A new series of germanium chalcophosphates with the formula A 4GeP4Q12 (A = K, Rb, Cs; Q = S, Se) have been synthesized. The selenium compounds are isostructural and crystallize in the polar orthorhombic space group Pca21. The sulfur analogues are isostructural to one another but crystallize in the centrosymmetric monoclinic space group C2/c. All structures contain the new molecular anion [GeP 4Q12]4-; however, the difference between the sulfides and selenides arises from the change in crystal packing. Each discrete molecule is comprised of two ethane-like P2Q6 units that chelate to a central tetrahedral Ge4+ ion in a bidentate fashion. The selenides were synthesized pure by stoichiometric reaction of the starting materials, whereas the sulfides contained second phases. The band gaps of the molecular salts are independent of the alkali metal counterions and have a value of 2.0 eV for the selenides and 3.0-3.1 eV for the sulfides. All A 4GeP4Se12 compounds melt congruently, and the potassium analogue can be quenched to give a glassy phase that retains its short-range order as shown by Raman spectroscopy and powder X-ray diffraction. Interestingly, K4GeP4Se12 is a phase-change material that reversibly converts between glassy and crystalline states and passes through a metastable crystalline state upon heating just before crystallizing into its slow-cooled form. Initial second harmonic generation (SHG) experiments showed crystalline K4GeP4Se12 outperforms the other alkali metal analogues and exhibits the strongest second harmonic generation response among reported quaternary chalcophosphates, ∼30 times that of AgGaSe2 at 730 nm. A more thorough investigation of the nonlinear optical (NLO) properties was performed across a range of wavelengths that is almost triple that of previous reports (λ = 1200-2700 nm) and highlights the importance of broadband measurements. Glassy K 4GeP4Se12 also exhibits a measurable SHG response with no poling.
ASJC Scopus subject areas
- Colloid and Surface Chemistry