the detector, allowing for spectral control of light reaching the detector. Importantly, this structure provides a fabrication-controlled alignment of the metasurface filter to the detector pixel and is entirely solid-state. Using single pixel devices, relative changes in the spectral response exceeding 8% have been realized. These proof-of-concept devices present a path toward solid-state hyperspectral imaging with independent pixel-to-pixel spectral control through a voltage-actuated dynamic response.

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Uncertainty in linewidth quantification of overlapping Raman bands

Review of Scientific Instruments

Saltonstall, Christopher B.; Beechem, Thomas E.; Amatya, Jatin; Floro, Jerrold; Norris, Pamela M.; Hopkins, Patrick E.

Spectral linewidths are used to assess a variety of physical properties, even as spectral overlap makes quantitative extraction difficult owing to uncertainty. Uncertainty, in turn, can be minimized with the choice of appropriate experimental conditions used in spectral collection. In response, we assess the experimental factors dictating uncertainty in the quantification of linewidth from a Raman experiment highlighting the comparative influence of (1) spectral resolution, (2) signal to noise, and (3) relative peak intensity (RPI) of the overlapping peaks. Practically, Raman spectra of SiGe thin films were obtained experimentally and simulated virtually under a variety of conditions. RPI is found to be the most impactful parameter in specifying linewidth followed by the spectral resolution and signal to noise. While developed for Raman experiments, the results are generally applicable to spectroscopic linewidth studies illuminating the experimental trade-offs inherent in quantification.

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Semiconductor Hyperbolic Metamaterials at the Quantum Limit

Scientific Reports

Montaño, Inès; Campione, Salvatore; Klem, John F.; Beechem, Thomas E.; Wolf, Omri; Sinclair, Michael B.; Luk, Ting S.

We study semiconductor hyperbolic metamaterials (SHMs) at the quantum limit experimentally using spectroscopic ellipsometry as well as theoretically using a new microscopic theory. The theory is a combination of microscopic density matrix approach for the material response and Green’s function approach for the propagating electric field. Our approach predicts absorptivity of the full multilayer system and for the first time allows the prediction of in-plane and out-of-plane dielectric functions for every individual layer constructing the SHM as well as effective dielectric functions that can be used to describe a homogenized SHM.

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Tunable dual-band graphene-based infrared reflectance filter

Optics Express

Goldflam, Michael G.; Ruiz, Isaac R.; Howell, Stephen W.; Wendt, J.R.; Sinclair, Michael B.; Peters, D.W.; Beechem, Thomas E.

We experimentally demonstrated an actively tunable optical filter that controls the amplitude of reflected long-wave-infrared light in two separate spectral regions concurrently. Our device exploits the dependence of the excitation energy of plasmons in a continuous and unpatterned sheet of graphene on the Fermi-level, which can be controlled via conventional electrostatic gating. The filter enables simultaneous modification of two distinct spectral bands whose positions are dictated by the device geometry and graphene plasmon dispersion. Within these bands, the reflected amplitude can be varied by over 15% and resonance positions can be shifted by over 90 cm-1. Electromagnetic simulations verify that tuning arises through coupling of incident light to graphene plasmons by a grating structure. Importantly, the tunable range is determined by a combination of graphene properties, device structure, and the surrounding dielectrics, which dictate the plasmon dispersion. Thus, the underlying design shown here isapplicable across a broad range of infrared frequencies.

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Polysulfide Speciation in the Bulk Electrolyte of a Lithium Sulfur Battery

Journal of the Electrochemical Society

McBrayer, Josefine D.; Beechem, Thomas E.; Perdue, Brian R.; Garzon, Fernando; Apblett, Christopher A.

In situ Raman microscopy was used to study polysulfide speciation in the bulk ether electrolyte during the discharge and charge of a Li-S electrochemical cell to assess the complex interplay between chemical and electrochemical reactions in solution. During discharge, long chain polysulfides and the S3- radical appear in the electrolyte at 2.4 V indicating a rapid equilibrium of the dissociation reaction to form S3-. When charging, however, an increase in the concentration of all polysulfide species was observed. This highlights the importance of the electrolyte to sulfur ratio and suggests a loss in the useful sulfur inventory from the cathode to the electrolyte.

