Alkaline Beryllium Borate NaBeB3O6 and ABe2B3O7 (A = K, Rb) as UV Nonlinear Optical Crystals
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Abstract
A new series of alkaline beryllium borates NaBeB(3)O(6), alpha-KBe(2)B(3)O(7), beta-KBe(2)B(3)O(7), gamma-KBe(2)B(3)O(7), and RbBe(2)B(3)O(7) were synthesized by spontaneous crystallization with molten fluxes based on A(2)O-B(2)O(3) (A = Na, K, Rb) solvent. For KBe(2)B(3)O(7), three polymorphous phases were found and are referred to as alpha-, beta-, and gamma-KBe(2)B(3)O(7) relative to their crystallization temperature from high to low. All of the materials are noncentrosymmetric except alpha-KBe(2)B(3)O(7). NaBeB(3)O(6) and alpha-KBe(2)B(3)O(7) consist of a new anionic group [Be(2)B(3)O(11)](9-), which is similar to a naphthalene molecule that is rarely found in inorganic matter. beta-KBe(2)B(3)O(7), gamma-KBe(2)B(3)O(7), and RbBe(2)B(3)O(7) consist of 2D alveolate beryllium borate layers [Be(2)BO(5)](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 NaBeB(3)O(6), beta-KBe(2)B(3)O(7), gamma-KBe(2)B(3)O(7), and RbBe(2)B(3)O(7) 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.
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