Phase transitions, ferroelectric behavior and second-order nonlinear optics of a new mixed sodium dihydrogen phosphate–arsenate

Abstract

Aiming at the development of new proton conducting solids, recent studies of the NaH 2PO 4·H 2O–NaH 2AsO 4·H 2O system have lead to the synthesis of a new compound NaH 2(PO 4) 0.48(AsO 4) 0.52·H 2O (NDAP). Calorimetric studies have confirmed the presence of four reversible phase transitions (abbreviated by PhT), at 257/270 (PhT, IV), 261/290 (PhT, III), 267/301 (PhT, II) and 317/317.5 K (PhT, I) (for cooling/heating processes, respectively). It is shown that the III and IV phase transitions are of a first order type, with a “order-disorder and displacive” character, accompanied by specific dielectric anomalies. The behavior of the dielectric constant ε′ r and of tan δ shows that, at 272 K, the (PhT, IV) could be ferroelectric–paraelectric. As for the (PhT, III) at 296 K, it leads to a superionic–protonic phase; a jump in the conductivity is associated to this transition with an unusual high value of conductivity 1.07×10 −4 Ω −1 cm −1 and a low activation energy 0.39 eV (Kh. Jarraya et al .). Quandratic nonlinear (NLO) properties of NDAP powder was confirmed efficiency of the grown crystal by the Kurtz and Perry second harmonic generation (SHG) technique.