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Polysulfide speciation in the bulk electrolyte of a lithium sulfur battery

Journal of the Electrochemical Society

McBrayer, Josefine D.; Beechem, Thomas E.; Perdue, Brian R.; Apblett, Christopher A.; Garzon, Fernando

In situ Raman microscopy was used to study polysulfide speciation in the bulk ether electrolyte during the discharge and charge of a Li-S electrochemical cell to assess the complex interplay between chemical and electrochemical reactions in solution. During discharge, long chain polysulfides and the S3− radical appear in the electrolyte at 2.4 V indicating a rapid equilibrium of the dissociation reaction to form S3−. When charging, however, an increase in the concentration of all polysulfide species was observed. This highlights the importance of the electrolyte to sulfur ratio and suggests a loss in the useful sulfur inventory from the cathode to the electrolyte.

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Integrating Resonant Structures with IR Detectors

Goldflam, Michael G.; Goldflam, Michael G.; Anderson, Evan M.; Anderson, Evan M.; Campione, Salvatore; Campione, Salvatore; Coon, Wesley T.; Coon, Wesley T.; Davids, Paul D.; Davids, Paul D.; Fortune, Torben R.; Fortune, Torben R.; Hawkins, Samuel D.; Hawkins, Samuel D.; Kadlec, Clark N.; Kadlec, Clark N.; Kadlec, Emil A.; Kadlec, Emil A.; Kim, Jin K.; Kim, Jin K.; Klem, John F.; Klem, John F.; Shaner, Eric A.; Shaner, Eric A.; Sinclair, Michael B.; Sinclair, Michael B.; Tauke-Pedretti, Anna; Tauke-Pedretti, Anna; Warne, Larry K.; Warne, Larry K.; Wendt, J.R.; Wendt, J.R.; Beechem, Thomas E.; Beechem, Thomas E.; Howell, Stephen W.; Howell, Stephen W.; McDonald, Anthony E.; McDonald, Anthony E.; Ruiz, Isaac R.; Ruiz, Isaac R.

Abstract not provided.

Experimental Determination of the Ionization Energies of MoSe2, WS2, and MoS2 on SiO2 Using Photoemission Electron Microscopy

ACS Nano

Keyshar, Keyshar; Kunttal, Kunttal; Berg, Morgann B.; Zhang, Zhang; Xiang, Xiang; Vajtai, Vajtai; Robert, Robert; Gupta, Gupta; Gautam, Gautam; Chan, Calvin C.; Beechem, Thomas E.; Ajayan, Ajayan; Pulickel, Pulickel; Mohite, Mohite; D., Aditya D.; Ohta, Taisuke O.

Here, the values of the ionization energies of transition metal dichalcogenides (TMDs) are needed to assess their potential usefulness in semiconductor heterojunctions for high-performance optoelectronics. Here, we report on the systematic determination of ionization energies for three prototypical TMD monolayers (MoSe2, WS2, and MoS2) on SiO2 using photoemission electron microscopy with deep ultraviolet illumination. The ionization energy displays a progressive decrease from MoS2, to WS2, to MoSe2, in agreement with predictions of density functional theory calculations. Combined with the measured energy positions of the valence band edge at the Brillouin zone center, we deduce that, in the absence of interlayer coupling, a vertical heterojunction comprising any of the three TMD monolayers would form a staggered (type-II) band alignment. This band alignment could give rise to long-lived interlayer excitons that are potentially useful for valleytronics or efficient electron–hole separation in photovoltaics.

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Designing graphene absorption in a multispectral plasmon-enhanced infrared detector

Optics Express

Goldflam, Michael G.; Fei, Zhe; Ruiz, Isaac R.; Howell, Stephen W.; Davids, Paul D.; Peters, D.W.; Beechem, Thomas E.

