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Nanoscale electron field emitters are known to produce more stable electron emissions than conventional emitters. This has been attributed to size effects; nanoscale emitters can operate with a small emission current and a low extraction voltage, which reduces the bombardment of residual gas ions on the emitter tip. However, our experiments discovered that nanoscale LaB

A material with a low work function exhibiting field-emission of electrons has long been sought as an ideal point electron source to generate a coherent electron beam with high brightness, long service life, low energy spread, and especially stable emission current. The quality and performance of the electron source are now becoming limiting factors for further improving the spatial resolution and analytical capabilities of the electron microscope. While tungsten (W) is still the only material of choice as a practically usable field emission filament since it was identified more than six decades ago, its electron optical performance remains unsatisfactory, especially the poor emission stability (>5% per hour), rapid current decay (20% in 10 hours), and relatively large energy spread (0.4 eV), even in an extremely high vacuum (10−9 Pa). Herein, we report a LaB6 nanoneedle structure having a sharpened tip apex with a radius of curvature of about 10 nm that is fabricated and finished using a focused ion beam (FIB) and show that it can produce a field emission electron beam meeting the application criteria with a high reduced brightness (1010 A m−2 sr−1 V−1), small energy spread (0.2 eV), and especially high emission stability (

Phonon transport across a vacuum gap separating intrinsic silicon crystals is predicted via the atomistic Green's function method combined with first-principles calculations of all interatomic force constants. The overlap of electron wave functions in the vacuum gap generates weak covalent interaction between the silicon surfaces, thus creating a pathway for phonons. Phonon transport, dominated by acoustic modes, exceeds near-field radiation for vacuum gaps smaller than ~ 1 nm. The first-principles-based approach proposed in this work is critical to accurately quantify the contribution of phonon transport to heat transfer in the extreme near field., 31 pages, 4 figures, 4 supplemental figures

Graphite-like BC2 has yet to be synthesized; however, it stably exists in the Sc2B1.1C3.2 compound, where the boron atoms are arranged as far apart from each other as possible. Recently, a theoretical study on monolayer BC2 reported that in the most stable structure, B atoms are positioned adjacent to each other. We anticipated that graphite-like BC2 might take a different structure based on the electric charge. Therefore, we carried out first principles calculations to investigate whether this is true or not. The most stable structure among the six possible structures changed with the increase in the negative electric charge, which well explained both the previous results without contradiction. The most stable structure was also dependent on the pressure. The Li intercalation potential for BC2 was calculated to investigate its applicability as an anode for lithium-ion batteries. Our results revealed that Li atoms can be intercalated into BC2 to yield Li1.5BC2, whose gravimetric capacity is approximately 3.1 times higher than that of LiC6. However, the most stable structure with intercalated Li atoms became unstable when all the Li atoms were extracted. This feature may hinder the repetitive charge–discharge cycle of the anode and hence needs to be carefully considered.

Herein, the work functions of group 4 and group 5 transition-metal (Ti, Zr, Hf, V, Nb, and Ta) carbides and transition-metal oxycarbides (TMCOs) were investigated by first-principles calculations for their potential application as electron emitters. The work functions of both groups decreased as the substitution of carbon atoms with oxygen proceeded, and the reduction in group 4 was more than that of group 5. In particular, ZrC1-x O x and HfC1-x O x (x ≥ 0.25) exhibited work functions of less than 3 eV, which were comparable with those of LaB6- and ZrO-coated tungsten. The reduction in the work functions could be explained by the rigid-band model of the electronic density of states. The increase in valence electrons increased the Fermi energy, while it demonstrated a less significant influence on the vacuum potential, resulting in a reduction in the work functions. The phonon dispersion curves indicated that the NaCl-type group 5 TMCOs were less stable than the group 4 TMCOs. This agrees with the experimental findings that TaC1-x O x was not synthesized and NbC1-x O x was synthesized only for smaller values of x (i.e., x < 0.28). From the viewpoints of the work functions and structural stabilities, group 4 (Ti, Zr, and Hf) TMCOs exhibit better potential for application as electron emitters than group 5 (V, Nb, and Ta) TMCOs.

