The emissions at 1,450 and 1,250 nm are a characteristic of Tm3+ in a low phonon energy host crystal. For Tm3+ in YAG or YLF, these emissions are quenched by multi-phonon relaxation, and the only IR emission observed is the broadband centred at 1,850 nm arising from the 3F4 level. Figure 2 Fluorescence from Tm 3+ :KPb 2 Cl 5 . Fluorescence
spectrum at 300 K between 1,100 and 2,000 nm of Tm3+:KPb2Cl5 that results from pumping GF120918 with an 805-nm laser diode. For the same 1,100- to 2,000-nm spectral range, a fluorescence spectrum from Tm3+:YCl3 at 300 K arising from pumping with a 0.35-W, 811-nm laser diode is shown in Figure 3[33]. Because YCl3 is also a low phonon energy host, the same three spectral features appear. In YCl3, the Tm3+ ions are at sites with higher symmetry than in KPb2Cl5. As a result, more of the Stark multiplet structure is resolvable in the emission lines in Figure 3
than in Figure 2. Also shown in Figure 3 is an overlap of a fluorescence spectrum at 400 K from the same crystal under the same pump conditions. As the temperature is increased, there is a small reduction in emission at 1,850 nm from the 3F4 level, but a doubling in 1,250-nm emission from the 3H5 level. The increase in emission from the 3H5 as the temperature is raised is an interesting and counterintuitive GSK2118436 in vivo result. The effect of a temperature increase on this emission is illustrated more graphically in Figure 4[33]. It shows
the normalized fluorescence intensity at three specific wavelengths as a function of temperature between 300 and 500 K. The wavelengths chosen reflect the populations of the first three excited states for Tm3+. The data show that the population of 3H5 state increases relative to the other states as the temperature rises. Figure 3 Fluorescence from Tm 3+ :YCl 3 . Comparison of fluorescence spectrum at 300 and 400 K between 1,100 Chloroambucil and 2,000 nm of Tm3+:YCl3 that results from pumping with an 811-nm laser diode. Figure 4 Temperature dependence of infrared fluorescence from Tm 3+ :YCl 3 . Normalized fluorescence intensity versus temperature between 300 and 500 K for Tm3+:YCl3. The fluorescence intensity of the 3 F4 level at 300 K is normalized to 1. The sample has a Tm3+ concentration of 0.7 × 1020 ions/cm3. Cross-relaxation in singly doped Tm3+ crystals The anomalous behaviour of the 1,200-nm fluorescence from the 3H5 state can be explained as arising from phonon-assisted cross-relaxation [34]. The processes illustrated in Figure 1 labelled C1 and C2 are both non-resonant and require phonon assistance to complete. C1 is the process already known in Tm3+-doped YAG and YLF that involves an interaction between a 3H4 ion activated by the pump and a 3H6 ion in the ground state to produce two 3F4 ions. The C1 process results in an excess of energy that must be converted to phonons.
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