Manipulation of Luminescence via Surface Site Occupation in Ln3+-Doped Nanocrystals.

Ln3+-doped (Ln = lanthanide) nanocrystals are garnering strong interest for their potential as optical materials in various applications. For that reason, a thorough understanding of photophysical processes and ways to tune them in these materials is of great importance. This study, using Eu3+-doped Sr2YF7 as a well-suited model system, underscores the (not unexpected) significance of surface site occupation of Ln3+ and also challenges the prevailing views about their contribution to the luminescence of the system. High-temperature cation exchange and epitaxial shell growth allow nanocrystals to exclusively feature Eu3+ residing at the surface or in the interior, thereby separating their spectral responses. Meticulous experiments reveal that nanocrystals with high doping concentrations exhibit luminescence primarily from surface Eu3+, in contrast to the popular belief that luminescence from surface Ln3+ is largely negligible. The present study shows, on the one hand, the necessity to revise common ideas and also reveals the potential for manipulating the luminescence of such materials through an, until now, unperceived way of surface engineering.

Size Control and Improved Aqueous Colloidal Stability of Surface-Functionalized ZnGa2O4:Cr3+ Bright Persistent Luminescent Nanoparticles.

Near-infrared (NIR)-emitting ZnGa2O4:Cr3+ (ZGO) persistent luminescent nanoparticles (PLNPs) have recently attracted considerable attention for diverse optical applications. The widespread use and promising potential of ZGO material in different applications arise from its prolonged post-excitation emission (several minutes to hours) that eliminates the need for continuous in situ excitation and the possibility of its excitation in different spectral regions (X-rays and UV-vis). However, the lack of precise control over particle size/distribution and its poor water dispersibility and/or limited colloidal stability required for certain biological applications are the major bottlenecks that limit its practical applications. To address these fundamental limitations, herein, we have prepared oleic acid (OA)-stabilized ZGO PLNPs with controlled size (7-12 nm, depending on the type of alcohol used in synthesis) and monodispersity. A further increase in size (8-21 nm), with a concomitant increase in persistent luminescence, could be achieved using a seed-mediated approach, employing the as-prepared ZGO PLNPs from the first synthesis as the seed and growing layers of the same material by adding fresh precursors. To remove their surface oleate groups and make the nanoparticles hydrophilic, two surface modification strategies were evaluated: modification with only poly(acrylic acid) (PAA) as the hydrophilic capping agent and modification with either PAA or cysteamine (Cys) as the hydrophilic capping agent in conjunction with BF4- as the intermediate surface modifier. The latter surface modifications involving BF4- conferred long-term (60 days and longer) colloidal stability to the nanoparticles in aqueous media, which is related to their favorable ζ potential values. The proposed generalized strategy could be used to prepare different kinds of surface-functionalized PLNPs with control of size, hydrophilicity, and colloidal stability and enhanced/prolonged persistent luminescence for diverse potential applications.

Factors of Importance for Arsenic Migration/Separation under Coffee-Ring Effect on Silver Nanofilms.

Surface-enhanced Raman spectroscopy (SERS) has been recognized as a promising analytical technique owing to its merit of nondestructive and fast detection capabilities. However, SERS usually suffers signal interferences from different analytes or a complicated matrix. Separation is an effective approach to solve the signal interference in the application of SERS. It was proposed that two concentric coffee rings could serve as a simple separation platform; however, there are still many questions to be answered for in-depth understanding. In this study, critical parameters during the formation of two concentric coffee rings are characterized for a better understanding of this phenomenon, including surface tension, surface morphology, and surface energy. Two arsenicals, including arsenate (AsV) and cacodylic acid (DMAV), are chosen to study the arsenicals' separation/migration mechanism due to their significant difference in chemical properties. In the typical coffee ring, these two arsenicals have signal interference and only DMAV is detected via SERS; however, they are detected along the radius of the two concentric coffee rings. The distribution of arsenicals on the two concentric coffee rings is further verified by the chromatographic method. Under this simple platform, interactions between the arsenicals and the surface of the silver nanofilm are pivotal to their migration/separation. By surface modification of silver nanofilm with small molecules, the surface polarity and surface ζ potential are manipulated. The signal dynamics of these two arsenicals are studied on these modified silver nanofilms. It is clear that the electrostatic interaction plays a more important role than the polarity in the arsenicals' migration. This study reveals the mechanism of small molecule migration/separation in the two concentric coffee rings and provides insights for future study of employing this simple platform.