We have examined graphene absorption in a range of graphene-based infrared devices that combine either monolayer or bilayer graphene with three different gate dielectrics. Electromagnetic simulations show that the optical absorption in graphene in these devices, an important factor in a functional graphene-based detector, is strongly dielectricdependent. These simulations reveal that plasmonic excitation in graphene can significantly influence the percentage of light absorbed in the entire device, as well as the graphene layer itself, with graphene absorption exceeding 25% in regions where plasmonic excitation occurs. Notably, the dielectric environment of graphene has a dramatic influence on the strength and wavelength range over which the plasmons can be excited, making dielectric choice paramount to final detector tunability and sensitivity.

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Dynamic Wavelength-Tunable Photodetector Using Subwavelength Graphene Field-Effect Transistors

Scientific Reports

Leonard, Francois L.; Spataru, Dan C.; Goldflam, Michael G.; Peters, D.W.; Beechem, Thomas E.

Dynamic wavelength tunability has long been the holy grail of photodetector technology. Because of its atomic thickness and unique properties, graphene opens up new paradigms to realize this concept, but so far this has been elusive experimentally. Here we employ detailed quantum transport modeling of photocurrent in graphene field-effect transistors (including realistic electromagnetic fields) to show that wavelength tunability is possible by dynamically changing the gate voltage. We reveal the phenomena that govern the behavior of this type of device and show significant departure from the simple expectations based on vertical transitions. We find strong focusing of the electromagnetic fields at the contact edges over the same length scale as the band-bending. Both of these spatially-varying potentials lead to an enhancement of non-vertical optical transitions, which dominate even in the absence of phonon or impurity scattering. We also show that the vanishing density of states near the Dirac point leads to contact blocking and a gate-dependent modulation of the photocurrent. Several of the effects discussed here should be applicable to a broad range of one-and two-dimensional materials and devices.

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Molecular beam epitaxy growth of SrO buffer layers on graphite and graphene for the integration of complex oxides

Journal of Crystal Growth

Ahmed, Adam S.; Wen, Hua; Ohta, Taisuke O.; Pinchuk, Igor V.; Zhu, Tiancong; Beechem, Thomas E.; Kawakami, Roland K.

We report the successful growth of high-quality SrO films on highly-ordered pyrolytic graphite (HOPG) and single-layer graphene by molecular beam epitaxy. The SrO layers have (001) orientation as confirmed by X-ray diffraction (XRD) while atomic force microscopy measurements show continuous pinhole-free films having rms surface roughness of <1.5 Å. Transport measurements of exfoliated graphene after SrO deposition show a strong dependence between the Dirac point and Sr oxidation. Subsequently, the SrO is leveraged as a buffer layer for more complex oxide integration via the demonstration of (001) oriented SrTiO3 grown atop a SrO/HOPG stack.

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Thermal conductivity of turbostratic carbon nanofiber networks

Journal of Heat Transfer

Bauer, Matthew L.; Saltonstall, Christopher B.; Leseman, Zayd C.; Beechem, Thomas E.; Hopkins, Patrick E.; Norris, Pamela M.

Composite material systems composed of a matrix of nanomaterials can achieve combinations of mechanical and thermophysical properties outside the range of traditional systems. The microstructure of the system dictates the rate, in which heat moves through the material. In this work, air/carbon nanofiber networks are studied to elucidate the system parameters influencing thermal transport. Thermal properties are measured with varying initial carbon fiber fill fraction, environment pressure, loading pressure, and heat treatment temperature (HTT) through a bidirectional modification of the 3ω technique. The nanostructure of the individual fibers is characterized with small angle X-ray scattering and Raman spectroscopy providing insight to individual fiber thermal conductivity. Measured thermal conductivity of the carbon nanofiber networks varied from 0.010 W/(m K) to 0.070 W/(m K). An understanding of the intrinsic properties of the individual fibers and the interactions of the two-phase composite is used to reconcile low measured thermal conductivities with predictive modeling. Accounting for fiber-to-fiber interactions and the nuanced changes in the composite as pressure is applied is necessary to successfully model thermal transport in system.

