A broadband-sensitive upconverter: Garnet-type Ca3Ga2Ge3O12 codoped with Er3+, Y3+, Li+, Ni2+, and Nb5+

We have developed a new broadband-sensitive photon upconversion (UC) material that can be used for transparent ceramic plates mounted on the rear faces of crystalline silicon solar cells. We selected the host material of a cubic crystal structure codoped with Er³⁺ and Ni²⁺ so that the Ni²⁺ dopants were fully activated to sensitize the Er³⁺ emitters. In garnet-type Ca₃Ga₂Ge₃O₁₂ with additional codopants of Nb⁵⁺ and Li⁺ for charge compensation, all the Ni²⁺ dopants occupied the six-coordinated Ga³⁺ sites, leading to highly efficient energy transfer from the Ni²⁺ to the Er³⁺. Formation of four-coordinated Ni²⁺ that quenches the UC emission of the Er³⁺ was prevented, because Ni²⁺ cannot substitute the four-coordinated Ge⁴⁺ much smaller than Ni²⁺. Consequently, energy dissipation from the Er³⁺ to the Ni²⁺ was well reduced compared with the previously developed Gd₃Ga₅O₁₂:Er,Ni,Nb in which the Ni²⁺ dopants partially occupied the four-coordinated Ga³⁺ sites. Additional introduction of Y³⁺ and Li⁺ enhanced optical transitions and improved the UC performance, owing to more enhanced lattice distortion, along with eliminating different phases. The optimal composition (Ca_0.6Er_0.1Y_0.1Li_0.2)₃(Ga_0.98Ni_0.01Nb_0.01)₂Ge₃O₁₂ exhibited a broadband sensitivity ranging from 1.1 μm (the absorption edge of silicon) to 1.6 μm for the UC emission at 0.98 μm.