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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Selective Deposition of Hard Boron-Carbon Microstructures on Silicon
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.
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- Award ID(s):
- 1655280
- PAR ID:
- 10218278
- Date Published:
- Journal Name:
- Materials
- Volume:
- 14
- Issue:
- 6
- ISSN:
- 1996-1944
- Page Range / eLocation ID:
- 1397
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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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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.more » « less
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A boron-rich boron–carbide material (B4+δC) was synthesized by spark plasma sintering of a ball-milled mixture of high-purity boron powder and graphitic carbon at a pressure of 7 MPa and a temperature of 1930 °C. This high-pressure, high-temperature synthesized material was recovered and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, Vickers hardness measurements, and thermal oxidation studies. The X-ray diffraction studies revealed a single-phase rhombohedral structure (space group R-3m) with lattice parameters in hexagonal representation as a = 5.609 ± 0.007 Å and c = 12.082 ± 0.02 Å. The experimental lattice parameters result in a value of δ = 0.55, or the composition of the synthesized compound as B4.55C. The high-resolution scans of boron binding energy reveal the existence of a B-C bond at 188.5 eV. Raman spectroscopy reveals the existence of a 386 cm−1 vibrational mode representative of C-B-B linear chain formation due to excess boron in the lattice. The measured Vickers microhardness at a load of 200 gf shows a high hardness value of 33.8 ± 2.3 GPa. Thermal gravimetric studies on B4.55C were conducted at a temperature of 1300 °C in a compressed dry air environment, and its behavior is compared to other high-temperature ceramic materials such as high-entropy transition metal boride. The high neutron absorption cross section, high melting point, high mechanical strength, and thermal oxidation resistance make this material ideal for applications in extreme environments.
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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.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/ma14061397
