Yttrium diboride has the same hexagonal crystal structure as aluminium diboride and magnesium diboride – an important superconducting material. Its Pearson symbol is hP3, space group P6/mmm (No 191), a = 0.33041 nm, c = 0.38465 nm and the calculated density is 5.05 g/cm³.^[3] In this structure, the boron atoms form graphite like sheets with yttrium atoms between them. YB₂ crystals are unstable to moderate heating in air – they start oxidizing at 400 °C and completely oxidize at 800 °C.^[4] YB₂ melts at ~2100 °C.^[5]

YB₄ has tetragonal crystal structure with space group P4/mbm (No. 127), Pearson symbol tP20, a = 0.711 nm, c = 0.4019 nm, calculated density 4.32 g/cm³.^[6] High-quality YB₄ crystals of few centimeters in size can be grown by the multiple-pass floating zone technique.^[7]

YB₆ is a black odorless powder having density of 3.67 g/cm³; it has the same cubic crystalline structure as other hexaborides (CaB₆, LaB₆, etc., see infobox).^[2] High-quality YB₆ crystals of few centimeters in size can be grown by the multiple-pass floating zone technique.^[7][8] YB₆ is a superconductor with the relatively high transition temperature (onset) of 8.4 K.^[8][9]

YB₁₂ crystals have a cubic structure with density of 3.44 g/cm³, Pearson symbol cF52, space group Fm3m (No. 225), a = 0.7468 nm.^[10] Its structural unit is ₁₂ cuboctahedron. The Debye temperature of YB₁₂ is ~1040 K, and it is not superconducting at temperatures above 2.5 K.^[11]

The structure of yttrium borides with B/Y ratio of 25 and above consists of a network of B₁₂ icosahedra. The boron framework of YB₂₅ is one of the simplest among icosahedron-based borides – it consists of only one kind of icosahedra and one bridging boron site. The bridging boron site is tetrahedrally coordinated by four boron atoms. Those atoms are another boron atom in the counter bridge site and three equatorial boron atoms of one of three B₁₂ icosahedra. The yttrium sites have partial occupancies of ca. 60–70%, and the YB₂₅ formula merely reflects the average atomic ratio [B]/[Y] = 25. Both the Y atoms and B₁₂ icosahedra form zigzags along the x-axis. The bridging boron atoms connect three equatorial boron atoms of three icosahedra and those icosahedra make up a network parallel to the (101) crystal plane (x-z plane in the figure). The bonding distance between the bridging boron and the equatorial boron atoms is 0.1755 nm, which is typical for the strong covalent B-B bond (bond length 0.17–0.18 nm); thus, the bridging boron atoms strengthen the individual network planes. On the other hand, the large distance between the boron atoms within the bridge (0.2041 nm) reveals a weaker interaction, and thus the bridging sites contribute little to the bonding between the network planes.^[12][13]

YB₂₅ crystals can be grown by heating a compressed pellet of yttria (Y₂O₃) and boron powder to ~1700 °C. The YB₂₅ phase is stable up to 1850 °C. Above this temperature it decomposes into YB₁₂ and YB₆₆ without melting. This makes it difficult to grow a single crystal of YB₂₅ by the melt growth method.^[12]

YB₅₀ crystals have orthorhombic structure with space group P2₁2₁2 (No. 18), a = 1.66251 nm, b = 1.76198 nm, c = 0.94797 nm. They can be grown by heating a compressed pellet of yttria (Y₂O₃) and boron powder to ~1700 ⁰C. Above this temperature YB₅₀ decomposes into YB₁₂ and YB₆₆ without melting. This makes it difficult to grow a single crystal of YB₅₀ by the melt growth method. Rare earth elements from Tb to Lu can also crystallize in the M₅₀ form.^[14]

YB₆₆ was discovered in 1960^[17] and its structure was solved in 1969.^[16] The structure is face-centered cubic, with space group Fm3c (No. 226), Pearson symbol cF1936 and lattice constant a = 2.3440(6) nm. There are 13 boron sites B1–B13 and one yttrium site. The B1 sites form one B₁₂ icosahedron and the B2–B9 sites make up another icosahedron. These icosahedra arrange in a thirteen-icosahedron unit (B₁₂)₁₂B₁₂ which is called supericosahedron. The icosahedron formed by the B1 site atoms is located at the center of the supericosahedron. The supericosahedron is one of the basic units of the boron framework of YB₆₆. There are two types of supericosahedra: one occupies the cubic face centers and another, which is rotated by 90°, is located at the center of the cell and at the cell edges. Thus, there are eight supericosahedra (1248 boron atoms) in the unit cell.^[15]

Another structure unit of YB₆₆ is B₈₀ cluster of 80 boron sites formed by the B10 to B13 sites.^[15] All those 80 sites are partially occupied and in total contain only ca. 42 boron atoms. The B₈₀ cluster is located at the body center of the octant of the unit cell, i.e., at the 8a position (1/4, 1/4, 1/4); thus, there are eight such clusters (336 boron atoms) per unit cell. Two independent structure analyses ^[15][16] came to the same conclusion that the total number of boron atoms in the unit cell is 1584. The boron framework structure of YB₆₆ is shown in the figure to the right. A schematic drawing under it indicates relative orientations of the supericosahedra, and the B₈₀ clusters are depicted by light green and dark green spheres, respectively; at the top surface of the unit cell, the relative orientations of the supericosahedra are indicated by arrows. There are 48 yttrium sites ((0.0563, 1/4, 1/4) for YB₆₂^[15]) in the unit cell. Fixing the occupancy of the Y site to 0.5 results in 24 Y atoms in the unit cell and the chemical composition of YB₆₆; this occupancy of 0.5 implies that the yttrium pair has always one Y atom with one empty site.^[16]

YB₆₆ has density 2.52 g/cm³, low thermal conductivity of 0.02 W/(cm·K), elastic constants c₁₁ = 3.8×10⁹ and c₄₄ = 1.6×10⁹ Newton/m² and Debye temperature of 1300 K.^[18] As all yttrium borides, YB₆₆ is a hard material and exhibits Knoop hardness of 26 GPa.^[19] High-quality YB₆₆ crystals of few centimeters in size can be grown by the multiple-pass floating zone technique and be used as X-ray monochromators.^[20]

The large unit cell of YB₆₆ results in large lattice constant of 2.344 nm.^[18] This property, together with high thermal and mechanical stability resulted in application of YB₆₆ as dispersive elements of X-ray monochromators for low energy radiation (1–2 keV).^[21][22]

• Crystal structure of boron-rich metal borides