An official website of the United States government
Abstract Electronic properties of silicon, the most important semiconductor material, are controlled through doping. The range of achievable properties can be extended by hyperdoping, i.e., doping to concentrations beyond the nominal equilibrium solubility of the dopant. Here, hyperdoping is achieved in a laser pyrolysis reactor capable of providing nonequilibrium conditions, where doping is governed by kinetics rather than thermodynamics. High resolution scanning transmission electron microscopy (TEM) with energy‐dispersive X‐ray spectroscopy shows that the boron atom distribution in the hyperdoped nanoparticles is relatively uniform. The hyperdoped nanoparticles demonstrate tunable localized surface plasmon resonance (LSPR) and are stable in air for periods of at least one year. The hyperdoped nanoparticles are also stable upon annealing at temperatures up to 600 °C. Furthermore, boron hyperdoping does not change the diamond cubic crystal structure of silicon, as demonstrated in detail by high flux synchrotron X‐ray diffraction and pair distribution function (PDF) analysis, supported by high‐resolution TEM analysis.
more »
« less
Distinguishing Elements at the Sub‐Nanometer Scale on the Surface of a High Entropy Alloy
Abstract Materials in crystalline form possess translational symmetry (TS) when the unit cell is repeated in real space with long‐ and short‐range orders. The periodic potential in the crystal regulates the electron wave function and results in unique band structures, which further define the physical properties of the materials. Amorphous materials lack TS due to the randomization of distances and arrangements between atoms, causing the electron wave function to lack a well‐defined momentum. High entropy materials provide another way to break the TS by randomizing the potential strength at periodic atomic sites. The local elemental distribution has a great impact on physical properties in high entropy materials. It is critical to distinguish elements at the sub‐nanometer scale to uncover the correlations between the elemental distribution and the material properties. Here, the use of synchrotron X‐ray scanning tunneling microscopy (SX‐STM) with sub‐nm scale resolution in identifying elements on a high entropy alloy (HEA) surface is demonstrated. By examining the elementally sensitive X‐ray absorption spectra with an STM tip to enhance the spatial resolution, the elemental distribution on an HEA's surface at a sub‐nm scale is extracted. These results open a pathway towards quantitatively understanding high entropy materials and their material properties.
more »
« less
- PAR ID:
- 10641250
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 36
- Issue:
- 28
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract High entropy oxides are a class of materials distinguished by the use of configurational entropy to drive material synthesis. These materials are being examined for their exciting physiochemical properties and hold promise in numerous fields, such as chemical sensing, electronics, and catalysis. Patterning and integration of high entropy materials into devices and platforms can be difficult due to their thermal sensitivity and incompatibility with many conventional thermally-based processing techniques. In this work, we present a laser-based technique, laser-induced thermal voxels, that combines the synthesis and patterning of high entropy oxides into a single process step, thereby allowing patterning of high entropy materials directly onto substrates. As a proof-of-concept, we target the synthesis and patterning of a well-characterized rock salt-phase high entropy oxide, (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)O, as well as a spinel-phase high entropy oxide, (Mg0.2Ni0.2Co0.2Cu0.2Zn0.2)Cr2O4. We show through electron microscopy and x-ray analysis that the materials created are atomically homogenous and are primarily of the rock salt or spinel phase. These findings show the efficacy of laser induced thermal voxel processing for the synthesis and patterning of high entropy materials and enable new routes for integration of high entropy materials within microscale platform and devices.more » « less
-
Abstract Lithium/fluorinated graphite (Li/CFx) primary batteries show great promise for applications in a wide range of energy storage systems due to their high energy density (>2100 Wh kg–1) and low self‐discharge rate (<0.5% per year at 25 °C). While the electrochemical performance of the CFxcathode is indeed promising, the discharge reaction mechanism is not thoroughly understood to date. In this article, a multiscale investigation of the CFxdischarge mechanism is performed using a novel cathode structure to minimize the carbon and fluorine additives for precise cathode characterizations. Titration gas chromatography, X‐ray diffraction, Raman spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, cross‐sectional focused ion beam, high‐resolution transmission electron microscopy, and scanning transmission electron microscopy with electron energy loss spectroscopy are utilized to investigate this system. Results show no metallic lithium deposition or intercalation during the discharge reaction. Crystalline lithium fluoride particles uniformly distributed with <10 nm sizes into the CFxlayers, and carbon with lower sp2content similar to the hard‐carbon structure are the products during discharge. This work deepens the understanding of CFxas a high energy density cathode material and highlights the need for future investigations on primary battery materials to advance performance.more » « less
-
Abstract Mott metal–insulator transitions possess electronic, magnetic, and structural degrees of freedom promising next‐generation energy‐efficient electronics. A previously unknown, hierarchically ordered, and anisotropic supercrystal state is reported and its intrinsic formation characterized in‐situ during a Mott transition in a Ca2RuO4thin film. Machine learning‐assisted X‐ray nanodiffraction together with cryogenic electron microscopy reveal multi‐scale periodic domain formation at and below the film transition temperature (TFilm ≈ 200–250 K) and a separate anisotropic spatial structure at and aboveTFilm. Local resistivity measurements imply an intrinsic coupling of the supercrystal orientation to the material's anisotropic conductivity. These findings add a new degree of complexity to the physical understanding of Mott transitions, opening opportunities for designing materials with tunable electronic properties.more » « less
-
Titanium nitride (TiN) materials have gained an interest over the past years due to their unique characteristics, such as thermal stability, extreme hardness, low production cost, and comparable optical properties to gold. In the present study, TiN nanoparticles were synthesized via a thermal benzene route to obtain black nanoparticles. Scanning electron microscopy (SEM) was carried out to examine the morphology. Further microscopic characterization was done where the final product was drop cast onto double-sided conductive carbon tape and sputter-coated with gold/palladium at a thickness of 4 nm for characterization by field emission scanning electron microscopy (FE-SEM) with energy dispersive X-Ray spectroscopy (EDS) that revealed they are spherical. ImageJ software was used to measure the average size of the particles to be 79 nm in diameter. EDS was used to determine the elements present in the sample and concluded that there were no impurities. Further characterization by Fourier Transform infrared (FTIR) spectroscopy was carried out to identify the characteristic peaks of TiN. X-ray diffraction (XRD) revealed typical peaks of cubic phase titanium nitride, and crystallite size was determined to be 14 nm using the Debye-Scherrer method. Dynamic light scattering (DLS) analysis revealed the size distribution of the TiN nanoparticles, with nanoparticles averaging at 154 nm in diameter. Zeta potential concluded the surface of the TiN nanoparticles is negatively charged.more » « less
