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At least 775 records · Page 43

Optoacoustic Microscopy for Investigation of Material Nanostructures-Embracing the Ultrasmall, Ultrafast, and the Invisible

The goal of this grant was the development of a new type of scanning acoustic microscope for nanometer resolution ultrasound imaging, based on ultrafast optoacoustics (>GHz). In the microscope, subpicosecond laser pulses was used to generate and detect very high frequency ultrasound with nanometer wavelengths. We report here on the outcome of the 3-year DOE/BES grant which involved the design, multifaceted construction, and proof-of-concept demonstration of an instrument that can be used for quantitative imaging of nanoscale material features – including features that may be buried so as to be inaccessible to conventional lightwave or electron microscopies. The research program has produced a prototype scanning optoacoustic microscope which, in combination with advanced computational modeling, is a system-level new technology (two patents issues) which offer novel means for precision metrology of material nanostructures, particularly those that are of contemporary interest to the frontline micro- and optoelectronics device industry. For accomplishing the ambitious technical goals, the research roadmap was designed and implemented in two phases. In Phase I, we constructed a “non-focusing” optoacoustic microscope instrument (“POAM”), with nanometer vertical (z-) resolution, while limited to approximately 10 micrometer scale lateral recolution. The Phase I version of the instrument which was guided by extensive acoustic and optical numerical modeling of the basic underlying acoustic and optical physics, featured nanometer scale close loop positioning between the optoacoustic transducer element and a nanostructured material sample under investigation. In phase II, we implemented and demonstrated a scanning version of the instrument (“SOAM”) where incident acoustic energy is focused, and scanned on lateral (x-y) spatial scale in the 100 nm range as per the goals of the project. In so doing we developed advanced numerical simulations to provide computational models of the focusing of multi-GHz acoustic waves to the nanometer scale and innovated a series fabrication approaches for a new type of broadband high-frequency acoustic focusing microscope objective by applying methods on nanoimprinting and focused-ion beam techniques. In the following, the Phase I and Phase II instrument development is reported as Section II. The first segment of this section describes the POAM instrument and its development, while including much of the underlying ultrafast acoustic physics which is common to all of our work for this grant. Then, the science and engineering of the SOAM instrument is described, including the methods of fabricating new types of acoustic microlenses. The results section is followed by reports on publications (Section III), Participants (Section IV), and statement of full use of the allocated grant funds (Section V).

36 MATERIALS SCIENCE↗

Maskless Lithography and in situ Visualization of Conductivity of Graphene using Helium Ion Microscopy

The remarkable mechanical and electronic properties of graphene make it an ideal candidate for next generation nanoelectronics. With the recent development of commercial-level single-crystal graphene layers, the potential for manufacturing household graphene-based devices has improved, but significant challenges still remain with regards to patterning the graphene into devices. In the case of graphene supported on a substrate, traditional nanofabrication techniques such as e-beam lithography (EBL) are often used in fabricating graphene nanoribbons but the multi-step processes they require can result in contamination of the graphene with resists and solvents. In this letter, we report the utility of scanning helium ion lithography for fabricating functional graphene nanoconductors that are supported directly on a silicon dioxide layer, and we measure the minimum feature size achievable due to limitations imposed by thermal fluctuations and ion scattering during the milling process. Further we demonstrate that ion beams, due to their positive charging nature, may be used to observe and test the conductivity of graphene-based nanoelectronic devices in situ.

36 MATERIALS SCIENCE↗

Two-Step Procedure of Fly Ash Modification as an Alternative Method for Creation of Functional Composite

An appropriate filler is a key component required to achieve an useful composite with expected properties. Not only sophisticated types of filler, like graphene are popular, but also more common ones, like silica flour or fly ash because of their low costs. Besides production costs, adequate size and possibility of functionalization of particles surface to create stable bonds with a matrix are essential in filler selection. To create an useful filler for epoxy resin based composites with use of a waste material, namely fly ash, two-step procedure was proposed. In the first part, raw material was sieved and five different ranges of the filler size were obtained. After mechanical tests with fracture toughness, tensile strength and Young Modulus, as well thermal conductivity, the best size of the fly ash was chosen for further modification. During the second step, filler was modified with coupling agent [3-(2-aminoethylamino)propyl]trimethoxysilane in order to enhance the coupling between particular components of composite. Presence of the silane layer was confirmed with infrared spectroscopy and scanning electron microscopy measurements, whilst prepared epoxy composite filled with silanized fly ash was examined similarly as previous composites. Obtained results have proved the significant influence of size of a filler and bonding to the matrix on mechanical and thermal properties of fly ash-epoxy resin composite. Proposed simple method of fly ash modification is an environmentally friendly way for utilization of the fly ash. Moreover, it creates an alternative material applicable in electrical devices as functional composite.

