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At least 1,153 records · Page 64

Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor

The rational bottom-up synthesis of atomically defined graphene nanoribbon (GNR) heterojunctions represents an enabling technology for the design of nanoscale electronic devices. Synthetic strategies used thus far have relied on the random copolymerization of two electronically distinct molecular precursors to yield GNR heterojunctions. In this paper we report the fabrication and electronic characterization of atomically precise GNR heterojunctions prepared through late-stage functionalization of chevron GNRs obtained from a single precursor. Post-growth excitation of fully cyclized GNRs induces cleavage of sacrificial carbonyl groups, resulting in atomically well-defined heterojunctions within a single GNR. The GNR heterojunction structure was characterized using bond-resolved scanning tunnelling microscopy, which enables chemical bond imaging at T = 4.5 K. Scanning tunnelling spectroscopy reveals that band alignment across the heterojunction interface yields a type II heterojunction, in agreement with first-principles calculations. Finally, GNR heterojunction band realignment proceeds over a distance less than 1 nm, leading to extremely large effective fields.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Large-scale synthesis of Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln{sup 3+} = Eu{sup 3+}, Tb{sup 3+}, Yb{sup 3+}/Er{sup 3+}, Yb{sup 3+}/Tm{sup 3+}, and Yb{sup 3+}/Ho{sup 3+}) microspheres and their photoluminescence properties

Graphical abstract: In this work, multicolor and monodisperse Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln{sup 3+} = Eu{sup 3+}, Tb{sup 3+}, Yb{sup 3+}/Er{sup 3+}, Yb{sup 3+}/Tm{sup 3+}, and Yb{sup 3+}/Ho{sup 3+}) microspheres were prepared by a homogeneous precipitation method followed by a subsequent calcination process. Display Omitted Highlights: ► Lu{sub 2}O{sub 3}:Ln{sup 3+} microspheres were prepared by a precipitation followed by a calcination process. ► Lu{sub 2}O{sub 3}:Eu{sup 3+}/Tb{sup 3+} samples exhibit respective red or green emissions. ► Lu{sub 2}O{sub 3}:Yb{sup 3+}/Er{sup 3+}/Tm{sup 3+}/Ho{sup 3+} exhibit emissions of green, blue, yellow-green, respectively. ► These finding may find potential applications in bioanalysis and field emission displays. -- Abstract: In this work, multicolor and monodisperse Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln{sup 3+} = Eu{sup 3+}, Tb{sup 3+}, Yb{sup 3+}/Er{sup 3+}, Yb{sup 3+}/Tm{sup 3+}, and Yb{sup 3+}/Ho{sup 3+}) microspheres were prepared by a homogeneous precipitation method followed by a subsequent calcination process. X-ray diffraction (XRD), Fourier transformed infrared (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra, and cathodoluminescence (CL) spectra were employed to characterize the samples. Upon ultraviolet and low-voltage electron beams excitation, Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln{sup 3+} = Eu{sup 3+} and Tb{sup 3+}) samples exhibit respective bright red (Eu{sup 3+}, {sup 5}D{sub 0} → {sup 7}F{sub 2}) and green (Tb{sup 3+}, {sup 5}D{sub 4} → {sup 7}F{sub 5}) down-conversion (DC) emissions. Under 980 nm NIR irradiation, Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln{sup 3+} = Yb{sup 3+}/Er{sup 3+}, Yb{sup 3+}/Tm{sup 3+}, and Yb{sup 3+}/Ho{sup 3+}) exhibit characteristic up-conversion (UC) emissions of green (Er{sup 3+}, {sup 4}S{sub 3/2}, {sup 2}H{sub 11/2} → {sup 4}I{sub 15/2}), blue (Tm{sup 3+}, {sup 1}G{sub 4} → {sup 3}H{sub 6}) and yellow-green (Ho{sup 3+}, {sup 5}F{sub 4}, {sup 5}S{sub 2} → {sup 5}I{sub 8}), respectively. These finding may find potential applications in bioanalysis, optoelectronic and nanoscale devices, field emission displays, and so on.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural and dielectric properties of yttrium substituted nickel ferrites

