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225 records · Page 13

Temperature-Agnostic Pt/Au Ohmic Contacts on n -Type Gallium Nitride for Self-Aligned MOSFETs

Five alternative metals are investigated as ohmic contacts to n-GaN including Cr/Au, Mo/Au, Pt/Au, Pd/Au, and Ge/Au. Ti-based contacts are traditionally used for ohmic contacts on n-GaN. However, conventional Ti/Al/Ni/Au metallization is found to be incompatible with a self-aligned process for GaN trench MOSFETs due to wet etch restrictions. Therefore, an alternative metallization is needed that is unreactive to the etch chemistry used in the self-aligned process. Additionally, the contact should remain ohmic following anneal at 900 °C so that contact formation can precede the anneal required for p-dopant activation. Here, in the present work, an n-GaN bilayer, consisting of a thin heavily doped contact layer (n 0 = 1 × 10 20 cm −3 ) atop a thick lesser doped layer, is used to demonstrate ohmic contacts of alternative metals with low specific contact resistance and extended thermal budget. Cr/Au ohmic contacts are demonstrated up to anneal temperatures of 800 °C, an increase of 200 °C compared to the highest known reports for Cr/Au contacts on n-GaN. Pt/Au metallization is demonstrated as an ohmic contact to n-GaN for the first time and exhibits true temperature-agnostic behavior up to anneal temperatures of 900 °C with specific contact resistance that is near parity with Ti/Al/Ni/Au. The temperature-agnostic behavior of Pt/Au ohmic contacts on the n-GaN bilayer, in addition to chemical compatibility with the self-aligned process, positions Pt/Au contacts as a key enabling element for self-aligned trench MOSFETs on GaN.

Reilly, Kevin James [Sandia National Laboratories ↗

Trace Chemical Detection Using Intercalated MXenes as a Signal Enhancing Substrate in Optical Probes

MXenes are 2D materials composed of layered transition metal nitrides or carbides. These materials are synthesized by HF exfoliation from MAX phases (Ti{sub 3}AlC{sub 2}). The 2D nanomaterial was synthesized by the removal of the 'A' element, resulting in a Mxene product (Ti{sub 3}C{sub 2}). MXenes have the general formula M{sub n+1}X{sub n}T{sub x}, where M is an early transition metal, X is Carbon and/or Nitrogen, and T accounts for surface terminated functional groups such as Fluoride, hydroxyl, and oxygen. These materials have very unique properties, similar to graphene, that allows them to be applied in a variety of trace detection techniques including surface-enhanced Raman spectroscopy (SERS). MXenes have also been demonstrated to selectively uptake uranyl ion, UO{sub 2}{sup 2+}. If this property can be combined with SERS or fluorescence detection, it may be possible to use MXenes as the basis for an alternative method to kinetic phosphorescence analysis (KPA) for trace uranyl measurements. Objectives: To confirm that MXene Nano materials are suitable substrates for SERS and sensor development by enhancing Raman signaling. To determine if certain MXene preparation methods yield materials that are more suitable for trace sensing methods. To determine uranyl uptake properties of these MXene materials and test them for analytical signals. Sample Preparation: Preparation of Ti{sub 3}C{sub 2}MXene (at FSU). MXenes were prepared by etching Al from Ti{sub 3}AlC{sub 2} (MAX phase)material. Two etching techniques yield different MXene products: LiF/HCl: Milder reaction, larger MXene flakes. HF: Harsher reaction, smaller flakes, larger layer separation. Products washed to remove etchant, vacuum filtered, and dried. Dried MXene flakes are air-stable. Film preparation for sensor testing (at SRNL): Suspend powder in diH{sub 2}O, purge with Ar, sonicate for 30 min. Centrifuge and collect supernate with suspended particles. Observed LiF-etched Mxene yielded a higher density of particles and darker collected solution. Drop-cast (4 ml) supernate onto slides and dried with Ar. For Rhodamine B (RhB) testing, drop-cast 4 ml drops onto Mxene spots and dried with Ar. Scanning Electron Microscopy conditions: 10 kV Beam energy, high vacuum; Working distance of 8 mm; beam penetration depth appx. 4 microns, beam spot size appx. 2 nanometers. Results: Detection of aluminum correlates with bright spots on image. Presence of aluminum shows that LiF/HCl etching was less thorough than HF etching. Trace Cl detection in LiF images suggests incomplete rinsing. HF has smaller feature size, more layer structure, and increased homogeneity, consistent with expectations. Macroscopic Raman spectroscopy measurements: 532 nm excitation, ∼50 mW with a ∼100 micron spot size (InPhotonics RPB probe). Kaiser Optical Holospec f/1.8 spectrometer with cooled (-60 deg.C) Andor iDus OE420 CCD. LiF 1x supernate showed good signal for trace measurements of Rhodamine B. HF and 1/4x LiF supernates showed little Mxene or Rhodamine B signal. Low deposition densities led to excess background signal from glass slides. For LiF film, response is linear with Rhodamine B concentration over range tested. Will retest with Raman microscope (∼1 micron spot size) to characterize SERS of more dilute LiF and HF etched Mxenes. Conclusions: The LiF etched material was more suitable for macroscopic SERS measurements because it was more concentrated, resulting in a thicker film than the HF etched Mxene and diluted LiF sample. However, the other materials may give greater SERS enhancements, which we hope to determine from measurements with the Raman microscope. From characterization with SEM we concluded that the HF etched Mxene is more uniform/homogenous and has smaller particle size than the LiF etched Mxene. There is still aluminum present in both samples indicating that etching wasn't complete, but the removal of the aluminum was more efficient in the HF method. Path Forward: Observe SERS with Raman microscopy, to obtain better signals for the more diluted samples and be able to compare enhancement effects for the different MXenes. Characterize uranyl sorption into MXene films and test Raman and fluorescence signals. Revisit the etching conditions to improve removal of aluminum. FSU and SRNL will continue to collaborate to create and characterize different Mxene materials and test their usefulness for sensor applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A neural master equation framework for multiscale modeling of molecular processes: application to atomic-scale plasma processes