A material with a low work function exhibiting field-emission of electrons has long been sought as an ideal point electron source to generate a coherent electron beam with high brightness, long service life, low energy spread, and especially stable emission current. The quality and performance of the electron source are now becoming limiting factors for further improving the spatial resolution and analytical capabilities of the electron microscope. While tungsten (W) is still the only material of choice as a practically usable field emission filament since it was identified more than six decades ago, its electron optical performance remains unsatisfactory, especially the poor emission stability (5% per hour), rapid current decay (20% in 10 hours), and relatively large energy spread (0.4 eV), even in an extremely high vacuum (10

The ternary borocarbide Sc2B1.1C3.2 is known to have a layered structure in which graphite-like BC2 layers and NaCl-like Sc2C layers are alternately stacked. Due to the complexity of the structure, X-ray analysis is unable to determine the precise structure of the BC2 layer, namely, how the boron atoms are arranged in the layer. Furthermore, the stacking manner of the two layers remains unclear. In this study, we have investigated the entire structure of Sc2B1.1C3.2 through first-principles calculations. The calculations reveal that the material is the most stable when B atoms are arranged to form 3 × 3 –R30° superlattices in the graphite-like layer. The interlayer bonding is mostly van der Waals-like, and the total energy is almost independent of the stacking method. The BC2 layer with the 3 × 3 –R30° structure can be regarded as an intermediate between similar graphite-like materials, BC and BC3. The electronic density of states of Sc2B1.1C3.2 exhibits metallic features, and electrons are transferred from Sc to B and C atoms, which compensates the lack of electrons in the BC2 layer. The origin of the undulation in the BC2 layer is not the inner electronic structure but the interaction between the BC2 and Sc2C layers. The weak localization found in the in-plane resistivity in experiments is explained by the domain boundaries of the 3 × 3 –R30° structure rather than the randomness of the arrangement of B atoms.

It is known that elemental boron has five polymorphs: α- and β-rhombohedral, α- and β-tetragonal, and the high-pressure γ phase. β-tetragonal (β-t) boron was first discovered in 1960, but there have been only a few studies since then. We have thoroughly investigated, using first-principles calculations, the atomic and electronic structures of β-t boron, the details of which were not known previously. The difficulty of calculation arises from the fact that β-t boron has a large unit cell that contains between 184 and 196 atoms, with 12 partially-occupied interstitial sites. This makes the number of configurations of interstitial atoms too great to calculate them all. By introducing assumptions based on symmetry and preliminary calculations, the number of configurations to calculate can be greatly reduced. It was eventually found that β-t boron has the lowest total energy, with 192 atoms (8 interstitial atoms) in an orthorhombic lattice. The total energy per atom was between those of α- and β-rhombohedral boron. Another tetragonal structure with 192 atoms was found to have a very close energy. The valence bands were fully filled and the gaps were about 1.16 to 1.54 eV, making it comparable to that of β-rhombohedral boron.

The structural stability of cagelike boron clusters with octahedral and tetrahedral symmetries has been investigated by means of first-principles calculations. Twenty-eight cluster models, ranging from B(10) to B(66), were systematically constructed using regular and semiregular polyhedra as prototypes. The binding energies per atom were, on the whole, slightly lower than those of icosahedral clusters B(80) and B(100), which are supposed to be the most stable in the icosahedral group. The larger clusters did not always have higher binding energies. Isothermal molecular dynamics simulations were performed to determine the deformation temperatures at which clusters began to break or change their structures. We found eight clusters that had nonzero deformation temperatures, indicating that they are in metastable states. The octahedral cluster B(18) had the highest deformation temperature among these, similar to that of icosahedral B(80) and B(100). The analysis of the electronic structure of B(18) showed that it attained this high stability owing to Jahn-Teller distortion.

