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High-entropy alloys (HEAs) are a class of multi-element materials that exhibit unique structural and functional properties. This study reports on the synthesis and characterization of a superconducting HEA, (NbTa)0.55(HfTiZr)0.45 fabricated using the vacuum arc melting technique. Scanning electron microscopy and energy-dispersive x-ray spectroscopy were employed to analyze the material's morphology and composition. X-ray diffraction analysis revealed a single-phase body-centered cubic (BCC) structure with a measured nanoindentation hardness of 6.4 GPa and Young's modulus of 132 GPa. This HEA superconductor was investigated by x-ray diffraction at Beamline 13BM-C, Advanced Photon Source, and the BCC phase was stable to the highest pressure of 50 GPa. Superconductivity was characterized by four-probe resistivity measurements in a quantum design physical property measurement system, yielding a superconducting transition temperature (Tc) of 7.2 K at ambient pressure and reaching a maximum of 10.1 K at the highest applied pressure of 23.6 GPa. The combination of high structural stability enhanced superconducting performance under pressure and superior mechanical properties highlights (NbTa)0.55(HfTiZr)0.45 as a promising superconductor under extreme environments. 

A microwave plasma chemical vapor deposition system was used to synthesize cubic boron nitride (cBN) coatings on diamond seeded silicon substrates using direct current (DC) bias. Effects of the argon (Ar) flow rate and bias voltage on the growth of the cBN coatings were investigated. Hydrogen (H2), argon (Ar), a mixture of diborane in H2 (95% H2, 5% B2H6), and N2 were used in the feed gas. A DC bias system was used for external biasing of the sample, which facilitates the goal of achieving sp3 bonded cBN. Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS) revealed the existence of sp3-bonded BN in the produced samples. With increasing Ar flow, the cBN content in the coating increases and reaches a maximum at the maximum Ar flow of 400 SCCM used in this study. High-resolution XPS scans for B1s and N1s indicate that the deposited coating contains more than 70% cBN. This study demonstrates that energetic argon ions generated in a microwave-induced plasma significantly increase cBN content in the coating. 

Boron nitride (BN) is primarily a synthetically produced advanced ceramic material. It is isoelectronic to carbon and, like carbon, can exist as several polymorphic modifications. Microwave plasma chemical vapor deposition (MPCVD) of metastable wurtzite boron nitride is reported for the first time and found to be facilitated by the application of direct current (DC) bias to the substrate. The applied negative DC bias was found to yield a higher content of sp3 bonded BN in both cubic and metastable wurtzite structural forms. This is confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Nano-indentation measurements reveal an average coating hardness of 25 GPa with some measurements as high as 31 GPa, consistent with a substantial fraction of sp3 bonding mixed with the hexagonal sp2 bonded BN phase. 

Microwave-induced plasma was used to anneal precursor powders containing five metal oxides with carbon and boron carbide as reducing agents, resulting in high entropy boride ceramics. Measurements of hardness, phase structure, and oxidation resistance were investigated. Plasma annealing for 45 min in the range of 1500–2000 °C led to the formation of predominantly single-phase (Hf, Zr, Ti, Ta, Mo)B2 or (Hf, Zr, Nb, Ta, Mo)B2 hexagonal structures characteristic of high entropy borides. Oxidation resistance for these borides was improved by as much as a factor of ten when compared to conventional commercial diborides. Vickers and nanoindentation hardness measurements show the indentation size effect and were found to be as much as 50% higher than that reported for the same high entropy boride configuration made by other methods, with average values reaching up to 38 GPa (for the highest Vickers load of 200 gf). Density functional theory calculations with a partial occupation method showed that (Hf, Zr, Ti, Ta, Mo)B2 has a higher hardness but a lower entropy forming ability compared to (Hf, Zr, Nb, Ta, Mo)B2, which agrees with the experiments. Overall, these results indicate the strong potential of using microwave-induced plasma as a novel approach for synthesizing high entropy borides. 

