Simultaneous Observation of Visible Upconversion and Near-Infrared Downconversion in SrF2:Nd3+/Yb3+/Er3+ Nanocrystals and Their Application for Detecting Metal Ions under Dual-Wavelength Excitation.

In this work, a sequence of Nd3+, Yb3+, and Er3+ tridoped SrF2 nanocrystals (NCs) is synthesized by a hydrothermal method. Both the efficient near-infrared downconversion luminescence (DCL) and visible upconversion luminescence (UCL) of the Er3+ and Nd3+ ions are simultaneously observed and systematically demonstrated under dual-wavelength excitation (808 and 980 nm continuous-wave lasers). Subsequently, the SrF2:Nd3+/Yb3+/Er3+ (15/4/0.2 mol %) NCs with the strongest luminescence were utilized for detecting the metal ion concentrations under 808 nm excitation. The results reveal that both the UCL and DCL gradually decrease as the metal ion concentrations increase, and high sensitivity is obtained for Cu2+ ions with a detection limit of 0.22 nM (∼650 nm) and 0.63 nM (∼976 nm). In addition, these SrF2:Nd3+/Yb3+/Er3+ NCs are further demonstrated to achieve a solid-state display under 980 nm excitation, exhibiting obvious "red" and "green" patterns by varying the doping rare earth ion concentrations.

Boltzmann- and Non-Boltzmann-Based Thermometers in the First, Second and Third Biological Windows for the SrF2:Yb3+, Ho3+ Nanocrystals Under 980, 940 and 915 nm Excitations.

Spectrally determination of temperature based on the lanthanide-doped nanocrystals (NCs) is a vital strategy to noninvasively measure the temperature in practical applications. Here, we synthesized a series of SrF2:Yb3+/Ho3+ NCs and simultaneously observed the efficient visible upconversion luminescence (UCL) and near-infrared (NIR) downconversion luminescence (DCL) under 980, 940 and 915 nm excitations. Subsequently, these NCs were further utilized for thermometers based on the Boltzmann (thermally coupled levels, TCLs) and non-Boltzmann (non-thermally coupled levels, NTCLs) of Ho3+ ions in the first (~ 650 nm), second (~ 1012 nm) and third (~ 2020 nm) biological windows (BW-I, BW-II and BW-III) under tri-wavelength excitations. The thermometric parameters including the relative sensitivity ([Formula: see text]) and temperature uncertainty ([Formula: see text]) are quantitatively determined on the I648/I541 (BW-I), I1186/I1012 (BW-II), and I1950/I2020 (BW-III) transitions of Ho3+ ions in the temperature range of 303-573 K. Comparative experimental results demonstrated that the thermometer has superior performances.

Excitation-Power-Dependent Upconversion Luminescence Competition in Single ß-NaYbF4:Er Microcrystal Pumped at 808 nm.

Controlling the upconversion luminescence (UCL) intensity ratio, especially pumped at 808 nm, is of fundamental importance in biological applications due to the water molecules exhibiting low absorption at this excitation wavelength. In this work, a series of ß-NaYbF4:Er microrods were synthesized by a simple one-pot hydrothermal method and their intense green (545 nm) and red (650 nm) UCL were experimentally investigated based on the single-particle level under the excitation of 808 nm continuous-wave (CW) laser. Interestingly, the competition between the green and red UCL can be observed in highly Yb3+-doped microcrystals as the excitation intensity gradually increases, which leads to the UCL color changing from green to orange. However, the microcrystals doped with low Yb3+ concentration keep green color which is independent of the excitation power. Further investigations demonstrate that the cross-relaxation (CR) processes between Yb3+ and Er3+ ions result in the UCL competition.

Dual-Wavelength Excited Intense Red Upconversion Luminescence from Er3+-Sensitized Y2O3 Nanocrystals Fabricated by Spray Flame Synthesis.