Graphical abstract: - Highlights: • Dense NiFe{sub 2−x}Y{sub x}O{sub 4} ceramics (with 0 ≤ x ≤ 0.3) were prepared. • Pure spinels were obtained for x ≤ 0.07 while for x ≥ 0.15 samples had secondary phases. • With addition of yttrium, ac conductivity slightly increased. • We suggest several effects that can explain the observed changes in ac conduction. • With addition of yttrium, dielectric constant increased while the tg δ decreased. - Abstract: The influence of Y{sup 3+} ions on structural and dielectric properties of nickel ferrites (NiFe{sub 2−x}Y{sub x}O{sub 4}, where 0 ≤ x ≤ 0.3) has been studied. The as-synthesized samples, prepared by the co-precipitation method, were analyzed by XRD and FTIR which suggested that Y{sup 3+} ions were incorporated into the crystal lattice for all the samples. However, the XRD analysis of the sintered samples showed that secondary phases appear in the samples with x > 0.07. The samples have densities greater than 90% TD and the SEM images showed that the grain size decreases with the addition of yttrium. Dielectric properties measured from 150 to 25 °C in the frequency range of 100 Hz–1 MHz showed that the addition of yttrium slightly increases the ac conductivity and decreases the tg δ therefore making the materials better suited for the use in microwave devices.

36 MATERIALS SCIENCE↗

Emergence of charge density waves and a pseudogap in single-layer TiTe 2

Two-dimensional materials constitute a promising platform for developing nanoscale devices and systems. Their physical properties can be very different from those of the corresponding three-dimensional materials because of extreme quantum confinement and dimensional reduction. Here in this paper we report a study of TiTe 2 from the single-layer to the bulk limit. Using angle-resolved photoemission spectroscopy and scanning tunneling microscopy and spectroscopy, we observed the emergence of a (2 × 2) charge density wave order in single-layer TiTe 2 with a transition temperature of 92 ± 3 K. Also observed was a pseudogap of about 28 meV at the Fermi level at 4.2 K. Surprisingly, no charge density wave transitions were observed in two-layer and multi-layer TiTe 2 , despite the quasi-two-dimensional nature of the material in the bulk. The unique charge density wave phenomenon in the single layer raises intriguing questions that challenge the prevailing thinking about the mechanisms of charge density wave formation.

36 MATERIALS SCIENCE↗

Photoelectric conversion on Earth’s surface via widespread Fe- and Mn-mineral coatings

Sunlight drives photosynthesis and associated biological processes, and also influences inorganic processes that shape Earth’s climate and geochemistry. Bacterial solar-to-chemical energy conversion on this planet evolved to use an intricate intracellular process of phototrophy. However, a natural nonbiological counterpart to phototrophy has yet to be recognized. In this work, we reveal the inherent “phototrophic-like” behavior of vast expanses of natural rock/soil surfaces from deserts, red soils and karst environments, all of which can drive photon-to-electron conversions. Using scanning electron microscopy, transmission electron microscopy, micro-Raman spectroscopy and X-ray absorption spectroscopy, Fe and Mn (oxyhydr)oxide-rich coatings were found in rock varnishes, as were Fe (oxyhydr)oxides on red soil surfaces and minute amounts of Mn oxides on karst rock surfaces. By directly fabricating a photoelectric detection device on the thin section of a rock varnish sample, we have recorded the first in situ photocurrent micromapping of the coatings, which behave as highly sensitive and stable photoelectric systems. Additional measurements of red soil and powder separated from the outermost surface of karst rocks yielded photocurrents that are also sensitive to irradiation. The prominent solar-responsive capability of the phototrophic-like rocks/soils is ascribed to the semiconducting Fe and Mn (oxyhydr)oxide mineral coatings. The native semiconducting Fe/Mn-rich coatings may play a role similar in part to photosynthetic systems and thus provide a distinctive driving force for redox (bio)geochemistry on Earth’s surfaces.