36 MATERIALS SCIENCE↗

The rotate-plus-shift C-arm trajectory. Part I. Complete data with less than 180° rotation

Purpose: In the last decade, C-arm-based cone-beam CT became a widely used modality for intraoperative imaging. Typically a C-arm CT scan is performed using a circular or elliptical trajectory around a region of interest. Therefore, an angular range of at least 180° plus fan angle must be covered to ensure a completely sampled data set. However, mobile C-arms designed with a focus on classical 2D applications like fluoroscopy may be limited to a mechanical rotation range of less than 180° to improve handling and usability. The method proposed in this paper allows for the acquisition of a fully sampled data set with a system limited to a mechanical rotation range of at least 180° minus fan angle using a new trajectory design. This enables CT like 3D imaging with a wide range of C-arm devices which are mainly designed for 2D imaging. Methods: The proposed trajectory extends the mechanical rotation range of the C-arm system with two additional linear shifts. Due to the divergent character of the fan-beam geometry, these two shifts lead to an additional angular range of half of the fan angle. Combining one shift at the beginning of the scan followed by a rotation and a second shift, the resulting rotate-plus-shift trajectory enables the acquisition of a completely sampled data set using only 180° minus fan angle of rotation. The shifts can be performed using, e.g., the two orthogonal positioning axes of a fully motorized C-arm system. The trajectory was evaluated in phantom and cadaver examinations using two prototype C-arm systems. Results: The proposed trajectory leads to reconstructions without limited angle artifacts. Compared to the limited angle reconstructions of 180° minus fan angle, image quality increased dramatically. Details in the rotate-plus-shift reconstructions were clearly depicted, whereas they are dominated by artifacts in the limited angle scan. Conclusions: The method proposed here employs 3D imaging using C-arms with less than 180° rotation range adding full 3D functionality to a C-arm device retaining both handling comfort and the usability of 2D imaging. This method has a clear potential for clinical use especially to meet the increasing demand for an intraoperative 3D imaging.

60 APPLIED LIFE SCIENCES↗

Visual Scanning Hartmann Optical Tester (VSHOT) Uncertainty Analysis (Milestone Report)

In 1997, an uncertainty analysis was conducted of the Video Scanning Hartmann Optical Tester (VSHOT). In 2010, we have completed a new analysis, based primarily on the geometric optics of the system, and it shows sensitivities to various design and operational parameters. We discuss sources of error with measuring devices, instrument calibrations, and operator measurements for a parabolic troughmirror panel test. These help to guide the operator in proper setup, and help end-users to understand the data they are provided. We include both the systematic (bias) and random (precision) errors for VSHOT testing and their contributions to the uncertainty. The contributing factors we considered in this study are: target tilt; target face to laser output distance; instrument vertical offset;laser output angle; distance between the tool and the test piece; camera calibration; and laser scanner. These contributing factors were applied to the calculated slope error, focal length, and test article tilt that are generated by the VSHOT data processing. Results show the estimated 2-sigma uncertainty in slope error for a parabolic trough line scan test to be +/-0.2 milliradians;uncertainty in the focal length is +/- 0.1 mm, and the uncertainty in test article tilt is +/- 0.04 milliradians.

