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1. Computational Predictions and Microwave Plasma Synthesis of Superhard Boron-Carbon Materials

   https://doi.org/10.3390/ma11081279  

   Baker, Paul; Catledge, Shane; Harris, Sumner; Ham, Kathryn; Chen, Wei-Chih; Chen, Cheng-Chien; Vohra, Yogesh (August 2018, Materials)

   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. 

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2. Machine learning and evolutionary prediction of superhard B-C-N compounds

   https://doi.org/10.1038/s41524-021-00585-7  

   Chen, Wei-Chih; Schmidt, Joanna N.; Yan, Da; Vohra, Yogesh K.; Chen, Cheng-Chien (July 2021, npj Computational Materials)

   Abstract We build random forests models to predict elastic properties and mechanical hardness of a compound, using only its chemical formula as input. The model training uses over 10,000 target compounds and 60 features based on stoichiometric attributes, elemental properties, orbital occupations, and ionic bonding levels. Using the models, we construct triangular graphs for B-C-N compounds to map out their bulk and shear moduli, as well as hardness values. The graphs indicate that a 1:1 B-N ratio can lead to various superhard compositions. We also validate the machine learning results by evolutionary structure prediction and density functional theory. Our study shows that BC₁₀N, B₄C₅N₃, and B₂C₃N exhibit dynamically stable phases with hardness values >40 GPa, which are superhard materials that potentially could be synthesized by low-temperature plasma methods. 

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3. Asymmetric twins in boron rich boron carbide

   https://doi.org/10.1039/C8CP01429A  

   Yang, Xiaokun; Goddard, William A.; An, Qi (January 2018, Physical Chemistry Chemical Physics)

   Twin boundaries (TBs) play an essential role in enhancing the mechanical, electronic and transport properties of polycrystalline materials. However, the mechanisms are not well understood. In particular, we considered that they may play an important role in boron rich boron carbide (B vr BC), which exhibits promising properties such as low density, super hardness, high abrasion resistance, and excellent neutron absorption. Here, we apply first-principles-based simulations to identify the atomic structures of TBs in B vr BC and their roles for the inelastic response to applied stresses. In addition to symmetric TBs in B vr BC, we identified a new type of asymmetric twin that constitutes the phase boundaries between boron rich boron carbide (B 13 C 2 ) and B vr BC (B 14 C). The predicted mechanical response of these asymmetric twins indicates a significant reduction of the ideal shear strength compared to single crystals B 13 C 2 and B 14 C, suggesting that the asymmetric twins facilitate the disintegration of icosahedral clusters under applied stress, which in turn leads to amorphous band formation and brittle failure. These results provide a mechanistic basis towards understating the roles of TBs in B vr BC and related superhard ceramics. 

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4. Hexagonal boron nitride grown using high atomic boron emission during microwave plasma chemical vapor deposition

   https://doi.org/10.1116/1.5123210  

   Chakrabarty, Kallol; Arnold, Ivan; Catledge, Shane_A (October 2019, Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films)

   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. 

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5. Using metal precursors to passivate oxides for area selective deposition

   https://doi.org/10.1116/6.0002413  

   Canova, Kinsey L.; Souqui, Laurent; Girolami, Gregory S.; Abelson, John R. (May 2023, Journal of Vacuum Science & Technology A)

   Although it has long been known that metal-containing compounds can serve as catalysts for chemical vapor deposition (CVD) of films from other precursors, we show that metal-containing compounds can also inhibit CVD nucleation or growth. For two precursors A and B with growth onset temperatures TgA < TgB when used independently, it is possible that B can inhibit growth from A when the two precursors are coflowed onto a substrate at a temperature (T) where TgA < T < TgB. Here, we consider three precursors: AlH3⋅NMe3 (Tg = 130 °C, Me = CH3), Hf(BH4)4 (Tg = 170 °C), and AlMe3 (Tg = 300 °C). We find that (i) nucleation of Al from AlH3⋅NMe3 is inhibited by Hf(BH4)4 at 150 °C on two oxide surfaces (Si with native oxide and borosilicate glass), (ii) nucleation and growth of HfB2 is inhibited by AlMe3 at 250 °C on native oxide substrates and on HfB2 nuclei, and (iii) nucleation of Al from AlH3⋅NMe3 is inhibited by AlMe3 at 200 °C on native oxide substrates. Inhibition by Hf(BH4)4 is transient and persists only as long as its coflow is maintained; in contrast, AlMe3 inhibition of HfB2 growth is more permanent and continues after coflow is halted. As a result of nucleation inhibition, AlMe3 coflow enhances selectivity for HfB2 deposition on Au (growth) over Al2O3 (nongrowth) surfaces, and Hf(BH4)4 coflow makes it possible to deposit Al on Al nuclei and not on the surrounding oxide substrate. We propose the following criteria to identify candidate molecules for other precursor–inhibitor combinations: (i) the potential inhibitor should have a higher Tg than the desired film precursor, (ii) the potential inhibitor should be unreactive toward the desired film precursor, and (iii) at the desired growth temperature, the potential inhibitor should adsorb strongly enough to form a saturated monolayer on the intended nongrowth surface at accessible inhibitor pressures. 

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