Er3+-sensitized upconversion nanoparticles (UCNPs) have attracted great attention due to their tunable upconversion (UC) emissions, low cytotoxicity, high resistance to photobleaching and especially multiple effective excitation wavelengths. However, detailed energy conversion between Er3+ and Tm3+ ions in Y2O3 UCNPs is still a problem, especially under multi-wavelength and variable pulse width excitation. In this work, we successfully fabricated a series of Er3+-sensitized Y2O3 nanocrystals by a spray flame synthesis method with a production rate of 40.5 g h-1. The as-prepared UCNPs are a pure cubic phase with a mean size of 14 nm. Excited by both 980 and 808 nm lasers, the tunable upconversion luminescence (UCL) from Er3+ ions was achieved by increasing the Er3+ doping concentration, co-doping Tm3+ ions and extending excitation pulse-width. The investigations of the lifetimes and the laser power dependence of UC emissions further support the proposed mechanism, which provides guidance for achieving effective color control in anticounterfeiting and multiplexed labeling applications. In addition, the red UC emission at about 5 mm beneath the tissue surface was observed in an ex vivo imaging experiment under the excitation of 808 nm laser, indicating that the Y2O3:Er3+/Tm3+ UCNPs have great prospects in further biological applications.

Revisiting the Enhanced Red Upconversion Emission from a Single ß-NaYF4:Yb/Er Microcrystal By Doping with Mn2+ Ions.

The presence of manganese ions (Mn2+) in Yb/Er-co-doped nanomaterials results in suppressing green (545 nm) and enhancing red (650 nm) upconversion (UC) emission, which can achieve single-red-band emission to enable applications in bioimaging and drug delivery. Here, we revisit the tunable multicolor UC emission in a single Mn2+-doped ß-NaYF4:Yb/Er microcrystal which is synthesized by a simple one-pot hydrothermal method. Excited by a 980 nm continuous wave (CW) laser, the color of the single ß-NaYF4:Yb/Er/Mn microrod can be tuned from green to red as the doping Mn2+ ions increase from 0 to 30 mol%. Notably, under a relatively high excitation intensity, a newly emerged emission band at 560 nm (2H9/2 → 4I13/2) becomes significant and further exceeds the traditional green (545 nm) emission. Therefore, the red-to-green (R/G) emission intensity ratio is subdivided into traditional (650 to 545 nm) and new (650 to 560 nm) R/G ones. As the doped Mn2+ ions increase, these two R/G ratios are in lockstep with the same tunable trends at low excitation intensity, but the tunable regions become different at high excitation intensity. Moreover, we demonstrate that the energy transfer (ET) between Mn2+ and Er3+ contributes to the adjustment of R/G ratio and leads to tunable multicolor of the single microrod. The spectroscopic properties and tunable color from the single microrod can be potentially utilized in color display and micro-optoelectronic devices.

Simultaneous size manipulation and red upconversion luminescence enhancement of CaF2:Yb3+/Ho3+ nanoparticles by doping with Ce3+ ions.

Harnessing the color tuning capability of upconversion nanoparticles (UCNPs) is of great significance in the field of advanced bioimaging and color display. Here, we report the tunable size and upconversion luminescence (UCL) multicolor in CaF2:Yb3+/Ho3+/Ce3+ UCNPs, which were synthesized by a facile hydrothermal method. It was found that the size of these UCNPs could be controlled (from 600 to 30 nm) by varying the concentration of Ce3+ ions. Under the excitation of a 980 nm continuous-wave (CW) laser, the UCL color of these UCNPs can be tuned from green to red as the doped Ce3+ ions gradually increase from 0 to 10 mol% and the red-to-green (R/G) ratio is enhanced remarkably. It is suggested that the cross-relaxation (CR) processes between Ho3+ and Ce3+ ions contribute to the tunable multicolor and enhancement of the R/G ratio. The mechanism of these processes is well supported by the time-resolved decay and near infrared (NIR) emission measurements.

Controlling the Two-Photon-Induced Photon Cascade Emission in a Gd(3+)/Tb(3+)-Codoped Glass for Multicolor Display.

