It is generally accepted that a lanthanide ions based upconversion material follows an activator low doping strategy (normally <3 mol%), because of the restriction of the harmful concentration quenching effect. Here, we demonstrate that this limitation can be broken in nanostructures. Simply by using an inert shell coating strategy, the concentration quenching effect for the activator (Er³⁺) could be eliminated and highly efficient upconversion luminescence realized in the activator fully doped nanostructure, e.g. NaErF₄@NaYF₄. More importantly, this novel nanostructure achieves some long-cherished desires, such as multiple-band co-excitation (∼800 nm, ∼980 nm and ∼1530 nm) and monochromic red emission. Proof-of-concept experiments are presented of the potential benefit of this structure in solar cells and anti-counterfeiting. This nanostructure offers new possibilities in realizing high upconversion emission and novel functionalities of lanthanide based nanomaterials.

Upconversion emission dynamics have long been believed to be determined by the activator and its interaction with neighboring sensitizers. Herein this assumption is, however, shown to be invalid for nanostructures. We demonstrate that excitation energy migration greatly affects upconversion emission dynamics. “Dopant ions’ spatial separation” nanostructures are designed as model systems and the intimate link between the random nature of energy migration and upconversion emission time behavior is unraveled by theoretical modelling and confirmed spectroscopically. Based on this new fundamental insight, we have successfully realized fine control of upconversion emission time behavior (either rise or decay process) by tuning the energy migration paths in various specifically designed nanostructures. This result is significant for applications of this type of materials in super resolution spectroscopy, high‐density data storage, anti‐counterfeiting, and biological imaging.

Relatively low efficiency is the bottleneck for the application of lanthanide‐doped upconversion nanoparticles (UCNPs). The high‐level doping strategy realized in recent years has not improved the efficiency as much as expected. It is argued that cross relaxation (CR) is not detrimental to upconversion. Here we combine theoretical simulation and spectroscopy to elucidate the role of CR in upconversion process of Er³⁺ highly doped (HD) UCNPs. It is found that if CR is purposively suppressed, upconversion efficiency can be significantly improved. Specifically, we demonstrate experimentally that inhibition of CR by introducing cryogenic environment (40 K) enhances upconversion emission by more than two orders of magnitude. This work not only elucidates the nature of CR and its non‐negligible adverse effects, but also provides a new perspective for improving upconversion efficiency. The result can be directly applied to cryogenic imaging and wide range temperature sensing.

Upconversion emission dynamics have long been believed to be determined by the activator and its interaction with neighboring sensitizers. Herein this assumption is, however, shown to be invalid for nanostructures. We demonstrate that excitation energy migration greatly affects upconversion emission dynamics. “Dopant ions’ spatial separation” nanostructures are designed as model systems and the intimate link between the random nature of energy migration and upconversion emission time behavior is unraveled by theoretical modelling and confirmed spectroscopically. Based on this new fundamental insight, we have successfully realized fine control of upconversion emission time behavior (either rise or decay process) by tuning the energy migration paths in various specifically designed nanostructures. This result is significant for applications of this type of materials in super resolution spectroscopy, high‐density data storage, anti‐counterfeiting, and biological imaging.