Lu, Anhuai↗

Beam-driven dynamics of aluminium dopants in graphene

Abstract Substituting heteroatoms into graphene can tune its properties for applications ranging from catalysis to spintronics. The further recent discovery that covalent impurities in graphene can be manipulated at atomic precision using a focused electron beam may open avenues towards sub-nanometer device architectures. However, the preparation of clean samples with a high density of dopants is still very challenging. Here, we report vacancy-mediated substitution of aluminium into laser-cleaned graphene, and without removal from our ultra-high vacuum apparatus, study their dynamics under 60 keV electron irradiation using aberration-corrected scanning transmission electron microscopy and spectroscopy. Three- and four-coordinated Al sites are identified, showing excellent agreement with ab initio predictions including binding energies and electron energy loss spectrum simulations. We show that the direct exchange of carbon and aluminium atoms predicted earlier occurs under electron irradiation, although unexpectedly it is less probable than the same process for silicon. We also observe a previously unknown nitrogen–aluminium exchange that occurs at Al–N double-dopant sites at graphene divacancies created by our plasma treatment.

36 MATERIALS SCIENCE↗

SU-F-T-169: A Periodic Quality Assurance Program for a Spot-Scanning Proton Treatment Facility

Purpose: To develop daily and monthly quality assurance (QA) programs in support of a new spot-scanning proton treatment facility using a combination of commercial and custom equipment and software. Emphasis was placed on efficiency and evaluation of key quality parameters. Methods: The daily QA program was developed to test output, spot size and position, proton beam energy, and image guidance using the Sun Nuclear Corporation rf-DQA™3 device and Atlas QA software. The program utilizes standard Atlas linear accelerator tests repurposed for proton measurements and a custom jig for indexing the device to the treatment couch. The monthly QA program was designed to test mechanical performance, image quality, radiation quality, isocenter coincidence, and safety features. Many of these tests are similar to linear accelerator QA counterparts, but many require customized test design and equipment. Coincidence of imaging, laser marker, mechanical, and radiation isocenters, for instance, is verified using a custom film-based device devised and manufactured at our facility. Proton spot size and position as a function of energy are verified using a custom spot pattern incident on film and analysis software developed in-house. More details concerning the equipment and software developed for monthly QA are included in the supporting document. Thresholds for daily and monthly tests were established via perturbation analysis, early experience, and/or proton system specifications and associated acceptance test results. Results: The periodic QA program described here has been in effect for approximately 9 months and has proven efficient and sensitive to sub-clinical variations in treatment delivery characteristics. Conclusion: Tools and professional guidelines for periodic proton system QA are not as well developed as their photon and electron counterparts. The program described here efficiently evaluates key quality parameters and, while specific to the needs of our facility, could be readily adapted to other proton centers.

60 APPLIED LIFE SCIENCES↗

An error reduction algorithm to improve lidar turbulence estimates for wind energy

Abstract. Remote-sensing devices such as lidars are currently being investigated as alternatives to cup anemometers on meteorological towers for the measurement of wind speed and direction. Although lidars can measure mean wind speeds at heights spanning an entire turbine rotor disk and can be easily moved from one location to another, they measure different values of turbulence than an instrument on a tower. Current methods for improving lidar turbulence estimates include the use of analytical turbulence models and expensive scanning lidars. While these methods provide accurate results in a research setting, they cannot be easily applied to smaller, vertically profiling lidars in locations where high-resolution sonic anemometer data are not available. Thus, there is clearly a need for a turbulence error reduction model that is simpler and more easily applicable to lidars that are used in the wind energy industry. In this work, a new turbulence error reduction algorithm for lidars is described. The Lidar Turbulence Error Reduction Algorithm, L-TERRA, can be applied using only data from a stand-alone vertically profiling lidar and requires minimal training with meteorological tower data. The basis of L-TERRA is a series of physics-based corrections that are applied to the lidar data to mitigate errors from instrument noise, volume averaging, and variance contamination. These corrections are applied in conjunction with a trained machine-learning model to improve turbulence estimates from a vertically profiling WINDCUBE v2 lidar. The lessons learned from creating the L-TERRA model for a WINDCUBE v2 lidar can also be applied to other lidar devices. L-TERRA was tested on data from two sites in the Southern Plains region of the United States. The physics-based corrections in L-TERRA brought regression line slopes much closer to 1 at both sites and significantly reduced the sensitivity of lidar turbulence errors to atmospheric stability. The accuracy of machine-learning methods in L-TERRA was highly dependent on the input variables and training dataset used, suggesting that machine learning may not be the best technique for reducing lidar turbulence intensity (TI) error. Future work will include the use of a lidar simulator to better understand how different factors affect lidar turbulence error and to determine how these errors can be reduced using information from a stand-alone lidar.

