Disputed Mechanism for NIR-to-Red Upconversion Luminescence in NaYF4:Yb(3+),Er(3+)

The most commonly proposed mechanisms for NIR-to-red upconversion in the well-studied material β-NaYF4:Er(3+),Yb(3+) are evaluated in order to resolve inconsistencies that persist in the literature. Each of four possible mechanisms is evaluated in terms of the direct analysis of spectroscopic data. It is shown that there are no important mechanisms that involve the first excited state of Er(3+), (4)I13/2, as an intermediate state. A large body of evidence overwhelmingly supports the proposed mechanism of Anderson et al., which suggests an intimate connection between NIR-to-red and NIR-to-blue upconversion. Namely, both red and blue upconversion are produced primarily by a three-photon excitation process that proceeds through the green emitting state to a dense manifold of states, (4)G/(2)K, above the blue emitting state, (2)H9/2. Competing relaxation mechanisms out of (4)G/(2)K determine the relative amounts of blue and red upconversion produced. Multiphonon relaxation from (4)G/(2)K results in blue upconversion, whereas back energy transfer from Er(3+)((4)G/(2)K) to Yb(3+)((2)F7/2) results in red emission.