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Thermal Design and Characterization of Heterogeneously Integrated InGaP/GaAs HBTs

IEEE Transactions on Components, Packaging and Manufacturing Technology

Choi, Sukwon; Peake, Gregory M.; Keeler, Gordon A.; Geib, K.M.; Briggs, R.D.; Beechem, Thomas E.; Shaffer, Ryan A.; Clevenger, Jascinda C.; Patrizi, G.A.; Klem, John F.; Tauke-Pedretti, Anna; Nordquist, Christopher N.

Flip-chip heterogeneously integrated n-p-n InGaP/GaAs heterojunction bipolar transistors (HBTs) with integrated thermal management on wide-bandgap AlN substrates followed by GaAs substrate removal are demonstrated. Without thermal management, substrate removal after integration significantly aggravates self-heating effects, causing poor $I$-$V$ characteristics due to excessive device self-heating. An electrothermal codesign scheme is demonstrated that involves simulation (design), thermal characterization, fabrication, and evaluation. Thermoreflectance thermal imaging, electrical-temperature sensitive parameter-based thermometry, and infrared thermography were utilized to assess the junction temperature rise in HBTs under diverse configurations. In order to reduce the thermal resistance of integrated devices, passive cooling schemes assisted by structural modification, i.e., positioning indium bump heat sinks between the devices and the carrier, were employed. By implementing thermal heat sinks in close proximity to the active region of flip-chip integrated HBTs, the junction-to-baseplate thermal resistance was reduced over a factor of two, as revealed by junction temperature measurements and improvement of electrical performance. The suggested heterogeneous integration method accounts for not only electrical but also thermal requirements providing insight into realization of advanced and robust III-V/Si heterogeneously integrated electronics.

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Size effects on the thermal conductivity of amorphous silicon thin films

Physical Review B

Braun, Jeffrey L.; Baker, Christopher H.; Giri, Ashutosh; Elahi, Mirza; Artyushkova, Kateryna; Beechem, Thomas E.; Norris, Pamela M.; Leseman, Zayd C.; Gaskins, John T.; Hopkins, Patrick E.

We investigate thickness-limited size effects on the thermal conductivity of amorphous silicon thin films ranging from 3 to 1636 nm grown via sputter deposition. While exhibiting a constant value up to ∼100 nm, the thermal conductivity increases with film thickness thereafter. The thickness dependence we demonstrate is ascribed to boundary scattering of long wavelength vibrations and an interplay between the energy transfer associated with propagating modes (propagons) and nonpropagating modes (diffusons). A crossover from propagon to diffuson modes is deduced to occur at a frequency of ∼1.8 THz via simple analytical arguments. These results provide empirical evidence of size effects on the thermal conductivity of amorphous silicon and systematic experimental insight into the nature of vibrational thermal transport in amorphous solids.

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Carbon Composite Microelectromechanical Systems (CMEMS)

Dyck, Christopher D.; Washburn, Cody M.; Rector, Michael N.; Finnegan, Patrick S.; Pfeifer, Kent B.; Beechem, Thomas E.; Blecke, Jill B.; Satches, Michael R.; Massey, Lee T.; Dyck, Christopher D.

Pyrolyzed carbon as a mechanical material is promising for applications in harsh environments. In this work, we characterized the material and developed novel processes for fabricating carbon composite micro-electromechanical systems (CMEMS) structures. A novel method of increasing Young's modulus and the conductivity of pyrolyzed AZ 4330 was demonstrated by loading the films with graphene oxide prior to pyrolysis. By incorporating 2 wt.% graphene stiffeners into the film, a 65% increase in Young's modulus and 11% increase in conductivity were achieved. By reactive ion etching pyrolyzed blanket AZ 50XT thick film photoresist, a high aspect ratio process was demonstrated with films >7.5um thick. Two novel multi-level, volume-scalable CMEMS processes were developed on 6" diameter wafers. Young's modulus of 23 GPa was extracted from nanoindentation measurements of pyrolyzed AZ 50XT films. The temperature-dependent resistance was characterized from room temperature to 500C and found to be nearly linear over this range. By fitting the results of self-heated bridges in an inert ambient, we calculated that the bridges survived to 1000C without failure. Transmission electron microscopy (TEM) results showed the film to be largely amorphous, containing some sub-micrometer sized graphite crystallites. This was consistent with our Raman analysis, which also showed the film to be largely sp 2 bonded. The calculated average density of pyrolyzed AZ 4330 films was 1.32 g/cm 2 . Thin level of disorder and the conductivity of thin film resistors were found to unchanged by 2Mrad gamma irradiation from a Co 60 source. Thin film pyrolyzed carbon resistors were hermetically sealed in a nitrogen ambient in 24-pin dual in-line packages (DIP's). The resistance was measured periodically and remained constant over 6 months' time.

