Nd3+-sensitized upconversion nanoparticles (UCNPs) can be excited by both 980 and 808 nm light, which is regarded as a particularly advantageous property of these particles. In this work, we demonstrate that the nanoparticles can exhibit significantly different response when excited at these two excitation wavelengths, showing dependence on the intensity of the excitation light and the way it is distributed in time. Specifically, with 808 nm excitation saturation in the emitted luminescence is more readily reached with increasing excitation intensities than upon 980 nm excitation. This is accompanied by delayed upconversion luminescence (UCL) kinetics and weaker UCL intensities. The different luminescence response at 808 and 980 nm excitation reported in this work is relevant in a manifold of applications using UCNPs as labels and sensors. This could also open new possibilities for multi-wavelength excitable UCNPs for upconversion color display and in laser-scanning microscopy providing selective readouts and sub-sectioning of samples.

In this study, we systematically investigate the decay characteristics of upconversion luminescence (UCL) under anti-Stokes excitation through numerical simulations based on rate-equation models. We find that a UCL decay profile generally involves contributions from the sensitizer's excited-state lifetime, energy transfer and cross-relaxation processes. It should thus be regarded as the overall temporal response of the whole upconversion system to the excitation function rather than the intrinsic lifetime of the luminescence emitting state. Only under certain conditions, such as when the effective lifetime of the sensitizer's excited state is significantly shorter than that of the UCL emitting state and of the absence of cross-relaxation processes involving the emitting energy level, the UCL decay time approaches the intrinsic lifetime of the emitting state. Subsequently, Stokes excitation is generally preferred in order to accurately quantify the intrinsic lifetime of the emitting state. However, possible cross-relaxation between doped ions at high doping levels can complicate the decay characteristics of the luminescence and even make the Stokes-excitation approach fail. A strong cross-relaxation process can also account for the power dependence of the decay characteristics of UCL.

The dearth of high upconversion luminescence (UCL) intensity at low excitation irradiance hinders the prevalent application of lanthanide-doped upconversion nanoparticles (UCNPs) in many fields ranging from optical bioimaging to photovoltaics. In this work, we propose to use microlens arrays (MLAs) as spatial light modulators to manipulate the distribution of excitation light fields in order to increase UCL, taking advantage of its nonlinear response to the excitation irradiance. We show that multicolored UCL from NaYF4:Yb3+,Er3+@NaYF4:Yb3+,Nd3+ and NaYF4:Yb3+,Tm3+@NaYF4:Yb3+,Nd3+ core/shell UCNPs can be increased by more than one order of magnitude under either 980 or 808 nm excitation, by simply placing a polymeric MLA onto the top of these samples. The observed typical green (525/540 nm) and red (654 nm) UCL bands from Er3+ and a blue (450/475 nm) UCL band from Tm3+ exhibit distinct enhancement factors due to their different multi-photon processes. Importantly, our ray tracing simulation reveals that the MLA is able to spatially confine the excitation light (980 and 808 nm) by orders of magnitude, thus amplifying UCL by more than 225-fold (the 450 nm UCL band of Tm3+) at low excitation irradiance. The proposed MLA method has immediate ramifications for the improved performance of all types of UCNP-based devices, such as UCNP-enhanced dye sensitized solar cells demonstrated here.

Facing the fact that selective detection of multiple narrow spectral bands in the near-infrared (NIR) region still poses a fundamental challenge, we have, in this work, developed NIR photodetectors (PDs) using photon upconversion nanocrystals (UCNCs) combined with perovskite films. In order to conquer the relatively high pumping threshold of UCNCs, we designed a novel cascade amplification strategy for upconversion luminescence (UCL) through cascading the superlensing effect of dielectric microlens arrays and the plasmonic effect of gold nanorods, which readily leads to a UCL enhancement by more than four orders of magnitude under weak light irradiation. By accommodating multiple optical active lanthanide ions in a core-shell-shell hierarchical architecture, the developed PDs on top can detect three well-separated narrow bands in the NIR region, i.e., 808, 980, and 1540 nm, respectively. Due to the large UCL enhancement, the obtained PDs demonstrate extremely high responsivity of 30.73, 23.15, 12.20 A/W and detectivity of 5.36, 3.45, 1.91x10^11 Jones for the 808, 980, and 1540 nm light detection, respectively, together with short response times in the range of 80-120 ms. Moreover, we demonstrate for the first time that the response to the excitation modulation frequency of a PD can be employed to discriminate the incident light wavelength. We believe that our work provides a novel insight for developing NIR PDs, and that it can spur the development of other applications using upconversion nanotechnology.

Lanthanide upconversion nanoparticles (UCNPs) are increasingly explored to develop high-security-level anti-counterfeiting and multiplexing applications, due to the availability of ample encoding dimensions. Among other applications, upconversion luminescence(UCL) kinetics-based optical encoding is particularly attractive as it provides an almost unlimited encoding capacity due to the ease of manipulating the UCL kinetics by chemical engineering. However, current decoding methods limit its applications because of a typically low throughput and high cost of the system. In this Letter, we propose a novel decoding approach for UCL kinetics-based optical encoding, which utilizes a pulsed excitation source with adjustable pulse duration and a low time-resolution and large-area detector. We develop a theoretical fitting model and show how fingerprint time constants of the UCNPs (the encoding identities) can be extracted from the correlation between the averaged UCL intensity and the pulse duration. Our new approach provides a high-throughput and cost-effective solution to decode UCL kinetics.