17 WIND ENERGY↗

Near-field scanning microwave microscopy of few-layer graphene.

Near-field microwave microscopy can be used as an alternative to atomic-force microscopy or Raman microscopy in determination of graphene thickness. We evaluated the values of AC impedance for few layer graphene. The impedance of mono and few-layer graphene at 4GHz was found predominantly active. Near-field microwave microscopy allows simultaneous imaging of location, geometry, thickness, and distribution of electrical properties of graphene without device fabrication. Our results may be useful for design of future graphene-based microwave devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Laser Additive Manufacturing Process Development for Bismuth Telluride Thermoelectric Material

Thermoelectric generators have strong potential for aerospace and aircraft applications. However, traditional manufacturing methods for thermoelectric devices severely limit device adaptability and consequently marketability. Laser powder bed fusion is an additive manufacturing method which shows promising potential for producing thermoelectric devices. Thermoelectric materials pose unique challenges compared to metals because of low thermal conductivity, brittle fracture characteristics, and irregular powder particle morphologies. Herein, we communicate processing procedures to fabricate thermoelectric parts of Bi 2 Te 3 through laser powder bed fusion. In this study, we identify the successful combination of key process parameters—laser power, scan speed, hatch distance, and powder layer thickness—to achieve high-quality parts in terms of density and physical properties, and we demonstrate the impact of process parameter variation on built part quality. While it cannot exclusively determine part quality, the volumetric energy density is a useful guide in deciding process parameters for thermoelectric materials, and the optimal value is between 9 and 11 J/mm 3 for Bi 2 Te 3 . We demonstrate successful fabrication of different freeform geometries of Bi 2 Te 3 powders. The results suggest it is possible to extend this method more broadly to other semiconductor materials, including thermoelectric power generation materials applicable for space applications.

36 MATERIALS SCIENCE↗

The site occupation and valence of Mn ions in the crystal lattice of Sr{sub 4}Al{sub 14}O{sub 25} and its deep red emission for high color-rendering white light-emitting diodes

Highlights: • Different valences of Mn ions in Sr{sub 4}Al{sub 14}O{sub 25} were identified using XANES and EPR. • Red luminescence was attributed to Mn{sup 4+} occupying the center of AlO{sub 6} octahedron. • The Mn{sup 3+} incorporated in the center of AlO{sub 4} tetrahedron was non-luminescent. • The bond-valence theory was used to analyze the effective valences of cations. • A white LED device with CRI up to Ra 93.23 was packaged by using the red phosphor. - Abstract: The synthesis and component of red phosphor, Sr{sub 4}Al{sub 14}O{sub 25}: Mn, were optimized for application in white light-emitting diodes. The microstructure and morphology were investigated by the X-ray diffraction and scanning electron microscopy. Different valences of Mn ions in Sr{sub 4}Al{sub 14}O{sub 25} were discriminated using the electron paramagnetic resonance and X-ray absorption near-edge structure spectroscopy techniques. The bond-valence theory was used to analyze the effective valences of Sr{sup 2+} and Al{sup 3+} in Sr{sub 4}Al{sub 14}O{sub 25}. As a result, the strong covalence of Al{sup 3+} in the AlO{sub 4} tetrahedron other than in the AlO{sub 6} octahedron is disclosed. The deep red emission is attributed to Mn{sup 4+} occupying the center of AlO{sub 6} octahedron. The mechanism of energy transfer is mainly through dipole–dipole interaction, revealed by the analyses of critical distance and concentration quench. A high color rendering white LED prototype with color-rendering index up to Ra 93.23 packaged by using the red phosphor demonstrates its applicability.