The crystal and electronic structures of α-tetragonal (α-t) boron were investigated by first-principles calculation. Application of a simple model assuming 50 atoms in the unit cell indicated that α-t boron had a metallic density of state, thus contradicting the experimental fact that it is a p-type semiconductor. The presence of an additional two interstitial boron atoms at the 4c site made α-t boron semiconductive and the most stable. The cohesive energy per atom was as high as those of α- and β-rhombohedral boron, suggesting that α-t boron is produced more easily than was previously thought. The experimentally obtained α-t boron in nanobelt form had about two interstitial atoms at the 8i sites. We consider that the shallow potential at 8i sites generates low-energy phonon modes, which increase the entropy and consequently decrease the free energy at high temperatures. Calculation of the electronic band structure showed that the highest valence band had a larger dispersion from Γ to Z than from Γ to X; this indicated a strong anisotropy in hole conduction.

α-Rhombohedral (α-rh) boron, which is the most stable of boron's polymorphs at low temperatures, has p-type semiconductive properties. There have been some attempts to dope the interstitial sites with alkali atoms to create metallic or n-type semiconductive α-rh boron, but this has yet to be achieved. In a previous work, we proposed the codoping of α-rh boron with Li and P or As, and revealed from first principles calculations that B12PLi and B12AsLi could be synthesized and become narrow-gap semiconductors. The band structure suggested that the mobility of electrons might be greater than that of holes. In this paper, based on these prospective results, we selected a new combination of dopants, Li and O, and theoretically studied such compounds as B12OLi and B12O2Li. The results showed that both of these materials are metallic, while the reaction energies of the Li insertion into B12O and B12O2 are lower (more unstable) than with B12PLi and B12AsLi. It was proved that the differences in the electronic structures are caused by the dangling bonds of the dopant atoms, O, P and As.

The electronic structure of liquid boron and cluster formation in expanded liquid boron have been investigated with first-principles molecular dynamics simulations. The calculated electronic density of states (DOS) exhibits a metallic feature, while liquid boron is known experimentally to be semiconductive. Since the DOS is not very sensitive to density, the electronic states near the Fermi level will consist mainly of dangling bonds, which explains the difference between the calculated and experimental results. Many types of clusters are formed in expanded liquid boron. This formation occurs in a very different way from that at low temperatures because expanded liquid boron has a high temperature and pressure that are close to the liquid-gas critical point. As the density is reduced, the coordination number in boron clusters decreases to about 2, indicating that the cluster geometry tends to be one- rather than two-dimensional, which is the most stable form at low temperatures. In fact, the analysis of small clusters proved that one-dimensional forms are dominant over two- and three-dimensional forms. This is because one-dimensional geometries have a more flexible structure and a high entropy value that consequently reduces the free energy at high temperatures.

The stability of lithium atoms in alpha-rhombohedral boron was investigated by first-principles calculations of total energies and molecular dynamics (MD) simulations. In the case of a low concentration (1.03 at. %), Li at the center of the icosahedral B12 site (the I-site) had a negative binding energy, which suggests Li at the I-site is unstable. However, MD simulations at temperatures below 750 K indicated that Li is still confined in the B12 cage under these conditions, which means Li at the I-site is metastable. Over 800 K, Li began to move away from the B12 site and settled at the tetrahedral site (the T-site) or at the octahedral site (the O-site). Li at the T-site also had a negative binding energy, but MD simulations indicated it was metastable up to 1400 K and did not move to other sites. Li at the O-site was energetically the most favorable, having a positive binding energy. In the case of a high concentration (7.69 at. %), the I-site changed to an unstable saddle point. At this concentration, the T-site was metastable and the O-site became the most stable. In MD simulations at 1400 K, Li atoms at the O-site never jumped to other sites regardless of concentration. Considering these facts, the diffusion coefficient of Li in alpha-rhombohedral boron would have to be very small below 1400 K.