Enhanced IR-driven photoelectrochemical responses of CdSe/ZnO heterostructures by up-conversion UV/visible light irradiation.

We, for the first time, report the development of infrared (IR)-driven photoelectrochemical (PEC) cells using up-conversion glass-ceramics as substrates, which is different from the previous strategies of decorating photocatalysts with up-conversion (UC) rare earth-doped fluoride nanoparticles to utilize IR light. Our approach is more efficient since the use of UC glass-ceramics as substrates of photocatalysts could overcome the chemical instability of fluoride nanoparticles, the blockage of incident light, and the limited exposure of photocatalysts to liquid electrolytes. Oxyfluoride glass-ceramics bearing (Yb,Er)-doped YF and (Yb,Tm)-doped YF nanocrystals turned out to generate UC green and ultraviolet/blue emissions, respectively, under 980 nm illumination. High-density ZnO nanorods were grown on the up-conversion glass-ceramic substrates by the hydrothermal method and they were subsequently overcoated with CdSe nanocrystals to obtain CdSe/ZnO heterostructures by the chemical bath deposition method. CdSe nanoparticles were excited by both the UC UV emission from Tm and the visible emission from Er and Tm, while ZnO nanorods were excited mostly by the UC UV emission from Tm. Because of the difference in the UC emissions from Er and Tm, two distinct carrier transportations, sensitization and type-II cascade, occurred in the identical CdSe/ZnO heterostructures. Eventually, CdSe/ZnO fabricated on the glass-ceramics bearing (Yb,Tm)-doped YF showed increased photocurrent density compared to that fabricated on the glass-ceramics bearing (Yb,Er)-doped YF due to the charge separation activated by the type-II cascade structure.