36 MATERIALS SCIENCE↗

Transparent ohmic contacts for solution-processed, ultrathin CdTe solar cells

Recently, solution-processing became a viable route for depositing CdTe for use in photovoltaics. Ultrathin (~500 nm) solar cells have been made using colloidal CdTe nanocrystals with efficiencies exceeding 12% power conversion efficiency (PCE) demonstrated by using very simple device stacks. Further progress requires an effective method for extracting charge carriers generated during light harvesting. Here, we explored solution-based methods for creating transparent Ohmic contacts to the solution-deposited CdTe absorber layer and demonstrated molecular and nanocrystal approaches to Ohmic hole-extracting contacts at the ITO/CdTe interface. Furthermore, we used scanning Kelvin probe microscopy to further show how the above approaches improved carrier collection by reducing the potential drop under reverse bias across the ITO/CdTe interface. Other methods, such as spin-coating CdTe/A 2 CdTe 2 (A = Na, K, Cs, N 2 H 5 ), can be used in conjunction with current/light soaking to improve PCE further.

14 SOLAR ENERGY↗

A new ion sensing deep atomic force microscope

Here we describe a new deep atomic force microscope (AFM) capable of ion sensing. A novel probe assembly incorporates a micropipette that can be used both for sensing ion currents and as the tip for AFM imaging. The key advance of this instrument over previous ion sensing AFMs is that it uses conventional micropipettes in a novel suspension system. This paper focuses on sensing the ion current passively while using force feedback for the operation of the AFM in contact mode. Two images are obtained simultaneously: (1) an AFM topography image and (2) an ion current image. As an example, two images of a MEMS device with a microchannel show peaks in the ion current as the pipette tip goes over the edges of the channel. This ion sensing AFM can also be used in other modes including tapping mode with force feedback as well as in non-contact mode by utilizing the ion current for feedback, as in scanning ion conductance microscopy. The instrument is gentle enough to be used on some biological samples such as plant leaves.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

TH-A-18C-10: Dynamic Intensity Weighted Region of Interest Imaging

Purpose: For image guidance tasks full image quality is not required throughout the entire image. With dynamic filtration of the kV imaging beam the noise properties of the CT image can be locally controlled, providing a high quality image around the target volume with a lower quality surrounding region while providing substantial dose sparing to the patient as well as reduced scatter fluence on the detector. Methods: A dynamic collimation device with 3mm copper blades has been designed to mount in place of the bowtie filter on the On-Board Imager (Varian Medical Systems). The beam intensity is reduced by 95% behind the copper filters and the aperture is controlled dynamically to conformally illuminate a given ROI during a standard cone-beam CT scan. A data correction framework to account for the physical effects of the collimator prior to reconstruction was developed. Furthermore, to determine the dose savings and scatter reduction a monte carlo model was built in BEAMnrc with specifics from the Varian Monte Carlo Data Package. The MC model was validated with Gafchromic film. Results: The reconstructed image shows image quality comparable to a standard scan in the specified ROI, with higher noise and streaks in the outer region but still sufficient information for alignment to high contrast structures. The monte carlo modeling showed that the scatter-to-primary ratio was reduced from 1.26 for an unfiltered scan to 0.45 for an intensity weighted scan, suggesting that image quality may be improved in the inner ROI. Dose in the inner region was reduced 10–15% due to reduced scatter and by as much as 75% in the outer region. Conclusion: Dynamic intensity-weighted ROI imaging allows reduction of imaging dose to sensitive organs away from the target region while providing images that retain their utility for patient setup and procedure guidance. Funding was provided in part by Varian Medical Systems and NIH Grants 1RO1CA120540, T32EB002103, S10 RR021039 and P30 CA14599. The contents of this work are solely the responsibility of the authors and do not necessarily represent the official views of any of the supporting organizations.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

