Barium borate is an inorganic compound, a borate of barium with a chemical formula BaB2O4 or Ba(BO2)2. It is available as a hydrate or dehydrated form, as white powder or colorless crystals. The crystals exist in the high-temperature α phase and low-temperature β phase, abbreviated as BBO; both phases are birefringent, and BBO is a common nonlinear optical material. Barium borate was discovered and developed by Chen Chuangtian and others of the Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences. Properties Crystal structure of BBO viewed nearly perpendicular to the c-axis. Colors: green – Ba, pink – B, red – O BBO viewed along the c axis Barium borate exists in three major crystalline forms: alpha, beta, and gamma. The low-temperature beta phase converts into the alpha phase upon heating to 925 °C. β-Barium borate (BBO) differs from the α form by the positions of the barium ions within the crystal. Both phases are birefringent, however the α phase possesses centric symmetry and thus does not have the same nonlinear properties as the β phase.[4] Alpha barium borate, α-BaB2O4 is an optical material with a very wide optical transmission window from about 190 nm to 3500 nm. It has good mechanical properties and is a suitable material for high-power ultraviolet polarization optics.[5] It can replace calcite, titanium dioxide or lithium niobate in Glan–Taylor prisms, Glan–Thompson prisms, walk-off beam splitters and other optical components. It has low hygroscopicity, and its Mohs hardness is 4.5. Its damage threshold is 1 GW/cm2 at 1064 nm and 500 MW/cm2 at 355 nm.[1] Beta barium borate, β-BaB2O4, is a nonlinear optical material transparent in the range ~190–3300 nm. It can be used for spontaneous parametric down-conversion. Its Mohs hardness is also 4.5.[1][2] The material exhibits a melting temperature of 1268 K, [6] with anisotropic thermal expansion coefficients: α 11 = 4 × 10 − 6 K − 1 {\displaystyle \alpha _{11}=4\times 10^{-6}K^{-1}} and α 33 = 36 × 10 − 6 K − 1 {\displaystyle \alpha _{33}=36\times 10^{-6}K^{-1}} α₃₃ = 36 × 10⁻⁶ K⁻¹.[7] Gamma barium borate, γ-BaB2O4, discovered recently, was produced by heating beta barium borate 900 °C under 3 GPa of pressure. It was found to have a monoclinic crystal structure.[8] Barium borate has strong negative uniaxial birefringence and can be phase-matched for type I (ooe) second-harmonic generation from 409.6 to 3500 nm. The temperature sensitivity of the indices of refraction is low, leading to an unusually large (55 °C) temperature phase-matching bandwidth.[2] Although the ambient-pressure α and β crystal phases contain only trigonal, sp2 hybridized, boron, BBO glass has around 40% of the boron on tetrahedral, sp3 hybridized, sites. In the liquid state the relative fractions of sp2 and sp3 boron are temperature-dependent, with the trigonal planar coordination favored at higher temperatures.[9]