Visible-to-Near-Infrared Mechanoluminescence in Bi-Activated Spinel Compounds for Multiple Information Anticounterfeiting.

Mechanoluminescence (ML) is the nonthermal luminescence generated in the process of force-to-light conversion, which has broad prospects in stress sensing, wearable devices, biomechanics, and multiple information anticounterfeiting. Multivalence emitter ions utilize their own self-reduction process to realize multiband ML without introducing another dopant, such as Eu3+/Eu2+, Sm3+/Sm2+, and Mn4+/Mn2+. However, self-reduction-induced ML in bismuth-activated materials has rarely been reported so far. In this work, a novel visible-to-near-infrared (vis-NIR) ML induced by the self-reduction of Bi3+ to Bi2+ in the spinel-type compound (MgGa2O4) is reported. The photoluminescence (PL) spectra, PL excitation (PLE) spectra, and PL lifetime curves demonstrate that Bi3+/Bi2+ ions are the main luminescence centers. Notably, the possible self-reduction model is proposed, where a magnesium vacancy (VMg″) is considered as the driving force for the self-reduction of Bi3+ to Bi2+. Furthermore, an oxygen vacancy (VO••) is confirmed by electron paramagnetic resonance (EPR) spectroscopy. Combined with thermoluminescence (TL) glow curves and ML spectra, a plausible trap-controlled ML mechanism is illustrated, where electron-hole (VO••/VMg″) pairs play a significant role in capturing electrons and holes. It is worth noting that the proof-of-concept dual-mode electronic signature application is implemented based on the flexible ML film, which improves the capabilities of signature anticounterfeiting for high-level security applications. Besides, multistimulus-responsive luminescence behaviors of the ML film are realized under the excitation of a 254 nm UV lamp, thermal disturbance, 980 nm laser, and mechanical stimuli. In general, this study provides new insights into designing vis-NIR ML materials toward wider application possibilities.

Transparent nanocrystal-in-glass composite fibers for multifunctional temperature and pressure sensing.

The pursuit of compact and integrated devices has stimulated a growing demand for multifunctional sensors with rapid and accurate responses to various physical parameters, either separately or simultaneously. Fluorescent fiber sensors have the advantages of robust stability, light weight, and compact geometry, enabling real-time and noninvasive signal detection by monitoring the fluorescence parameters. Despite substantial progress in fluorescence sensors, achieving multifunctional sensing in a single optical fiber remains challenging. To solve this problem, in this study, we present a bottom-up strategy to design and fabricate thermally drawn multifunctional fiber sensors by incorporating functional nanocrystals with temperature and pressure fluorescence responses into a transparent glass matrix. To generate the desired nanocrystal-in-glass composite (NGC) fiber, the fluorescent activators, incorporated nanocrystals, glassy core materials, and cladding matrix are rationally designed. Utilizing the fluorescence intensity ratio technique, a self-calibrated fiber sensor is demonstrated, with a bi-functional response to temperature and pressure. For temperature sensing, the NGC fiber exhibits temperature-dependent near-infrared emission at temperatures up to 573 K with a maximum absolute sensitivity of 0.019 K-1. A pressure-dependent upconversion emission is also realized in the visible spectral region, with a linear slope of -0.065. The successful demonstration of multifunctional NGC fiber sensors provides an efficient pathway for new paradigms of multifunctional sensors as well as a versatile strategy for future hybrid fibers with novel combinations of magnetic, optical, and mechanical properties.

Realizing Near Infrared Mechanoluminescence Switch in LAGO:Cr Based on Oxygen Vacancy.

Mechanoluminescence (ML) materials are featured with the characteristic of "force to light" in response to external stimuli, which have made great progress in artificial intelligence and optical sensing. However, how to effectively enable ML in the material is a daunting challenge. Here, a Lu3 Al2 Ga3 O12 :Cr3+ (LAGO: Cr3+ ) near infrared (NIR) ML material peaked at 706 nm is reported, which successfully realizes the key to unlock ML by the lattice-engineering strategy Ga3+ substitution for Al3+ to "grow" oxygen vacancy (Ov ) defects. Combined with thermoluminescence measurements, the observed ML is due to the formation of defect levels and the ML intensity is proportional to it. It is confirmed by X-ray photoelectron spectroscopy and electron paramagnetic resonance that such a process is dominated by Ov , which plays a crucial role in turning on ML in this compound. In addition, potential ML emissions from 4 T2 and 2 E level transitions are discussed from both experimental and theoretical aspects. This study reveals the mechanism of the change in ML behavior after cation substitution, and it may have important implications for the practical application of Ov defect-regulated turn-on of ML.

