화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.132, No.25, 8779-8786, 2010
Alkaline Beryllium Borate NaBeB3O6 and ABe(2)B(3)O(7) (A = K, Rb) as UV Nonlinear Optical Crystals
A new series of alkaline beryllium borates NaBeB3O6, alpha-KBe2B3O7, beta-KBe2B3O7, gamma-KBe2B3O7, and RbBe2B3O7 were synthesized by spontaneous crystallization with molten fluxes based on A(2)O-B2O3 (A = Na, K, Rb) solvent. For KBe2B3O7, three polymorphous phases were found and are referred to as alpha-, beta-, and gamma-KBe2B3O7 relative to their crystallization temperature from high to low. All of the materials are noncentrosymmetric except alpha-KBe2B3O7. NaBeB3O6 and a-KBe2B3O7 consist of a new anionic group [Be2B3O11](9-), which is similar to a naphthalene molecule that is rarely found in inorganic matter. beta-KBe2B3O7, gamma-KBe2B3O7, and RbBe2B3O7 consist of 2D alveolate beryllium borate layers [Be2BO5](infinity), which are connected by strong covalent bonds. The UV-vis diffuse reflectance spectroscopy on powder samples indicated that the short-wavelength absorption edges of noncentrosymmetric materials are all below 200 nm. Second-harmonic generation (SHG) on powder samples was measured using the Kurtz and Perry technique, which indicated that NaBeB3O6, beta-KBe2B3O7, gamma-KBe2B3O7, and RbBe2B3O7 are all phase matchable materials, and their measured SHG coefficients were approximately 1.60, 0.75, 0.68, and 0.79 times as large as that of d(36) (KDP), respectively.