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Measuring Li+ inventory losses in LiCoO2/graphite cells using raman microscopy

Journal of the Electrochemical Society

Snyder, Chelsea M.; Apblett, Christopher A.; Grillet, Anne M.; Beechem, Thomas E.; Duquette, David

The contribution from loss of Li+ inventory to capacity fade is described for slow rates (C/10) and long-term cycling (up to 80 cycles). It was found through electrochemical testing and ex-situ Raman analysis that at these slow rates, the entirety of capacity loss up to 80 cycles can be explained by loss of Li+ inventory in the cell. The Raman spectrum of LiCoO2 is sensitive to the state of lithiation and can therefore be leveraged to quantify the state of lithiation for individual particles. With these Raman derived estimates, the lithiation state of the cathode in the discharged state is compared to electrochemical data as a function of cycle number. High correlation is found between Raman quantifications of cycleable lithium and the capacity fade. Additionally, the linear relationship between discharge capacity and cell overpotential suggests that the loss of capacity stems from an impedance rise of the electrodes, which based on Li inventory losses, is caused by SEI formation and repair.

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Oxidation of ultrathin GaSe

Applied Physics Letters

Beechem, Thomas E.; Kowalski, Brian M.; Brumbach, Michael T.; McDonald, Anthony E.; Spataru, Dan C.; Howell, Stephen W.; Ohta, Taisuke O.; Pask, Jesse A.; Kalugin, Nikolai G.

Oxidation of exfoliated gallium selenide (GaSe) is investigated through Raman, photoluminescence, Auger, and X-ray photoelectron spectroscopies. Photoluminescence and Raman intensity reductions associated with spectral features of GaSe are shown to coincide with the emergence of signatures emanating from the by-products of the oxidation reaction, namely, Ga2Se3 and amorphous Se. Photoinduced oxidation is initiated over a portion of a flake highlighting the potential for laser based patterning of two-dimensional heterostructures via selective oxidation.

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Thermal transport in tantalum oxide films for memristive applications

Applied Physics Letters

Landon, Colin D.; Wilke, Rudeger H.T.; Brumbach, Michael T.; Brennecka, Geoffrey L.; Blea-Kirby, Mia A.; Ihlefeld, Jon I.; Marinella, Matthew J.; Beechem, Thomas E.

The thermal conductivity of amorphous TaOx memristive films having variable oxygen content is measured using time domain thermoreflectance. Thermal transport is described by a two-part model where the electrical contribution is quantified via the Wiedemann-Franz relation and the vibrational contribution by the minimum thermal conductivity limit for amorphous solids. The vibrational contribution remains constant near 0.9 W/mK regardless of oxygen concentration, while the electrical contribution varies from 0 to 3.3 W/mK. Thus, the dominant thermal carrier in TaOx switches between vibrations and charge carriers and is controllable either by oxygen content during deposition, or dynamically by field-induced charge state migration.

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Error and uncertainty in Raman thermal conductivity measurements

Review of Scientific Instruments

Beechem, Thomas E.; Yates, Luke Y.; Graham, Sam G.