SU-E-T-04: 3D Dose Based Patient Compensator QA Procedure for Proton Radiotherapy

Purpose: In proton double-scattering radiotherapy, compensators are the essential patient specific devices to contour the distal dose distribution to the tumor target. Traditional compensator QA is limited to checking the drilled surface profiles against the plan. In our work, a compensator QA process was established that assess the entire compensator including its internal structure for patient 3D dose verification. Methods: The fabricated patient compensators were CT scanned. Through mathematical image processing and geometric transformations, the CT images of the proton compensator were combined with the patient simulation CT images into a new series of CT images, in which the imaged compensator is placed at the planned location along the corresponding beam line. The new CT images were input into the Eclipse treatment planning system. The original plan was calculated to the combined CT image series without the plan compensator. The newly computed patient 3D dose from the combined patientcompensator images was verified against the original plan dose. Test plans include the compensators with defects intentionally created inside the fabricated compensators. Results: The calculated 3D dose with the combined compensator and patient CT images reflects the impact of the fabricated compensator to the patient. For the test cases in which no defects were created, the dose distributions were in agreement between our method and the corresponding original plans. For the compensator with the defects, the purposely changed material and a purposely created internal defect were successfully detected while not possible with just the traditional compensator profiles detection methods. Conclusion: We present here a 3D dose verification process to qualify the fabricated proton double-scattering compensator. Such compensator detection process assesses the patient 3D impact of the fabricated compensator surface profile as well as the compensator internal material and structure changes. This research receives funding support from CURA Medical Technologies.

60 APPLIED LIFE SCIENCES↗

Novel Applications of Near-Field Scanning Optical Microscopy (NSOM)

The Near-Field Scanning Optical Microscope (NSOM) was used to image a wide array samples using a variety of standard and non-standard operating conditions on a custom system built in Org. 5625. The ability of this technique to produce high-quality images was assessed during this one-year LDRD. To obtain details about the devices imaged, as well as the experimental details, please refer to the classified report from the project manager, Rich Dondero, or the NSP IA lead, Kristina Czuchlewski.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Novel Applications of Scanning Ultrafast Electron Microscopy (SUEM)

The Scanning Ultrafast Electron Microscope (SUEM) was used to image a wide array samples using a variety of standard and non-standard operating conditions on a custom system built in Org. 8942. The ability of this technique to produce high-quality images was assessed during this one year LDRD. To obtain details about the devices imaged, as well as the experimental details, please refer to the classified report from the project manager, Rich Dondero, or the NSP IA lead, Kristina Czuchlewski.

47 OTHER INSTRUMENTATION↗

In-Situ Study of Microstructure Evolution of Spinodal Decomposition in an Al-Rich High-Entropy Alloy

High-entropy alloys (HEAs) are materials which leverage the entropy of mixing to motivate the formation of single-phase solid solutions, even of immiscible elements. While these materials are well-recognized for their application to structural engineering, there is increasing interest in the use of HEAs for functional applications such as memory storage and energy devices. The current work investigates the HEA Al 1.3 CoCrCuFeNi, which has been previously shown to be single-phase at high temperatures, but undergoes phase separation at lower temperatures, transforming the structural and the functional properties. This phase separation is investigated at high temperatures with in-situ small angle neutron scattering (SANS) and scanning transmission electron microscopy (EDS). These techniques show that increasing the temperature up to 800°C, the microstructure of the HEA adiabatically disorders and abruptly homogenizes near 700°C, which is consistent with spinodal decomposition. Overall, the microstructural evolution proceeds mainly by the atomistic redistribution of the constituent elements within simple crystal lattices, producing coherent phase mixtures.

36 MATERIALS SCIENCE↗