Plasma-surface interactions (PSI) play a crucial role in microelectronics fabrication; however, their multiscale nature and array of complex, often unknown interactions make computational modeling of PSIs extremely difficult. To this end, we propose a general neural master equation (NME) framework that uses master equations to describe the dynamics of a molecular process, wherein neural networks learned from atomistic simulations represent unknown transitions between different system states. By leveraging the physics-based structure of master equations and data-driven state transitions, the NME framework promotes generalizability and physics interpretability, and can bridge disparate length and time scales. The framework is demonstrated for multiscale modeling of Si atomic layer etching and reactive ion etching, where the learned NME-based surface kinetic models exhibit good predictive and extrapolative capabilities for predicting experimentally relevant observables as a function of process parameters. The NME-based surface kinetic models obey physical constraints, which are violated in models based on neural ordinary differential equations. The proposed NME framework for multiscale modeling of molecular processes can pave the way for the discovery of new chemistries and materials in atomic-scale plasma processes.

Chemical engineering↗

Magnification Determination for AGHCF Metallographic Images

Metallographic images generated in the Alpha Gamma Hot Cell Facility (AGHCF) have been used for quantitative and qualitative characterization of irradiated metallic fuel pins. Individual high-magnification images (micrographs) contained in AGHCF file folders and experimental notebooks are in the form of polaroid photographs labeled with AGHCF identification number, magnification, and surface condition (as-polished or etched). Low magnification composite images (photomosaics) are also available for fuel cross sections, for radial strips from the fuel center to the cladding outer diameter, and for circumferential strips of the cladding and outer fuel region. The individual images do not have scale bars. Only a few of the composite images contain scale bars. The purpose of this work is to describe and apply methods for checking the magnification (50X to 500X) of individual images and for determining the magnification (~25X to ~100X) of composite images. The metallographic images used to verify and/or determine magnification were generated during the 1989 to 1993 timeframe for cross sections of U-10Zr/HT9 fuel rods irradiated in EBR-II and for cross sections of irradiated U-10Zr/HT9 fuel-rod samples following elevated-temperature tests conducted in the out-of-pile AGHCF Fuel Behavior Test Apparatus (FBTA). Procedures are documented in the AGHCF Operations Manual for preparation of metallographic samples, for calibration verification, and for constructing composites from individual images. Calibration verification of magnification was performed at least semiannually. One standard used for calibration verification was a glass slide with vertical lines indicating distances of 1 mm, 0.1 mm and 0.01mm. Guidance is provided in the current work for determining magnification from images of the standard. In addition to the periodic calibration verification, consistency checks are recommended to verify the magnification of images taken between the routine calibration verifications. For cladding samples with or without significant fuel-cladding chemical interaction (FCCI), images taken at different magnifications (e.g., 150X and 200X) of the unaffected cladding thickness can be compared. This process is independent of changes in cladding thickness due to swelling and creep. For images taken at only one magnification of cladding regions with no FCCI, the cladding thickness determined from the images may be compared to the nominal as-built cladding thickness (15.0 ± 0.5 mils for examples used in current work)). This procedure works best for cladding that has not experienced significant swelling and/or creep (e.g., ≤2% circumferential strain at the cladding outer surface). Composite images were constructed by pasting together higher magnification images and photographing