We reported the first observation of the two-photon-induced quantum cutting phenomenon in a Gd(3+)/Tb(3+)-codoped glass in which two photons at ~400 nm are simultaneously absorbed, leading to the cascade emission of three photons in the visible spectral region. The two-photon absorption induced by femtosecond laser pulses allows the excitation of the energy states in Gd(3+) which are inactive for single-photon excitation and enables the observation of many new electric transitions which are invisible in the single-photon-induced luminescence. The competition between the two-photon-induced photon cascade emission and the single-photon-induced emission was manipulated to control the luminescence color of the glass. We demonstrated the change of the luminescence color from red to yellow and eventually to green by varying either the excitation wavelength or the excitation power density.

Three-photon-induced blue emission with narrow bandwidth from hot flower-like ZnO nanorods.

ZnO nanorods (NRs) self-organized into flowers were synthesized at different temperatures ranging from 100°C to 180°C by using the hydrothermal method. The existence of Zn interstitials (Zn(i)) was confirmed by X-ray photoelectron spectroscopy and a larger amount of Zn(i) was found in the ZnO NRs prepared at higher temperatures. A redshift of the emission peak of more than 15 nm was observed for the ZnO NRs under single photon excitation. The nonlinear optical properties of the flower-like ZnO NRs were characterized by using focused femtosecond laser light and strong three-photon-induced luminescence was observed at an excitation wavelength of ~750 nm. More interestingly, a large redshift of the emission peak was observed with increasing excitation intensity, resulting in efficient blue emission with a narrow bandwidth of ~30 nm. It was confirmed that the large redshift originates from the heating of the ZnO NRs to a temperature of more than 800°C and the closely packed ZnO NRs in the flowers play a crucial role in heat accumulation. The stable and efficient three-photon-induced blue emission from such ZnO NRs may find potential applications in the fields of optical display, high-temperature sensors and light therapy of tumors.

Enhanced second harmonic generation of MoS2 layers on a thin gold film.

The linear and nonlinear optical properties of thin MoS2 layers exfoliated on an Au/SiO2 substrate were investigated both numerically and experimentally. It was found that the MoS2 layers with different thicknesses exhibited different colors on the gold film. The reflection spectra of the MoS2 layers with different thicknesses were calculated by using the finite-difference time-domain technique and the corresponding chromaticity coordinates were derived. The electric field enhancement factors at both the fundamental light and the second harmonic were calculated and the enhancement factors for second harmonic generation (SHG) were estimated for the MoS2 layers with different thicknesses. Different from the MoS2 layers on a SiO2/Si substrate where the maximum SHG was observed in the single-layer MoS2, the maximum SHG was achieved in the 17 nm-thick MoS2 layer on the Au/SiO2 substrate. As compared with the MoS2 layers on the SiO2/Si substrate, a significant enhancement in SHG was found for the MoS2 layers on the Au/SiO2 substrate due to the strong localization of the electric field. More interestingly, it was demonstrated experimentally that optical data storage can be realized by modifying the SHG intensity of a MoS2 layer through thinning its thickness.

Efficient blue light emission from In0.16Ga0.84N/GaN multiple quantum wells excited by 2.48-µm femtosecond laser pulses.

We report on the efficient blue light emission from In0.16Ga0.84N/GaN multiple quantum wells excited by femtosecond laser pulses with long wavelengths ranging from 1.24 to 2.48 µm. It is found that the trap states in GaN barrier layers lead to an efficient cascade multiphoton absorption in which the carriers are generated through simultaneous absorption of n (n=1 and 2) photons to the trap states, followed by simultaneous absorption of m (m=3, 4, and 5) photons to the conduction band. The dependence of the upconversion luminescence on excitation intensity exhibits a slope between n and n+m, which is in good agreement with the prediction based on the rate equation model.

Controllable color display induced by excitation-intensity-dependent competition between second and third harmonic generation in ZnO nanorods.

We investigated the second and third harmonic generation (SHG and THG) in ZnO nanorods (NRs) by using a femtosecond laser (optical parametric amplifier with tunable wavelengths) with a long excitation wavelength of 1350 nm and a low repetition rate of 1 kHz. The damage threshold for ZnO NRs in this case was sufficiently large, enabling us to observe the competition between SHG and THG. The transition from red to blue emission and the mixing of red and blue light with different ratios were successfully demonstrated by simply varying excitation intensity, implying the potential applications of ZnO NRs in all-optical display.