Exploration of Rare Earth Elements and Absorption-Emission Features in Rare Earth (La-Lu) Orthophosphates

Mining of rare earth elements (REEs) followed by application of mined REEs to wide range of application, has been of immense interest for both, geologists and phosphor engineers. In the present contribution, we will focus on a) exploring laser-induced fluorescence (LIF) for REE exploration in our project “inSPECtor”; and b) combining absorption-emission characteristics to understand f-f and f-d transitions in rare earth orthophosphates (La-Lu)PO4. Orthophosphate deposits in nature are important for technological and environmental challenges faced by high-tech industry. It has been shown recently that the phosphorites can be considered as the primary source of REEs to solve the global rare earth supply shortage [1]. The existing technologies in rare earth exploration are based on diffuse-reflectance measurements (for example, Hyperspectral Imaging). However, the spectral features of REEs are due to sharp 4f-4f intraconfigurational transitions, which are sufficiently distinct to enable spectral classification. LIF is an important technique which records REE features in spectral as well as the time domain. Recently, we started a project “inSPECtor” to develop a single sensor system, which combines hyperspectral imaging (or diffuse reflectance spectra) with laser induced fluorescence (for spectral and time resolution from ns to ms). From an application point of view, the Rare earth orthophosphates (REPO4) are important compounds for application in light emitting diodes (LEDs), plasma display panels (PDPs) and fluorescent lamps [2]. The lower atomic number lanthanides (La-Gd) based orthophosphates crystallise with monoclinic structure (P21/n space group) at moderately high temperatures; while the higher atomic number lanthanides based orthophosphates possess tetragonal xenotime-type structure (I41/amd space group). The luminescence properties in a lattice of orthophosphates are expected to be controlled by the type of REEs and their coordination around PO43- tetrahedra. However, PO43- (which forms host valence and conduction band), is transparent itself in visible-UV region and does not absorb, up to approximately 175 nm [3]. Hence, the type of rare earth ion, which increases in ionic radii by approximately 22% from La-Lu, control the electronic structure and optical properties therein. Some of the REPO4, for example-LaPO4, GdPO4, YPO4 and LuPO4; have been explored recently for their charge carrier trapping and relevant applications in storage devices [4]. However, information for other REPO4 is limited and no clear information, relevant to their absorption-emission features, charge storage/release could be found. We present results on our extensive investigation in both these directions; the new sensor and fundamental properties.

References:

[1] P. Emsbo, P.I.McLaughlin, G.N.Breit, E.A.du Bray, A.E.Koenig, Gondwana Res., 27 (2015) 776-785.
[2] J. George, C.Ryan, R.K.Brow, J. Am. Ceram. Soc. 97 (2014) 2249-2255.
[3] P.Melnikov, A.M.Massabni, O.Malta, Phosphorus, Sulfur and Silicon and Related Elements, 1996, pp. 1-1.
[4] T.Lyu, P.Dorenbos, J.Mater.Chem. C, 6 (2018) 369-379.