Near-Infrared Dual-Modal Sensing of Force and Temperature in Total Knee Replacement Using Mechanoluminescent Phosphor of Sr3Sn2O7: Nd, Yb.

Knee replacement surgery confronts challenges including patient dissatisfaction and the necessity for secondary procedures. A key requirement lies in dual-modal measurement of force and temperature of artificial joints during postoperative monitoring. Here, a novel non-toxic near-infrared (NIR) phosphor Sr3Sn2O7:Nd, Yb, is designed to realize the dual-modal measurement. The strategy is to entail phonon-assisted upconversion luminescence (UCL) and trap-controlled mechanoluminescence (ML) in a single phosphor well within the NIR biological transmission window. The phosphor is embedded in medical bone cement forming a smart joint in total knee replacements illustrated as a proof-of-concept. The sensing device can be charged in vitro by a commercial X-ray source with a safe dose rate for ML, and excited by a low power 980 nm laser for UCL. It attains impressive force and temperature sensing capabilities, exhibiting a force resolution of 0.5% per 10 N, force detection threshold of 15 N, and a relative temperature sensitive of up to 1.3% K-1 at 309 K. The stability against humidity and thermal shock together with the robustness of the device are attested. This work introduces a novel methodological paradigm, paving the way for innovative research to enhance the functionality of artificial tissues and joints in living organisms.

High-Pressure Near-Infrared Luminescence Studies of Fe3+-Activated LiGaO2.

A 0.25% iron (Fe3+)-doped LiGaO2 phosphor was synthesized by a high-temperature solid-state reaction method. The phosphor was characterized utilizing X-ray diffraction (XRD), scanning electron microscopy (SEM), high-pressure photoluminescence, and photoluminescence decay measurement techniques using diamond anvil cells (DACs). The powder X-ray analysis shows that the phosphor is a ß polymorph of LiGaO2 with an orthorhombic crystallographic structure at room temperature. The SEM result also confirms the presence of well-dispersed micro-rod-like structures throughout the sample. The photoluminescence studies in the near-infrared (NIR) range were performed at ambient, low-temperature, and high-pressure conditions. The synthesized phosphor exhibits a photoluminescence band around 746 nm related to the 4T1 → 6A1 transition with a 28% quantum efficiency at ambient conditions, which shifts toward longer wavelengths with the increase of pressure. The excitation spectra of Fe3+ are very well fitted with the Tanabe-Sugano crystal-field theory. The phosphor luminescence decays with a millisecond lifetime. The high-pressure application transforms the ß polymorph of LiGaO2 into a trigonal α structure at the pressure of about 3 GPa. Further increase of pressure quenches the Fe3+ luminescence due to the amorphization process of the material. The prepared phosphor exhibits also mechanoluminescence properties in the NIR spectral region.

Cation-defect-induced self-reduction towards efficient mechanoluminescence in Mn2+-activated perovskites.

Mechanoluminescent (ML) materials have shown promising prospects for various applications, e.g. in stress sensing, information anti-counterfeiting and bio stress imaging fields. However, the development of trap-controlled ML materials is still limited, because the trap formation mechanism is not always clear. Here, inspired by a defect-induced Mn4+ → Mn2+ self-reduction process in suitable host crystal structures, a cation vacancy model is creatively proposed to determine the potential trap-controlled ML mechanism. Combined with the theoretical prediction and experimental results, both the self-reduction process and ML mechanism are clarified in detail, where the contribution of and defects dominates the ML luminescent process. Electrons/holes are mainly captured by the anionic/cationic defects, followed by the combination of electrons and holes to transfer energy to the Mn2+ 3d states under mechanical stimuli. Based on the multi-mode luminescent features excited by X-ray, 980 nm laser and 254 nm UV lamp, together with the excellent persistent luminescence and ML, a potential application in advanced anti-counterfeiting is demonstrated. These results will deepen the understanding of the defect-controlled ML mechanism, and inspire more defect-engineering strategies to develop more high-performance ML phosphors for practical application.

Efficient and Broadband Emission in Dy3+-Doped Glass-Ceramic Fibers for Tunable Yellow Fiber Laser.