We investigated error and uncertainty in Raman thermal conductivity measurements via finite element based numerical simulation of two geometries often employed -- Joule-heating of a wire and laser-heating of a suspended wafer. Using this methodology, the accuracy and precision of the Raman-derived thermal conductivity are shown to depend on (1) assumptions within the analytical model used in the deduction of thermal conductivity, (2) uncertainty in the quantification of heat flux and temperature, and (3) the evolution of thermomechanical stress during testing. Apart from the influence of stress, errors of 5% coupled with uncertainties of ±15% are achievable for most materials under conditions typical of Raman thermometry experiments. Error can increase to >20%, however, for materials having highly temperature dependent thermal conductivities or, in some materials, when thermomechanical stress develops concurrent with the heating. A dimensionless parameter -- termed the Raman stress factor -- is derived to identify when stress effects will induce large levels of error. Together, the results compare the utility of Raman based conductivity measurements relative to more established techniques while at the same time identifying situations where its use is most efficacious.

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Thermal flux limited electron Kapitza conductance in copper-niobium multilayers

Applied Physics Letters

Cheaito, Ramez; Hattar, Khalid M.; Gaskins, John T.; Yadav, Ajay K.; Duda, John C.; Beechem, Thomas E.; Ihlefeld, Jon I.; Piekos, Edward S.; Baldwin, Jon K.; Misra, Amit; Hopkins, Patrick E.

We study the interplay between the contributions of electron thermal flux and interface scattering to the Kapitza conductance across metal-metal interfaces through measurements of thermal conductivity of copper-niobium multilayers. Thermal conductivities of copper-niobium multilayer films of period thicknesses ranging from 5.4 to 96.2 nm and sample thicknesses ranging from 962 to 2677 nm are measured by time-domain thermoreflectance over a range of temperatures from 78 to 500 K. The Kapitza conductances between the Cu and Nb interfaces in multilayer films are determined from the thermal conductivities using a series resistor model and are in good agreement with the electron diffuse mismatch model. Our results for the thermal boundary conductance between Cu and Nb are compared to literature values for the thermal boundary conductance across Al-Cu and Pd-Ir interfaces, and demonstrate that the interface conductance in metallic systems is dictated by the temperature derivative of the electron energy flux in the metallic layers, rather than electron mean free path or scattering processes at the interface.

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Plasmonic nanoantennas for enhanced midwave and longwave infrared imaging

Proceedings of SPIE - The International Society for Optical Engineering

Peters, D.W.; Davids, Paul S.; Kim, Jin K.; Beechem, Thomas E.; Howell, Stephen W.; Leonhardt, Darin L.; Ohta, Taisuke O.; Wendt, J.R.; Montoya, John A.

Conversion of plane waves to surface waves prior to detection allows key advantages in changes to the architecture of the detector pixels in a focal plane array. We have integrated subwavelength patterned metal nanoantennas with various detector materials to incorporate these advantages: midwave infrared indium gallium arsenide antimonide detectors and longwave infrared graphene detectors. Nanoantennas offer a means to make infrared detectors much thinner by converting incoming plane waves to more tightly bound and concentrated surface waves. Thinner architectures reduce both dark current and crosstalk for improved performance. For graphene detectors, which are only one or two atomic layers thick, such field concentration is a necessity for usable device performance, as single pass plane wave absorption is insufficient. Using III-V detector material, we reduced thickness by over an order of magnitude compared to traditional devices. We will discuss Sandia's motivation for these devices, which go beyond simple improvement in traditional performance metrics. The simulation methodology and design rules will be discussed in detail. We will also offer an overview of the fabrication processes required to make these subwavelength structures on at times complex underlying devices based on III-V detector material or graphene on silicon or silicon carbide. Finally, we will present our latest infrared detector characterization results for both III-V and graphene structures.

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Planarized arrays of aligned, untangled multiwall carbon nanotubes with Ohmic back contacts

Journal of Materials Research

Rochford, C.; Limmer, Steven J.; Howell, Stephen W.; Beechem, Thomas E.; Siegal, Michael P.