the composite to generate a negative from which the hard-copy photograph was developed. The primary purpose of the composite images was to identify interesting areas of the fuel and cladding for imaging at higher magnification. However, procedures are recommended in the current work for determining composite magnifications to allow quantitative characterization of the fuel. Composites are not recommended for determining cladding thickness or FCCI depth because magnifications are too low (generally ≤110X) and image contrast is low. Fuel cross-section composites were created by pasting together 50X or 75X images. The nominal magnification for the photographed fuel cross-section composites is 25.4X. A more precise magnification can be determined by comparing the average cladding outer diameter measured from the composite to the average cladding outer diameter measured by profilometry. Radial-strip composites were constructed by pasting together high-magnification (150X or 250X) images. The nominal magnification of radial-strip composites photographs is about 100X. A more precise method for determining the magnification of radial strips is to compare the cladding thick

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Surface deposition of nanometer scale carbon structures on Bi 2 Sr 2 CaCu 2 O 8+δ using a low-cost scanning electron microscope

In this work, we investigate optically active nanostructures on Bi 2 Sr 2 CaCu 2 O 8+δ (BSCCO). The nanostructures are constructed from carbon nanocrystals formed using the electron beam of a scanning electron microscope to locally decompose residual hydrocarbons at the BSCCO surface. Atomic force microscopy is used to characterize the dimensions of these structures as a function of beam exposure time. This technique has been used to induce localized intercalation to form carbon nanoparticles up to tens of nanometers into a variety of 2D materials. Cross-sectional scanning transmission electron microscopy in BSCCO shows the presence of these carbon deposits on the surface, but there is no evidence they penetrate into the BSCCO substrate. Therefore, this technique is not suitable for localized intercalation in BSCCO, and it does have promise as a cost-effective approach to pattern nanometer scale etch stops.

2D materials↗

DOE Plasma Science Center - Predictive Control of Plasma Kinetics: Multi-Phase and Bounded Systems (Final Report DE-SC0001939)

Low temperature plasmas (LTPs) are the plasmas of electron-volt (eV) physics and eV technologies. LTPs have characteristic electron temperatures of a few eV and fractional ionizations that are typically small. Since LTPs have electron temperatures commensurate with the threshold energies of excited states in neutral atoms and molecules, power transfer from electrons to these atoms and molecules efficiently produces activated species (e.g., radicals, excited states, photons). Acceleration of ions in the sheaths of LTPs to energies of tens to hundreds of eV enable activation of surface modifying processes – sputtering, etching, deposition. With such properties, LTPs are often and beneficially used in technological devices, ranging from etching and deposition in microelectronics and solar cell fabrication, to hardening of surgical instruments. LTPs harbor fundamental science issues that are intellectually challenging and rewarding. At the same time, there are enormous societal benefits that are enabled by LTPs. The entire present-day and future information technology infrastructure owes its very existence to LTPs. Renewable energy sources, such as solar cell arrays, could not be economically produced in the absence of deposition and etching by LTPs. In acknowledgment of the importance of LTPs, the DOE Office of Fusion Energy Sciences supported the Plasma Science Center for Predictive Control of Plasma Kinetics: Multi-Phase and Bounded Systems from August 2009 to July 2021, consisting of an initial 5-year grant, 3 funded extensions and 2 no-cost extensions. This is the final report of the Center in which the productivity of the Center is discussed in terms of publications, impact and personnel. High-lights of the research performed in the Center are provided.

