Theoretical calculation and experimental research for structural stability and electronic properties induced by certain cluster defects in ADP crystal

Ammonium dihydrogen phosphate (NH 4 H 2 PO 4 , ADP) is an excellent nonlinear optical crystal and has had wide application. It was the same type of potassium dihydrogen phosphate (KH 2 PO 4 , KDP) with a similar crystal structure. The difference in structure and properties of ADP crystal in the presence of defects, especially cluster defects, was one of the important issues of concern in the research. In this work, first-principles calculation, coupled with HSE06 functional and the van der Waals-Wannier function method, was applied to investigate the structural stability and electronic properties induced by oxygen vacancy cluster defects and Fe P 2- +V O 2+ cluster defects. And some spectra experiments, such as Raman spectroscopy, the Fourier transform infrared spectroscopy and the ultraviolet absorption spectroscopy, were also applied to investigate the detailed influence for ADP crystal doped with different Fe 3+ concentration, which was grown with the “point-seed” rapid growth method. Combined with the theoretical results and the spectra tests, it confirmed that the structural changes in ADP crystal caused by oxygen vacancy cluster defect and Fe P 2- +V O 2+ cluster defect were smaller than that in KDP crystal, mainly due to the restriction of hydrogen bonds and NH 4 + group. With the increase of defect concentration, the microstructure stress could also damage the crystal structure due to the microscopic stress induced by Fe 3+ . The defect states moved towards right from 1.1 eV to 6.6 eV with the concentration of oxygen vacancy increasing. Similarly, the defect state composed of Fe 3d and O 2p states induced by Fe P 2- defect also moved to the conduction band minimum. The absorption peaks around 220-350 nm induced by Fe P 2- defect and Fe P 2- +V O 2+ cluster defect were along the xy plane. It provided a good suggestion based on the calculation that it was very important to minimize defects or control cluster defect concentration during crystal growth.