Vertically aligned, untangled planarized arrays of multiwall carbon nanotubes (MWNTs) with Ohmic back contacts were grown in nanopore templates on arbitrary substrates. The templates were prepared by sputter depositing Nd-doped Al films onto W-coated substrates, followed by anodization to form an aluminum oxide nanopore array. The W underlayer helps eliminate the aluminum oxide barrier that typically occurs at the nanopore bottoms by instead forming a thin WO3 layer. The WO3 can be selectively etched to enable electrodeposition of Co catalysts with control over the Co site density. This led to control of the site density of MWNTs grown by thermal chemical vapor deposition, with W also serving as a back electrical contact. Ohmic contact to MWNTs was confirmed, even following ultrasonic cutting of the entire array to a uniform height.

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Characterization of Switching Filament Formation in TaOx Memristive Memory Films

Marinella, Matthew J.; Marinella, Matthew J.; Howell, Stephen W.; Howell, Stephen W.; Decker, Seth D.; Decker, Seth D.; Hughart, David R.; Hughart, David R.; Lohn, Andrew L.; Lohn, Andrew L.; Mickel, Patrick R.; Mickel, Patrick R.; Apodaca, Roger A.; Apodaca, Roger A.; Bielejec, Edward S.; Bielejec, Edward S.; Beechem, Thomas E.; Beechem, Thomas E.; Wolfley, Steven L.; Wolfley, Steven L.; Stevens, James E.; Brennecka, Geoffrey L.

Abstract not provided.

Application of plasmonic subwavelength structuring to enhance infrared detection

Proceedings of SPIE - The International Society for Optical Engineering

Peters, David W.; Davids, Paul D.; Kim, Jin K.; Leonhardt, Darin L.; Beechem, Thomas E.; Howell, Stephen W.; Ohta, Taisuke O.; Wendt, J.R.; Montoya, John A.

Nanoantennas are an enabling technology for visible to terahertz components and may be used with a variety of detector materials. We have integrated subwavelength patterned metal nanoantennas with various detector materials for infrared detection: midwave infrared indium gallium arsenide antimonide detectors, longwave infrared graphene detectors, and shortwave infrared germanium detectors. Nanoantennas offer a means to make infrared detectors much thinner, thus lowering the dark current and improving performance. The nanoantenna converts incoming plane waves to more tightly bound and concentrated surface waves. The active material only needs to extend as far as these bound fields. In the case of graphene detectors, which are only one or two atomic layers thick, such field concentration is a necessity for usable device performance, as single pass absorption is insufficient. The nanoantenna is thus the enabling component of these thin devices. However nanoantenna integration and fabrication vary considerably across these platforms as do the considerations taken into account during design. Here we discuss the motivation for these devices and show examples for the three material systems. Characterization results are included for the midwave infrared detector. © 2014 SPIE.

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Accelerating the development of transparent graphene electrodes through basic science driven chemical functionalization

Chan, Calvin C.; Beechem, Thomas E.; Ohta, Taisuke O.; Brumbach, Michael T.

Chemical functionalization is required to adapt graphenes properties to many applications. However, most covalent functionalization schemes are spontaneous or defect driven and are not suitable for applications requiring directed assembly of molecules on graphene substrates. In this work, we demonstrated electrochemically driven covalent bonding of phenyl iodoniums onto epitaxial graphene. The amount of chemisorption was demonstrated by varying the duration of the electrochemical driving potential. Chemical, electronic, and defect states of phenyl-modified graphene were studied by photoemission spectroscopy, spatially resolved Raman spectroscopy, and water contact angle measurement. Covalent attachment rehybridized some of the delocalized graphene sp2 orbitals to localized sp3 states. Control over the relative spontaneity (reaction rate) of covalent graphene functionalization is an important first step to the practical realization of directed molecular assembly on graphene. More than 10 publications, conference presentations, and program highlights were produced (some invited), and follow-on funding was obtained to continue this work.

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Carotenoid distribution in living cells of haematococcus pluvialis (chlorophyceae)

PLoS ONE

Collins, Aaron M.; Jones, Howland D.; Han, Danxiang; Hu, Qiang; Beechem, Thomas E.; Timlin, Jerilyn A.