36 MATERIALS SCIENCE↗

Atomic layer deposition of nanofilms on porous polymer substrates: Strategies for success

Atomic layer deposition (ALD) is a versatile technique for engineering the surfaces of porous polymers, imbuing the flexible, high-surface-area substrates with inorganic and hybrid material properties. Previously reported enhancements include fouling resistance, electrical conductance, thermal stability, photocatalytic activity, hydrophilicity, and oleophilicity. However, there are many poorly understood phenomena that introduce challenges in applying ALD to porous polymers. In this paper, we address five common challenges and ways to overcome them: (1) entrapped precursor, (2) embrittlement, (3) film fracture, (4) deformation, and (5) pore collapse. These challenges are often interrelated and can exacerbate one another. To investigate these phenomena, we applied various ALD chemistries to porous polymers including polyethersulfone, polysulfone, polyvinylidene fluoride, and polycarbonate track-etched membranes. Reaction-diffusion modeling revealed why certain precursors and processing conditions result in embrittling subsurface material growth, entrapment of unreacted precursors, and nongrowth. We quantify the limits of ALD processing temperatures that are dictated by thermal expansion mismatch and can lead to fractured ALD films. The results herein allow us to make recommendations to avoid, mitigate, or overcome the difficulties encountered when performing ALD and plasma-enhanced ALD on porous polymers. We intend this article to serve as a “lessons learned” guide informed by previous experience to provide a better understanding of the difficulties and limitations of ALD on porous polymers and knowledge-based guidelines for successful depositions. This knowledge can accelerate future research and help experimentalists navigate and troubleshoot as they expose porous polymers to reactive precursor vapors.

36 MATERIALS SCIENCE↗

Continuous Encodable Reshaping of Gold Nanocrystals through Facet Modulation

Shape control of nanocrystals (NCs) is crucial for tuning their assembly behavior and functional properties, yet the precise manipulation of facet composition remains challenging. Here, we present a nanocrystal reshaping strategy to control and modulate the facets of gold (Au) NCs. Our one-pot approach, conducted at room temperature, requires only initial Au NCs, Au 3+ ions, and surfactants, distinguishing it from conventional reduction-mediated “etching-and-regrowth” methods. Detailed structural studies using electron microscopy, small-angle X-ray scattering (SAXS), and UV−vis spectroscopy reveal the surfactant-encoded pathway for NC transformation from shaped particles to spheres and then into various polyhedral shapes while preserving the individual particles' volume. The proposed reshaping mechanism involves the dissolution of surface Au atoms into Au + complexes in the presence of Au 3+ and surfactant, followed by surfactant-guided redeposition and formation of facets with different atomic planes. Using the ethanol oxidation reaction (EOR) as a probe, we observe a quasi-linear decrease in onset potential and an increase in activity with increasing {100} facet exposure. This work broadens synthetic strategies by offering precise NC reshaping and facet control.

36 MATERIALS SCIENCE↗

Subthreshold Erosion of an Organic Polymer Induced by Multiple Shots of an X-Ray Free-Electron Laser

We report solids irradiated by energetic photons can be eroded in two modes, depending on the radiation intensity. High average, low-peak power sources, e.g., synchrotron radiation and high-order harmonics, induce desorption of the material at a low etch rate. In contrast, high-peak-power radiation from extreme ultraviolet and x-ray lasers usually causes a massive removal of the material even by a single shot. In this contribution, an effective material erosion is reported in PMMA exposed to multiple accumulated pulses generated by the free-electron x-ray-laser Linac Coherent Light Source (LCLS, tuned at a photon energy of 830 eV in this study, operated in Menlo Park at Stanford, CA, USA) at a fluence below the single-pulse ablation threshold. The effect is caused by polymer-chain scissions initiated by single photons carrying enough energy to break the C—C bounds. High efficiency of the erosion is supposed to occur due to a correlation of the single-photon effects. The subthreshold damage exhibits a nonlinear dose dependence resulting from a competition between chain scissions and cross-linking processes. The cross-linking is proven by Raman spectroscopy of the irradiated polymer. Two theoretical models of the x-ray free-electron-laser-induced erosion are suggested, which provide an excellent agreement with the experimental results.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