14 SOLAR ENERGY↗

Fallout Cloud Regimes

The U.S. Department of Defense (DOD), Department of Energy (DOE), and other organizations maintain operational nuclear explosion and atmospheric dispersion models to provide critical guidance on the expected effects of an accidental or deliberate explosion of a nuclear weapon (in this paper simply referred to as “device”). To be effective, these models must represent, as accurately as possible, the complex interactions of the blast, fire, and residual radiological hazards with the environment and population. One hundred atmospheric nuclear tests that form the basis for many models were conducted at the Nevada Test Site (NTS) (now referred to as the Nevada Nuclear Security Site, NNSS) in a dry desert environment. Other environments should be studied, but have less data available and are beyond the scope of the work presented in this paper. The debris clouds produced by the NTS tests, frequently called “mushroom clouds,” are familiar, with common structural elements such as a buoyant cap connected to a skirt of raised dust at the desert surface by a thin, dirt-filled stem. The film scanning project at LLNL has investigated historical film records of nuclear weapons tests. Here, we summarize findings showing that the mushroom cloud behavior for historic U.S. tests conducted in Nevada, has similar characteristics based on the distance of the device from the ground surface or Height of Burst (HOB), scaled by the energy release, or yield, of the device. This scaled height is referred to as the scaled-height-of-burst (SHOB). The findings discussed below show that mushroom clouds look and behave similarly when detonated at the same SHOB. The amount of residual radiation that is produced by a nuclear detonation is proportional to the yield. But, the amount of that residual radiation that actually becomes local fallout is strongly dependent on the SHOB and the type of surface over which the detonation occurs. In order to develop a more comprehensive model that predicts the fraction of the residual radiation that becomes local fallout, it is convenient to define a series of regimes based on SHOB values in which all detonations that occur within a given regime can be modeled using the same algorithms. The purpose of this paper is to provide a framework for defining different regimes, and, in a qualitative way, a basic understanding of the fundamental characteristics of each of these regimes.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Magnetic functionalization and catalytic behavior of magnetic nanoparticles during laser photochemical graphitization of polyimide

We report laser-assisted photochemical graphitization of polyimides (PIs) into functional magnetic nanocomposites using laser irradiation of PI in the presence of magnetite nanoparticles (MNPs). PI Kapton sheets covered with MNP were photochemically treated under ambient conditions using a picosecond pulsed laser (1064 nm) to obtain an electrically conductive material. Scanning electron microscopy of the treated material revealed a layered magnetic nanoparticle/graphite (MNP/graphite) nanocomposite structure. Four probe conductivity measurements indicated that the nanocomposite has an electrical conductivity of 1550 ± 60 S/m. Superconducting quantum interference device magnetometer-based magnetic characterization of the treated material revealed an anisotropic ferromagnetic response in the MNP/graphite nanocomposite compared to the isotropic response of MNP. Raman spectroscopy of the MNP/graphite nanocomposite revealed a fourfold improvement in graphitization, suppression in disorder, and decreased nitrogenous impurities compared to the graphitic material obtained from laser treatment of just PI sheets. X-ray photoelectron spectroscopy, x-ray diffraction, and energy-dispersive x-ray spectroscopy were used to delineate the phase transformations of MNP during the formation of MNP/graphite nanocomposite. Post-mortem characterization indicates a possible photocatalytic effect of MNP during MNP/graphite nanocomposite formation. Under laser irradiation, MNP transformed from the initial Fe 3 O 4 phase to γ-Fe 2 O 3 and Fe 5 C 2 phases and acted as nucleation spots to catalyze the graphitization process of PI.

36 MATERIALS SCIENCE↗

Imaging Spatial Variations of Optical Bandgaps in Perovskite Solar Cells

A fast, nondestructive, camera-based method to capture optical bandgap images of perovskite solar cells (PSCs) with micrometer-scale spatial resolution is developed. This imaging technique utilizes well-defined and relatively symmetrical band-to-band luminescence spectra emitted from perovskite materials, whose spectral peak locations coincide with absorption thresholds and thus represent their optical bandgaps. The technique is employed to capture relative variations in optical bandgaps across various PSCs, and to resolve optical bandgap inhomogeneity within the same device due to material degradation and impurities. Degradation and impurities are found to both cause optical bandgap shifts inside the materials. The results are confirmed with micro-photoluminescence spectroscopy scans. The excellent agreement between the two techniques opens opportunities for this imaging concept to become a quantified, high spatial resolution, large-area characterization tool of PSCs. This development continues to strengthen the high value of luminescence imaging for the research and development of this photovoltaic technology.

