Coupling between the protons and PO4 tetrahedra in H+-ion-irradiated TlH2PO4

Abstract

We studied hydrogen-bonded TlH2PO4 (TDP) ferroelectrics treated with proton-beam bombardment. The TDP material was irradiated with a 1-MeV proton beam at a dose of 1015/cm2. To analyze the local microscopic structure of TDP, we conducted 1H combined rotation and multiple pulse spectroscopy (CRAMPS), nuclear magnetic resonance (NMR), and high-resolution 31P NMR measurements. The isotropic chemical shifts of hydrogen and phosphor nuclei exhibited displacive features throughout the antiferroelectric, ferroelastic, and paraelastic phases that were attributed to the interplay of PO4 lattice deformation and the microscopic hydrogen bond network. The temperature dependence of the isotropic chemical shift σiso in 1H and high resolution 31P NMR revealed that the electronic charge redistribution was induced by proton-beam irradiation and the material’s elastic properties. We examined the proton-lattice relationship in terms of the proton’s location in a local double minimum well and the displacive character of the PO4 lattice.