Boron crystal structure

The melting and boiling points of the aluminium halides, in contrast to the boron compounds, are irregular. It might reasonably be expected that aluminium, being a more metallic element than boron, would form an ionic fluoride and indeed the fact that it remains solid until 1564 K. when it sublimes, would tend to confirm this, although it should not be concluded that the fluoride is, therefore, wholly ionic. The crystal structure is such that each aluminium has a coordination number of six, being surrounded by six fluoride ions. 

It is stable up to 2000 K and melts under pressure at 2500 K. The crystal structure of aluminium nitride resembles that of boron nitride and diamond, but unlike both of these it is rapidly and exothermically hydrolysed by cold water ... 

Figure 6.1 The icosahedron and some of its symmetry elements, (a) An icosahedron has 12 vertices and 20 triangular faces defined by 30 edges, (b) The preferred pentagonal pyramidal coordination polyhedron for 6-coordinate boron in icosahedral structures as it is not possible to generate an infinite three-dimensional lattice on the basis of fivefold symmetry, various distortions, translations and voids occur in the actual crystal structures, (c) The distortion angle 0, which varies from 0° to 25°, for various boron atoms in crystalline boron and metal borides.

Figure 6.4 Crystal structure of ar-tetragonal boron. This was originally thought to be B50 (4Bi2 + 2B) but is now known to be either B50C2 or B50N2 in which the 2C (or 2N) occupy the 2(b) positions the remaining 2B are distributed statistically at other vacant sites in the lattice. Note that this reformulation solves three problems which attended the description of the or-tetragonal phase as a crystalline modification of pure B ...

Saitoh, H., Yoshida, K., and Yarborough, W., Crystal Structure of New Composition Boron Rich Boron Nitride Using Raman Spectroscopy, J. Mater. Res., 8(1) 8-11 (Jan. 1993)... 

Boron implant with laser anneal. Boron atoms are accelerated into the backside of the CCD, replacing about 1 of 10,000 silicon atoms with a boron atom. The boron atoms create a net negative charge that push photoelectrons to the front surface. However, the boron implant creates defects in the lattice structure, so a laser is used to melt a thin layer (100 nm) of the silicon. As the silicon resolidihes, the crystal structure returns with some boron atoms in place of silicon atoms. This works well, except for blue/UV photons whose penetration depth is shorter than the depth of the boron implant. Variations in implant depth cause spatial QE variations, which can be seen in narrow bandpass, blue/UV, flat fields. This process is used by E2V, MIT/LL and Samoff. 

Table 2. Crystal Structures and Boron Coordination of Platinum Metal Borides WITH Isolated B Atoms (Owing to Defect Boron Sublattice)...

Figure 1. The crystal structure of ThB4-type tetraborides. (a) The covalent boron skeleton, (b) Atomic arrangement in MB4 (projected along 5).

In the crystal structure of these phases with tetragonal symmetry (P4/mbm, D h) the boron covalent sublattice is formed by chains of octahedra, developing along the c axis and by pairs of B atoms, bonding the octahedra in the xOy plane (see Fig. 1). The resulting three-dimensional skeleton contains tunnels parallel to the c axis that are filled by metal atoms . ... 

Hexaborides of a CaBg type are formed by K, the alkaline earths, Y and the larger lanthanides, as well as Th and some actinides ". The crystal structure of these compounds with cubic symmetry (Pm3m, O, ) (see Fig. 1) is characterized by a three-dimensional skeleton of Bg boron octahedra, the interstices of which are filled by metal atoms. The connection between two octahedra is by a B—B bond of length 1.66 X 10 pm, whereas the B—B bond lengths in one octahedron are 1.76 X 10 pm. ... 

Elements dissolved in boron influence its crystal structure. Dissolved impurities also influenee the physical and chemical properties of boron, especially the electrical properties, because boron is a semiconductor. Preparation of solid solutions in jS-rh boron requires a careful choice of crucible material. To avoid contamination, boron nitride or a cold, coinage-metal crucible should be used or the levitation or floating-zone melting techniques applied. 

