Tero Laihinen

Mechanisms of Tenebrescence and Persistent Luminescence in Synthetic Hackmanite Na8Al6Si6O24(Cl,S)(2)

Synthetic hackmanites, Na8Al6Si6O24(Cl,S)2, showing efficient purple tenebrescence and blue/white persistent luminescence were studied using different spectroscopic techniques to obtain a quantified view on the storage and release of optical energy in these materials. The persistent luminescence emitter was identified as impurity Ti(3+) originating from the precursor materials used in the synthesis, and the energy storage for persistent luminescence was postulated to take place in oxygen vacancies within the aluminosilicate framework. Tenebrescence, on the other hand, was observed to function within the Na4(Cl,S) entities located in the cavities of the aluminosilicate framework. The mechanism of persistent luminescence and tenebrescence in hackmanite is presented for the first time.

Solar UV index and UV dose determination with photochromic hackmanites: from the assessment of the fundamental properties to the device

Extended exposure to sunlight or artificial UV sources is a major cause of serious skin and eye diseases such as cancer. There is thus a great need for convenient materials for the easy monitoring of UV doses. While organic photochromic molecules are tunable for responses under different wavelengths of UV radiation, they suffer from rather poor durability because the color changes involve drastic changes in molecular structure. Inorganic materials, on the other hand, are durable, but they have lacked tunability. Here, by combining computational and empirical data, we confirm the mechanism of coloration in the hackmanites, nature-based materials, and introduce a new technique called thermotenebrescence. With knowledge of the mechanism, we show that we can control and thus tune the energy of electronic states of synthetic hackmanites (Na,M)8Al6Si6O24(Cl,S)2 so that their body color is sensitive to the solar UV index as well as UVA, UVB or UVC radiation levels. Finally, we demonstrate that it is possible to use images taken with an inexpensive cell phone to quantify the radiation dose or UV index. The hackmanite materials thus show great potential for use in portable healthcare both in everyday life and in laboratories.

EXAFS study of cation reordering in NaYF4：Yb3＋,Tb3＋ up-conversion luminescence materials

The NaYF4:Yb3+, Tb3+ (xYb: 0.20, xTb: 0.04) materials were prepared using the co-precipitation method. The as-prepared material was washed either with or without water in addition to ethanol and thereafter annealed for 5 h at 500 °C. This resulted in materials with moderate or very high up-conversion luminescence intensity, respectively. The structural study carried out with X-ray powder diffraction revealed microstrains in the rare earth (R) sublattice that were relaxed for the material with very high up-conversion intensity thus decreasing energy losses. The local structural details were investigated with R LIII and Y K edge extended X-ray absorption fine structure (EXAFS) using synchrotron radiation. Around 10 mol.% of the Yb3+ ions were found to occupy the Na site in the material with very high up-conversion intensity. These Yb species formed clusters with the Tb3+ ions occupying the regular Na/R sites. Such clustering enhanced the energy transfer between Yb3+ and Tb3+ thus intensifying the up-conversion emission.