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《Journal of The Chinese Rare Earth Society》 1983-01
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CERTAIN CRITERIONS ON f→f TRANSITION EMISSION OF Eu~(2+) ION

Shi Chunshan and Ye Zeren (Changchun Institute of Applied Chemistry, Academia Sinica)  
The necessary condition for producing transition between ~6P_J states and ~8S_(7/2) states of the 4f~7 configuration of Eu~(2+) ion in host lattice is that, the lowest crystal field component of the 4f~6 5d must be situated above the ~6P_J states. Therefore, the crystal field splitting degree should be small and electrons exchanging effect between 4f~6 and 5d should be weak. In order to make such kind of crystal field environment surrounding Eu~(2+) ion in host lattice, special method combined crystallography with chemistry should be used. In fact, it is difficult to put this special method into practice. For this reason, it is essential to seek certain criterions which may intuitively characterize f→f transition emission of Eu~(2+) ion in host lattice from the view-point of chemistry.Crystal field environment surrounding Eu~(2+) ion is one of the most important criterions. It was proved by experiments that energy of ~6_(7/2) state ranges from 27700 cm~(-1) to 28000 cm~(-1). When the bottom of 5d energy band is lower than 27000 cm~(-1), only d→f transition emission of Eu~(2+) ion has been observed. When the bottom of 5d energy band is higher than 30000cm~(-1), only pure f→f transition emission of Eu~(2+) ion exists. Both f→f and d→f transitions may exist simultaneousely if the bottom of 5d energy band situates between 27000cm~(-1) to 30000cm~(-1). The f→f transition emission of Eu~(2+) ion in host lattice depends on the energy difference between ~6P_(7/2) and 5d states.The substitution of Eu~(2+) ion is affected by the ionic radius and the electronegativity of cations in host. The crystal field intensity surrounding Eu~(2+) ion decreases with the increase of ionic radius of M~(2+) in alkaline earths (M=Ca, St, Ba) fluoride. The bottom of 5d energy band increases with the decrease of electronegativity of substituted cation.The larger the coordination number (N) of Eu~(2+) is, the higher the energy of 5d band bottom locates. When N=8, only d→f transition emission can be observed. Both f→f and d→f have been observed if N lies from 8 to 12.Besides those criteria mentioned above, the nature of cations and anions in host lattice is also important for bringing about f→f transition emission of Eu~(2+) ion. The neighbouring cations of Eu~(2+) ion should be small and highly charged, It is effective for bringing about f→f transition or increasing its emission intensity, if the mole fraction of these cations icreases properly.
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