14 SOLAR ENERGY↗

Facile healing of cracks in organic–inorganic halide perovskite thin films

Organic-inorganic halide perovskite (OIHP) thin films at the heart of the burgeoning thin-film perovskite solar cells (PSCs) technology possess poor mechanical properties, which is likely to limit the long-term reliability of PSCs as they are poised for commercialization. In an effort to address this issue, in this work we demonstrate that through-thickness cracks induced by bending-tension in thin films of the two prototypical OlHPs, methylammonium lead triiodide (MAPbl(3)) and formamidinium lead triiodide (FAPbl(3)), can be healed easily. This is through the application of either a moderate compressive stress (bending-compression) at room temperature or a simple heat-treatment at modest temperatures. The crack-healing process is found to be time-dependent, which indicates that facile mass-transport in OlHPs plays a key role in this phenomenon. An explanation for this phenomenon is provided, one based on the fundamentals of brittle fracture. This discovery has broad implications for the prevention and/or restoration of the overall performance, environmental stability, and mechanical reliability of PSCs, and other devices.

36 MATERIALS SCIENCE↗

Far Infrared Synchrotron Near-Field Nanoimaging and Nanospectroscopy

Here, scattering scanning near-field optical microscopy (s-SNOM) has emerged as a powerful imaging and spectroscopic tool for investigating nanoscale heterogeneities in biology, quantum matter, and electronic and photonic devices. However, many materials are defined by a wide range of fundamental molecular and quantum states at far-infrared (FIR) resonant frequencies currently not accessible by s-SNOM. Here we show ultrabroadband FIR s-SNOM nanoimaging and spectroscopy by combining synchrotron infrared radiation with a novel fast and low-noise copper-doped germanium (Ge:Cu) photoconductive detector. This approach of FIR synchrotron infrared nanospectroscopy (SINS) extends the wavelength range of s-SNOM to 31 μm (320 cm –1 , 9.7 THz), exceeding conventional limits by an octave to lower energies. We demonstrate this new nanospectroscopic window by measuring elementary excitations of exemplary functional materials, including surface phonon polariton waves and optical phonons in oxides and layered ultrathin van der Waals materials, skeletal and conformational vibrations in molecular systems, and the highly tunable plasmonic response of graphene.

47 OTHER INSTRUMENTATION↗

Atomic-scale visualization of defect-induced localized vibrations in GaN

Phonon engineering is crucial for thermal management in GaN-based power devices, where phonon-defect interactions limit performance. However, detecting nanoscale phonon transport constrained by III-nitride defects is challenging due to limited spatial resolution. Here, we used advanced scanning transmission electron microscopy and electron energy loss spectroscopy to examine vibrational modes in a prismatic stacking fault in GaN. By comparing experimental results with ab initio calculations, we identified three types of defect-derived modes: localized defect modes, a confined bulk mode, and a fully extended mode. Additionally, the PSF exhibits a smaller phonon energy gap and lower acoustic sound speeds than defect-free GaN, suggesting reduced thermal conductivity. Our study elucidates the vibrational behavior of a GaN defect via advanced characterization methods and highlights properties that may affect thermal behavior.

36 MATERIALS SCIENCE↗

Flexible and High Performance Supercapacitors Based on NiCo2O4for Wide Temperature Range Applications

Binder free nanostructured NiCo 2 O 4 were grown using a facile hydrothermal technique. X-ray diffraction patterns confirmed the phase purity of NiCo 2 O 4 . The surface morphology and microstructure of the NiCo 2 O 4 analyzed by scanning electron microscopy (SEM) showed flower-like morphology composed of needle-like structures. The potential application of binder free NiCo 2 O 4 as an electrode for supercapacitor devices was investigated using electrochemical methods. The cyclic voltammograms of NiCo2O4 electrode using alkaline aqueous electrolytes showed the presence of redox peaks suggesting pseudocapacitance behavior. Quasi-solid state supercapacitor device fabricated by sandwiching two NiCo 2 O 4 electrodes and separating them by ion transporting layer. The performance of the device was tested using cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. The device showed excellent flexibility and cyclic stability. The temperature dependent charge storage capacity was measured for their variable temperature applications. Specific capacitance of the device was enhanced by ~150% on raising the temperature from 20 to 60°C. Hence, the results suggest that NiCo 2 O 4 grown under these conditions could be a suitable material for high performance supercapacitor devices that can be operated at variable temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Confocal Microscopy on Light-emitting Nanostructures and X-ray Imaging Detectors Based on Color Centers in Lithium Fluoride

