Structure analysis of a Mn-doped willemite-type compound, H0.12(Zn1.89(3)Mn0.05(1)□0.06)Si1.00(1)O4

Large single crystals of a well-known green phosphor, Mn-doped willemite (α-Zn2SiO4)-type compound were grown from molten MnF2/Li2MoO4. In this structure Mn2+ and defects partially replace Zn2+ at two independent sites, and there are no cation species in the middle of six-membered ring channels. As a consequence of 3% defective sites (□), this structure may have protons for ensuring its electrostatic neutrality. Although the position of H+ could not be clearly found the present study indicates the presence of protons in the vicinity of oxygens to make relative short H⋯O bonds below 1.6 Å. Two unusual, broad IR bands about 1780 and 2360 cm−1 can be explained by disordering of strongly bonded O···H groups. This compound represents a structural unit, H0.12(Zn1.89(3)Mn0.05(1)□0.06)Si1.00(1)O4, based on X-ray single crystal diffraction, electron microprobe, and FT-IR spectroscopy. - Graphical abstract: A willemite-type compound, H0.12(Zn1.89(3)Mn0.05(1)□0.06)Si1.00(1)O4 exhibits protons near to oxygens in the skirt of four- and six-membered ring channels, as a result of defects at two crystallographically different Zn sites. Display Omitted - Highlights: • Structure properties of a 0.05 Mn-doped α-Zn2SiO4 compound using X-ray single crystal diffraction. • Static disorder of Zn, Mn, and defects in the framework of α-Zn2SiO4. • Sign of strong H⋯O bonds, observed in FT-IR spectroscopy