Haematococcus pluvialis is a freshwater unicellular green microalga belonging to the class Chlorophyceae and is of commercial interest for its ability to accumulate massive amounts of the red ketocarotenoid astaxanthin (3,3′-dihydroxy-β,β-carotene-4,4′-dione). Using confocal Raman microscopy and multivariate analysis, we demonstrate the ability to spectrally resolve resonance-enhanced Raman signatures associated with astaxanthin and β-carotene along with chlorophyll fluorescence. By mathematically isolating these spectral signatures, in turn, it is possible to locate these species independent of each other in living cells of H. pluvialis in various stages of the life cycle. Chlorophyll emission was found only in the chloroplast whereas astaxanthin was identified within globular and punctate regions of the cytoplasmic space. Moreover, we found evidence for β-carotene to be co-located with both the chloroplast and astaxanthin in the cytosol. These observations imply that β-carotene is a precursor for astaxanthin and the synthesis of astaxanthin occurs outside the chloroplast. Our work demonstrates the broad utility of confocal Raman microscopy to resolve spectral signatures of highly similar chromophores in living cells. © 2011 Collins et al.

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Enabling graphene nanoelectronics

Ohta, Taisuke O.; McCarty, Kevin F.; Beechem, Thomas E.; Pan, Wei P.; Biedermann, Laura B.; Ross III, Anthony J.; Gutierrez, Carlos G.

Recent work has shown that graphene, a 2D electronic material amenable to the planar semiconductor fabrication processing, possesses tunable electronic material properties potentially far superior to metals and other standard semiconductors. Despite its phenomenal electronic properties, focused research is still required to develop techniques for depositing and synthesizing graphene over large areas, thereby enabling the reproducible mass-fabrication of graphene-based devices. To address these issues, we combined an array of growth approaches and characterization resources to investigate several innovative and synergistic approaches for the synthesis of high quality graphene films on technologically relevant substrate (SiC and metals). Our work focused on developing the fundamental scientific understanding necessary to generate large-area graphene films that exhibit highly uniform electronic properties and record carrier mobility, as well as developing techniques to transfer graphene onto other substrates.

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Electrostatic transfer of epitaxial graphene to glass

Biedermann, Laura B.; Beechem, Thomas E.; Ross III, Anthony J.; Pan, Wei P.; Ohta, Taisuke O.; Howell, Stephen W.

We report on a scalable electrostatic process to transfer epitaxial graphene to arbitrary glass substrates, including Pyrex and Zerodur. This transfer process could enable wafer-level integration of graphene with structured and electronically-active substrates such as MEMS and CMOS. We will describe the electrostatic transfer method and will compare the properties of the transferred graphene with nominally-equivalent 'as-grown' epitaxial graphene on SiC. The electronic properties of the graphene will be measured using magnetoresistive, four-probe, and graphene field effect transistor geometries [1]. To begin, high-quality epitaxial graphene (mobility 14,000 cm2/Vs and domains >100 {micro}m2) is grown on SiC in an argon-mediated environment [2,3]. The electrostatic transfer then takes place through the application of a large electric field between the donor graphene sample (anode) and the heated acceptor glass substrate (cathode). Using this electrostatic technique, both patterned few-layer graphene from SiC(000-1) and chip-scale monolayer graphene from SiC(0001) are transferred to Pyrex and Zerodur substrates. Subsequent examination of the transferred graphene by Raman spectroscopy confirms that the graphene can be transferred without inducing defects. Furthermore, the strain inherent in epitaxial graphene on SiC(0001) is found to be partially relaxed after the transfer to the glass substrates.

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First approximations of phonon thermal transport at solid-graphite interfaces

Hopkins, Patrick E.; Beechem, Thomas E.

This model predicts thermal boundary conductance at interfaces where one material comprising the junction is characterized by high elastic anisotropy (i.e, graphite). The thermal properties of graphite are determined through a simplified vibrational model, where the bulk structure is treated as an linear assembly of two-dimensional systems. This model is validated at temperatures above cryogenic through comparison to experimentally determined values of specific heat. Elastic processes are accounted for through traditional diffuse transport theory. Inelastic contributions due to multi-phonon processes are also addressed and quantified.

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177 Results
177 Results