Confocal Laser Scanning Microscope (CLSM) is a versatile and powerful optical instrument which is gaining a strong increase of interest for biological investigations and also for the characterization of materials, microstructures and devices. We exploit its capability for the characterization of light-emitting micro and nano-structures based on color centers in lithium fluoride. CLSM was successfully used as an advanced optical reading system to detect X-ray micro-radiographies of biological specimens stored in LiF imaging detectors.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Interface energetics and atomic structure of epitaxial La{sub 1−x}Sr{sub x}CoO{sub 3} on Nb:SrTiO{sub 3}

The energetics at oxide semiconductor/La{sub 1−x}Sr{sub x}CoO{sub 3} heterojunctions, including the respective alignment of the valence and conduction bands, govern charge transfer and have to be determined for the design of future La{sub 1−x}Sr{sub x}CoO{sub 3}-based devices. In this letter, the electronic and atomic structures of epitaxial La{sub 1−x}Sr{sub x}CoO{sub 3} on Nb-doped strontium titanate are revealed by scanning transmission electron microscopy, electron energy loss spectroscopy, and in situ x-ray and ultra violet photoelectron spectroscopies. For LaCoO{sub 3}, a valence band (VB) offset of 2.8 ± 0.1 eV is deduced. The large offset is attributed to the orbital contributions of the Co 3d states to the VB maximum of the LaCoO{sub 3} thin films, with no evidence of interface dipole contributions. The sensitivity of the valence band orbital character to spin state ordering and oxygen vacancies is assessed using density functional theory.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Soft x-ray spectromicroscopy using compact scanning transmission x-ray microscope at the photon factory

We report the stability and recent performances of a new type of scanning transmission X-ray microscopy. The optics and compact design of the microscope realized mobility and robust performance. Detailed consideration to the vibration control will be described. The insertion device upgraded to elliptical polarization undulator enabled linear dichroism and circular dichroism experiments.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Towards the development of a hybrid-integrated chip interferometer for online surface profile measurements

Non-destructive testing and online measurement of surface features are pressing demands in manufacturing. Thus optical techniques are gaining importance for characterization of complex engineering surfaces. Harnessing integrated optics for miniaturization of interferometry systems onto a silicon wafer and incorporating a compact optical probe would enable the development of a handheld sensor for embedded metrology applications. In this work, we present the progress in the development of a hybrid photonics based metrology sensor device for online surface profile measurements. The measurement principle along with test and measurement results of individual components has been presented. For non-contact measurement, a spectrally encoded lateral scanning probe based on the laser scanning microscopy has been developed to provide fast measurement with lateral resolution limited to the diffraction limit. The probe demonstrates a lateral resolution of ∼3.6 μm while high axial resolution (sub-nanometre) is inherently achieved by interferometry. Further the performance of the hybrid tuneable laser and the scanning probe was evaluated by measuring a standard step height sample of 100 nm.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Space-Charge-Limited van der Waals Spin Transistor

Integrating semiconducting and magnetic materials could combine transistorlike operation with nonvolatility and enable architectures such as logic in memory. Here, in this work, we employ correlated electrical transport and scanning nitrogen-vacancy center magnetic imaging to elucidate a spin transistor concept that amalgamates vertical and lateral hopping transport inside a 2D antiferromagnetic semiconductor, mechanistically distinct from vertical tunneling devices. Our device, based on a monolayer-bilayer junction in CrSBr, displays giant, gate-tunable magnetoresistance driven by the dual action of electrostatic doping on space-charge-limited lateral conduction and interlayer exchange coupling. Moreover, we visualize a field-trainable, layer-sharing effect that selects between coherent or domain-wall reversal at the spin-flip transition, enabling multilevel, memristive conductance states. Our layer-dependent space charge mechanism for convergent electrical and magnetic control opens opportunities to address limitations in contemporary computing.

2-dimensional systems↗

Aluminum Nitride Based MEMS IF Filter Array for Analog Spectral Processors

The purpose of this project was to enable new levels of performance in radio frequency systems, such as adaptability, size and stability, based on aluminum nitride microresonator technology. Early in the project, in 2008, Sandia developed arrays of filters for realizing high scan rate spectrum analyzers at 20 MHz and Rockwell Collins demonstrated a high scan rate spectrum analyzer leveraging this technology in 2009. The filter arrays, because of the transduction physics, demonstrated massively reduced size, loss and impedance compared to existing filter technologies. These device level benefits translated to reduced size and power for the spectrum analyzers at the system level.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