Moisture-Resistant Mn4+ -Doped Core-Shell-Structured Fluoride Red Phosphor Exhibiting High Luminous Efficacy for Warm White Light-Emitting Diodes.

K2 TiF6 :Mn4+ is a highly efficient narrow-band emission red phosphor with promising applications in white light-emitting diodes (LEDs) and wide-gamut displays. Nevertheless, the poor moisture-resistant properties of this material hinder commercialization. A convenient reverse cation-exchange strategy is introduced for constructing a core-shell-structured K2 TiF6 :Mn4+ @K2 TiF6 phosphor. The outer K2 TiF6 shell acts as a shield for preventing moisture in the air from hydrolyzing the internal MnF6 2- group, while effectively cutting off the path of energy migration to surface defects, thereby increasing the emission efficiency (especially for the phosphors doped with high concentrations of Mn4+ ). Employed as a red phosphor, the packaged white LED exhibits an extraordinarily high luminous efficacy of 162 lm W-1 , a correlated color temperature (CCT) of 3510 K, and a color rendering index of 93 (Ra ). Aging tests performed on this device at 85 °C and 85 % humidity for 480 h retain up to 89 % luminous efficacy. The findings could facilitate commercial application of K2 TiF6 :Mn4+ @K2 TiF6 phosphor.

Heterogeneous Oxysulfide@Fluoride Core/Shell Nanocrystals for Upconversion-Based Nanothermometry.

Lanthanide (Ln3+)-doped upconversion nanoparticles (UCNPs) often suffer from weak luminescence, especially when their sizes are ultrasmall (less than 10 nm). Enhancing the upconversion luminescence (UCL) efficiency of ultrasmall UCNPs has remained a challenge that must be undertaken if any practical applications are to be envisaged. Herein, we present a Ln3+-doped oxysulfide@fluoride core/shell heterostructure which shows efficient UCL properties under 980 nm excitation and good stability in solution. Through epitaxial heterogeneous growth, a ∼4 nm optically inert ß-NaYF4 shell was coated onto ∼5 nm ultrasmall Gd2O2S:20%Yb,1%Tm. These Gd2O2S:20%Yb,1%Tm@NaYF4 core/shell UCNPs exhibit a more than 800-fold increase in UCL intensity compared to the unprotected core, a 180-fold increase in luminescence decay time of the 3H4 → 3H6 Tm3+ transition from 5 to 900 µs, and an upconversion quantum yield (UCQY) of 0.76% at an excitation power density of 155 W/cm2. Likewise, Gd2O2S:20%Yb,2%Er@NaYF4 core/shell UCNPs show a nearly 5000-fold increase of their UCL intensity compared to the Gd2O2S:20%Yb,2%Er core and a maximum UCQY of 0.61%. In the Yb/Er core-shell UCNP system, the observed variation of luminescence intensity ratio seems to originate from a change in lattice strain as the temperature is elevated. For nanothermometry applications, the thermal sensitivities based on thermally coupled levels are estimated for both Yb/Tm and Yb/Er doped Gd2O2S@NaYF4 core/shell UCNPs.

Multiple emission bands NIR-persistent luminescence mSiO2@Zn0.6Ca0.4Ga2O4:Cr3+,Yb3+ nanoparticles for biological applications.

Persistent luminescence nanoparticles (PLNPs) emitting in the NIR window (700-1700 nm) have shown great promise in the field of fluorescence imaging due to their unique properties, including the absence of in situ excitation and low optical scattering in tissues. However, they are still facing some challenges, such as irregular shape, wide size distribution and poor persistent luminescence performance. Here, we report a facile mesoporous template method for synthesizing mSiO2@Zn0.6Ca0.4Ga2O4:Cr3+,Yb3+ (mSiO2@ZCGO) persistent luminescent nanoparticles, which show a regular morphology and a size of about 69 nm. In addition, these nanocrystals exhibit persistent luminescence in multi-NIR windows, the first infrared window (∼696 nm of Cr3+ emission) and second infrared window (∼1000 nm of Yb3+ emission). Under illumination of a 254 nm UV lamp for 10 min, the persistent time of Cr3+ ions and Yb3+ ions lasted more than 120 min and 10 min, respectively. In particular, the NIR persistent emission of mSiO2@ZCGO could be stimulated by soft X-ray, which is beneficial to long-term imaging in deep tissues. The optical penetration length of Yb3+ ions persistent luminescence was evaluated to be 2.8 mm. These results demonstrate the great promise of mSiO2@ZCGO for deep-tissue bio-imaging.

