Superhard boron-carbon materials are of prime interest due to their non-oxidizing properties at high temperatures compared to diamond-based materials and their non-reactivity with ferrous metals under extreme conditions. In this work, evolutionary algorithms combined with density functional theory have been utilized to predict stable structures and properties for the boron-carbon system, including the elusive superhard BC5 compound. We report on the microwave plasma chemical vapor deposition on a silicon substrate of a series of composite materials containing amorphous boron-doped graphitic carbon, boron-doped diamond, and a cubic hard-phase with a boron-content as high as 7.7 at%. The nanoindentation hardness of these composite materials can be tailored from 8 GPa to as high as 62 GPa depending on the growth conditions. These materials have been characterized by electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, X-ray diffraction, and nanoindentation hardness, and the experimental results are compared with theoretical predictions. Our studies show that a significant amount of boron up to 7.7 at% can be accommodated in the cubic phase of diamond and its phonon modes and mechanical properties can be accurately modeled by theory. This cubic hard-phase can be incorporated into amorphous boron-carbon matrices to yield superhard materials with tunable hardness values.
more »
« less
Synthesis and Properties of Plasmonic Boron‐Hyperdoped Silicon Nanoparticles
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
- Award ID(s):
- 1809439
- PAR ID:
- 10435595
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 29
- Issue:
- 8
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Pd nanoparticles anchored on Nb-doped TiO 2 with functionalized carbon support (denoted as Pd/Nb–TiO 2 –C) is synthesized through a controllable hydrolysis and impregnation method. The as-synthesized catalyst is characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Pd nanoparticles exhibit a uniform distribution with an average particle size of 3 nm. The electrochemical performance is tested by cyclic voltammetry (CV) and chronoamperometry (CA). Compared with Pd supported by functionalized carbon (Pd/C), Pd/Nb–TiO 2 –C demonstrates 15.7% higher metallic Pd content, 23% higher electrochemical active surface area, 75% higher current density in ethanol electro-oxidation, 5% higher durability, and better tolerance of carbonaceous species. The performance enhancement is attributed to the increased conductivity from Nb-doping and the synergistic effect between Pd and TiO 2 .more » « less
-
Abstract X-ray analysis is one of the most robust approaches to extract quantitative information from various materials and is widely used in various fields ever since Raimond Castaing established procedures to analyze electron-induced X-ray signals for materials characterization ‘70 years ago’. The recent development of aberration-correction technology in a (scanning) transmission electron microscopes (S/TEMs) offers refined electron probes below the Å level, making atomic-resolution X-ray analysis possible. In addition, the latest silicon drift detectors allow complex detector arrangements and new configurational designs to maximize the collection efficiency of X-ray signals, which make it feasible to acquire X-ray signals from single atoms. In this review paper, recent progress and advantages related to S/TEM-based X-ray analysis will be discussed: (i) progress in quantification for materials characterization including the recent applications to light element analysis, (ii) progress in analytical spatial resolution for atomic-resolution analysis and (iii) progress in analytical sensitivity toward single-atom detection and analysis in materials. Both atomic-resolution analysis and single-atom analysis are evaluated theoretically through multislice-based calculation for electron propagation in oriented crystalline specimen in combination with X-ray spectrum simulation.more » « less
-
Abstract The controlled creation and manipulation of defects in 2D materials has become increasingly popular as a means to design and tune new material functionalities. However, defect characterization by direct atomic-scale imaging is often severely limited by surface contamination due to a blanket of hydrocarbons. Thus, analysis techniques that can characterize atomic-scale defects despite the contamination layer are advantageous. In this work, we take inspiration from X-ray absorption spectroscopy and use broad-beam electron energy loss spectroscopy (EELS) to characterize defect structures in 2D hexagonal boron nitride (hBN) based on averaged fine structure in the boron K-edge. Since EELS is performed in a transmission electron microscope (TEM), imaging can be performed in-situ to assess contamination levels and other factors such as tears in the fragile 2D sheets, which can affect the spectroscopic analysis. We demonstrate the TEM-EELS technique for 2D hBN samples irradiated with different ion types and doses, finding spectral signatures indicative of boron–oxygen bonding that can be used as a measure of sample defectiveness depending on the ion beam treatment. We propose that even in cases where surface contamination has been mitigated, the averaging-based TEM-EELS technique can be useful for efficient sample surveys to support atomically resolved EELS experiments.more » « less
-
Abstract Deploying energy storage and carbon capture at scale is hindered by the substantial endothermic penalty of decomposing CaCO3to CaO and CO2, and the rapid loss of CO2absorption capacity by CaO sorbent particles due to sintering at the high requisite decomposition temperatures. The decomposition reaction mechanism underlying sorbent deactivation remains unclear at the atomic level and nanoscale due to past reliance on postmortem characterization methods with insufficient spatial and temporal resolution. Thus, elucidating the important CaCO3decomposition reaction pathway requires direct observation by time‐resolved (sub‐)nanoscale methods. Here, chemical and structural dynamics during the decomposition of CaCO3nanoparticles to nanoporous CaO particles comprising high‐surface‐area CaO nanocrystallites are examined. Comparing in situ transmission electron microscopy (TEM) and synchrotron X‐ray diffraction experiments gives key insights into the dynamics of nanoparticle calcination, involving anisotropic CaCO3thermal distortion before conversion to thermally dilated energetically stable CaO crystallites. Time‐resolved TEM uncovered a novel CaO formation mechanism involving heterogeneous nucleation at extended CaCO3defects followed by sweeping reaction front motion across the initial CaCO3particle. These observations clarify longstanding, yet incomplete, reaction mechanisms and kinetic models lacking accurate information about (sub‐)nanoscale dynamics, while also demonstrating calcination of CaCO3without sintering through rapid heating and precise temperature control.more » « less
An official website of the United States government