A novel approach is demonstrated for the synthesis of the high entropy transition metal boride (Ta, Mo, Hf, Zr, Ti)B2 using a single heating step enabled by microwave-induced plasma. The argon-rich plasma allows rapid boro-carbothermal reduction of a consolidated powder mixture containing the five metal oxides, blended with graphite and boron carbide (B4C) as reducing agents. For plasma exposure as low as 1800 °C for 1 h, a single-phase hexagonal AlB2-type structure forms, with an average particle size of 165 nm and with uniform distribution of the five metal cations in the microstructure. In contrast to primarily convection-based (e.g., vacuum furnace) methods that typically require a thermal reduction step followed by conversion to the single high-entropy phase at elevated temperature, the microwave approach enables rapid heating rates and reduced processing time in a single heating step. The high-entropy phase purity improves significantly with the increasing of the ball milling time of the oxide precursors from two to eight hours. However, further improvement in phase purity was not observed as a result of increasing the microwave processing temperature from 1800 to 2000 °C (for fixed ball milling time). The benefits of microwave plasma heating, in terms of allowing the combination of boro-carbothermal reduction and high entropy single-phase formation in a single heating step, are expected to accelerate progress in the field of high entropy ceramic materials. 

Abstract We report bias enhanced nucleation and growth of boron-rich deposits through systematic study of the effect of a negative direct current substrate bias during microwave plasma chemical vapor deposition. The current flowing through a silicon substrate with an applied bias of −250 V was investigated for a feedgas containing fixed hydrogen (H₂) flow rate but with varying argon (Ar) flow rates for 1330, 2670, and 4000 Pa chamber pressure. For 1330 and 2670 Pa, the bias current goes through a maximum with increasing Ar flow rate. This maximum current also corresponds to a peak in substrate temperature. However, at 4000 Pa, no maximum in bias current or substrate temperature is observed for the range of argon flow rates tested. Using these results, substrate bias pre-treatment experiments were performed at 1330 Pa in an Ar/H₂plasma, yielding the maximum bias current. Nucleation density of boron deposits were measured after subsequent exposure to B₂H₆in H₂plasma and found to be a factor of 200 times higher than when no bias and no Ar was used. Experiments were repeated at 2670 and 4000 Pa (fixed bias voltage and Ar flow rate) in order to test the effect of chamber pressure on the nucleation density. Compared to 4000 Pa, we find nearly 7 times higher boron nucleation densities for both 1330 and 2670 Pa when the substrate was negatively biased in the Ar/H₂plasma. Results are explained by incorporating measurements of plasma optical emission and by use of heterogeneous nucleation theory. The optimal conditions at 1330 Pa for nucleation were used to grow boron-rich amorphous films with measured hardness as high as 58 GPa, well above the 40 GPa threshold for superhardness. 

Boron-rich B-C compounds with high hardness have been recently synthesized by the chemical vapor deposition (CVD) method. In this paper, we present our successful efforts in the selective growth of microstructures of boron-carbon compounds on silicon substrates. This was achieved by combining microfabrication techniques such as maskless lithography and sputter deposition with the CVD technique. Our characterization studies on these B-C microstructures showed that they maintain structural and mechanical properties similar to that of their thin-film counterparts. The methodology presented here paves the way for the development of microstructures for microelectromechanical system (MEMS) applications which require custom hardness and strength properties. These hard B-C microstructures are an excellent choice as support structures in MEMS-based devices. 

Boron nitride (BN) is a member of Group III nitrides and continues to spark interest among the scientific community for its mechanical properties, chemical inertness, thermal conductivity, and electrical insulating properties. In this study, microwave plasma chemical vapor deposition is used to synthesize BN on silicon substrates. Feed gas mixtures of H2, NH3, and B2H6 are used for a range of systematically varied power, pressure, and flow rate conditions. Plasma optical emission from atomic boron is shown to increase nonlinearly by nearly a factor of five with decreasing chamber pressure in the range from 100 to 10 Torr. Copious amounts of atomic boron in the plasma may be beneficial under some growth conditions for producing high hardness boron-rich nitrides, such as B13N2, B50N2, or B6N, which, to date, have only been synthesized under high pressure/high temperature conditions. Despite the higher atomic boron emission in the plasma at low pressure, BN coatings grown at 15 Torr result in hexagonal BN (B/N ratio of 1), regardless of the B2H6 flow rate used in the range of 0.6–3.0 sccm.