Synthesis and optical properties of a Y3(Al/Ga)5O12:Ce3+,Cr3+,Nd3+ persistent luminescence nanophosphor: a promising near-infrared-II nanoprobe for biological applications.

Persistent luminescence nanophosphors (PLNPs) emitting in the second near-infrared window (1000-1700 nm, NIR-II) are emerging as one promising class of in vivo bio-imaging agents due to their unique advantages including non-autofluorescence and low optical scattering in tissues. Currently, it remains a great challenge to synthesize nanosized lanthanide-doped inorganic NIR-II phosphors with a good persistent luminescence performance. Herein, we present a salt microemulsion method for synthesizing Ce3+, Cr3+, Nd3+ codoped Y3(Al/Ga)5O12 nanocrystals, which generate multi-wavelength persistent luminescence in the visible (∼508 nm, 5d1→ 4f of Ce3+), the first near-infrared window (∼890 nm, 4F3/2→4I9/2 of Nd3+) and NIR-II (∼1063 nm, 4F3/2→4I11/2 of Nd3+) regions. Under illumination of a 410 nm diode (3 W) for 10 min, the observed duration time of NIR-II persistent luminescence is as long as 60 min at room temperature. Moreover, the persistent luminescence can be excited efficiently by multiple excitation sources including a blue diode, white LEDs and an X-ray generator, which is crucial for deep tissue imaging applications. By comparing the penetration depth between NIR-I and NIR-II persistent luminescence through chicken breast, we prove that NIR-II photons exhibit a deeper optical penetration length (3.9 mm) than that of the NIR-I ones (2.5 mm). In addition, the NIR signals can still be detected 3 min after ceasing the excitation source by a small animal imaging system (InGaAs detector) when the thickness of the covering chicken breast is 20 mm. These results show great promise for Y3(Al/Ga)5O12:Ce3+,Cr3+,Nd3+ nanocrystals as a PLNP for bio-imaging applications with deep penetration depth and a high signal-to-noise ratio.

Near-infrared-triggered photon upconversion tuning in all-inorganic cesium lead halide perovskite quantum dots.

All-inorganic CsPbX3 (X = Cl, Br, and I) perovskite quantum dots (PeQDs) have shown great promise in optoelectronics and photovoltaics owing to their outstanding linear optical properties; however, nonlinear upconversion is limited by the small cross-section of multiphoton absorption, necessitating high power density excitation. Herein, we report a convenient and versatile strategy to fine tuning the upconversion luminescence in CsPbX3 PeQDs through sensitization by lanthanide-doped nanoparticles. Full-color emission with wavelengths beyond the availability of lanthanides is achieved through tailoring of the PeQDs bandgap, in parallel with the inherent high conversion efficiency of energy transfer upconversion under low power density excitation. Importantly, the luminescent lifetimes of the excitons can be enormously lengthened from the intrinsic nanosecond scale to milliseconds depending on the lifetimes of lanthanide ions. These findings provide a general approach to stimulate photon upconversion in PeQDs, thereby opening up a new avenue for exploring novel and versatile applications of PeQDs.

Cooperative and non-cooperative sensitization upconversion in lanthanide-doped LiYbF4 nanoparticles.

Lanthanide (Ln3+)-doped upconversion nanoparticles (UCNPs) have attracted tremendous interest owing to their potential bioapplications. However, the intrinsic photophysics responsible for upconversion (UC) especially the cooperative sensitization UC (CSU) in colloidal Ln3+-doped UCNPs has remained untouched so far. Herein, we report a unique strategy for the synthesis of high-quality LiYbF4:Ln3+ core-only and core/shell UCNPs with tunable particle sizes and shell thicknesses. Energy transfer UC from Er3+, Ho3+ and Tm3+ and CSU from Tb3+ were comprehensively surveyed under 980 nm excitation. Through surface passivation, we achieved efficient non-cooperative sensitization UC with absolute UC quantum yields (QYs) of 3.36%, 0.69% and 0.81% for Er3+, Ho3+ and Tm3+, respectively. Particularly, we for the first time quantitatively determined the CSU efficiency for Tb3+ with an absolute QY of 0.0085% under excitation at a power density of 70 W cm-2. By means of temperature-dependent steady-state and transient UC spectroscopy, we unraveled the dominant mechanisms of phonon-assisted cooperative energy transfer (T > 100 K) and sequential dimer ground-state absorption/excited-state absorption (T < 100 K) for the CSU process in LiYbF4:Tb3+ UCNPs.