The materials for solid solutions of transition elements in -rh boron are prepared by arc melting the component elements or by solid-state diffusion of the metal into /3-rhombohedral (/3-rh) boron. Compositions as determined by crystal structure and electron microprobe analyses together with the unit cell dimensions are given in Table 1. The volume of the unit cell (VT ) increases when the solid solution is formed. As illustrated in Fig. 1, V increases nearly linearly with metal content for the solid solution of Cu in /3-rh boron. In addition to the elements listed in Table 1, the expansion of the unit cell exceeds 7.0 X 10 pm for saturated solid solutions " of Ti, V, Co, Ni, As, Se and Hf in /3-rh boron, whereas the increase is smaller for the remaining elements. The solubility of these elements does not exceed a few tenths at %. The microhardness of the solid solution increases with V, . Boron is a brittle material, indicating the accommodation of transition-element atoms in the /3-rh boron structure is associated with an increase in the cohesion energy of the solid. 

With boron and an appropriate amount of some sort of alkaline metal halide present in the starting materials for the solid-state reactions, then we obtain zirconium cluster materials belonging to the 6-14 family. Single-crystal X-ray data of products from iodine-rich reactions were used to determine the crystal structures of Na[(Zr6B)Cl3.87(5)lio.i3], and Cs[(Zr6B)Cl2.i6(5)lii.84] [21]. Both phases... 

Interstitial Solid Solutions Interstitial solid solutions involve occupation of a site by introduced ions or atoms, which is normally empty in the crystal structure, and no ions or atoms are left out. Many metals form interstitial solid solutions in which small atoms (e.g., hydrogen, carbon, boron, nitrogen) enter empty interstitial sites within the host structure of the metal. Palladium metal is well known for its ability to absorb an enormous volume of hydrogen gas, and the product hydride is an interstitial sohd solution of formula PdH, 0 0.7, in which hydrogen atoms occupy... 

Boron is as unusual in its structures as it is in its chemical behavior. Sixteen boron modifications have been described, but most of them have not been well characterized. Many samples assumed to have consisted only of boron were possibly boron-rich borides (many of which are known, e.g. YB66). An established structure is that of rhombohedral a-B12 (the subscript number designates the number of atoms per unit cell). The crystal structures of three further forms are known, tetragonal -B50, rhombohedral J3-B105 and rhombohedral j3-B 320, but probably boron-rich borides were studied. a-B50 should be formulated B48X2. It consists of B12 icosahedra that are linked by tetrahedrally coordinated X atoms. These atoms are presumably C or N atoms (B, C and N can hardly be distinguished by X-ray diffraction). 

The prototype hard metals are the compounds of six of the transition metals Ti, Zr, and Hf, as well as V, Nb, and Ta. Their carbides all have the NaCl crystal structure, as do their nitrides except for Ta. The NaCi structure consists of close-packed planes of metal atoms stacked in the fee pattern with the metalloids (C, N) located in the octahedral holes. The borides have the A1B2 structure in which close-packed planes of metal atoms are stacked in the simple hexagonal pattern with all of the trigonal prismatic holes occupied by boron atoms. Thus the structures are based on the highest possible atomic packing densities consistent with the atomic sizes. 

The hardest of the transition-metal borides are the diborides. Their characteristic crystal structure (Figure 10.6) consists of plane layers of close-packed metal atoms separated by plane openly-patterned layers of boron atoms ( chicken-wire pattern). If the metal atoms in the hexagonal close-packed layer have a spacing, d, then the boron atoms have a spacing of d/V3. 

Figure 10.7 illustrates the prototype hexaboride crystal structure, that of lanthanum hexaboride. It consists of a simple cubic array of boron octahedra surrounding a metal atom at the body center of each cube. The octahedra are linked by B-B bonds connecting their comers. This makes the overall structure relatively hard with approximately the hardness of boron itself since plastic shear must break B-B bonds. The open volumes surrounded by boron octahedra are occupied by the relatively large lanthanum atoms as the figure shows schematically. 

Figure 10.7 Crystal structure of Lanthanum Hexaboride (prototypre hexaboride). The black circles represent boron octahedra. They form a simple cubic arrangement surrounding the central metal atom.

An alternative version of the lanthanum hexaboride crystal structure has the boron octahedra occupying the body centered positions of the cubic array of lanthanum atoms (Figure 10.8). This version makes it clear that in order to plastically shear the structure, the boron octahedra must be sheared. Note that the octahedra are linked together both internally and externally by B-B bonds. 

Because of its relatively loosely bound outermost electron, and its small size, boron reacts readily with other atoms (including itself) to form a variety of crystal structures. The B-B bond is only about 12 percent longer (1.75 A) than the very strong C—C bond (1.54 A). It not only forms very hard compounds with carbon and nitrogen, but also with oxygen. 

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