Yellow lasers are of great interest in biology, medicine and display technology. However, nonlinear emission of near-infrared lasers at yellow still presents particularly complex optical alignment to date. Here, to the best of our knowledge, we demonstrate the fabrication of a NaLa(WO4)2: Dy3+ glass-ceramic fiber (GCF) for the first time. More importantly, the emission band of the GCF, which is around 575 nm, has a wide full-width half maximum (FWHM) of 18~22 nm, which is remarkably larger than that of the Dy3+-doped YAG crystal (<7 nm). The precursor fiber (PF) was drawn using the molten core drawing (MCD) method. In particular, benefiting from the in situ nanocrystals fabricated in the amorphous fiber core after thermal treatment, the resultant glass-ceramic fiber exhibits a five-times enhancement of luminescence intensity around 575 nm, compared with the precursor fiber, while retaining its broadband emission. Overall, this work is anticipated to offer a high potential GCF with prominent bandwidth for the direct access of a tunable yellow laser.

Ratiometric mechanoluminescence in single Pr3+ -activated LiGa5 O8.

Mechanoluminescence (ML) materials have found potential applications in information storage, anti-counterfeiting, and stress sensing. Conventional stress sensing based on absolute ML intensity is prone to significant mistakes owing to the unpredictability of measurement surroundings. However, implementing a ratiometric ML sensing technique may considerably ameliorate this issue. In this study, a single activator-doped gallate material (LiGa5 O8 :Pr3+ ) is proposed to determine the relationship between the ML intensity and the change in local positional symmetry that occurs when the material is subjected to stress. The sensing reliability of the ML intensity ratio under different factors (Force; Content; Thickness and Materials) is systematically analyzed, where the factor that has the greatest effect on the proportional ML is the concentration, with the ML intensity asymmetry ratio decreasing from 1.868 to 1.300 varying concentration at constant stress. The colour-resolved visualization of stress sensing is further realized, which opens a new path for a ratiometric ML-based strategy to improve the reliability of stress sensing.

Anionic Regulation toward Bi3+ Selective Occupation for Full-Spectrum White Light Emission.

An activator's selective occupation of a host is of great significance for designing high-quality white light-emitting diode phosphors, while achieving a full-spectrum single-phase white light emission phosphor is challenging. In this study, a boron phosphate solid-solution Na2Y2(BO3)2-x(PO4)xO:0.005 Bi3+ (NYB2-xPxO:0.005 Bi3+) white phosphor was designed by selectively occupying Bi3+ activators in the mixed anionic groups. The substitutes of the anionic unit (BO3)3- by the (PO4)3- unit are supposed to force part of the Bi3+ ion to enter the Na lattice site, which produces an intense orange-red emission peaked at 590 nm. In parallel, spectral tuning from blue to white light and an internal quantum efficiency of 56.42% was obtained, and the thermal stabile luminescence intensity remains at 94.2% of the initial intensity after four heating-cooling cycles from 30 to 210 °C (luminescent intensity is 83.6% of room temperature (RT) at 150 °C, with excellent thermal stability and recovery performance). Finally, an excellent color rendering index (Ra = 90.8 and R9 = 85) was demonstrated for white light-emitting diode devices using only an NYB1.5P0.5O:0.005 Bi3+ phosphor and a near-ultraviolet (n-UV) 365 nm LED chip. This work delves into the different selective occupancy of Bi3+ ions and explores a new avenue for the design of phosphors for full-spectrum white light emission.

Interplay of defect levels and rare earth emission centers in multimode luminescent phosphors.

Multimode luminescence generally involves tunable photon emissions in response to various excitation or stimuli channels, which demonstrates high coding capacity and confidentiality abilities for anti-counterfeiting and encryption technologies. Integrating multimode luminescence into a single stable material is a promising strategy but remains a challenge. Here, we realize distinct long persistent luminescence, short-lived down/upconversion emissions in NaGdTi2O6:Pr3+, Er3+ phosphor by emloying interplay of defect levels and rare earth emission centers. The materials show intense colorful luminescence statically and dynamically, which responds to a wide spectrum ranging from X-ray to sunlight, thermal disturbance, and mechanical force, further allowing the emission colors manipulable in space and time dimensions. Experimental and theoretical approaches reveal that the Pr3+ ↔ Pr4+ valence change, oxygen vacancies and anti-site TiGd defects in this disordered structure contributes to the multimode luminescence. We present a facile and nondestructive demo whose emission color and fade intensity can be controlled via external manipulation, indicating promise in high-capacity information encryption applications.

Dual near infrared emission in Ag2Se quantum dots via Pb doping for broadband mini light-emitting diodes.

Dual emission almost covering the entire NIR-II region with the maximum full width at half maximum of 542 nm was achieved by doping small amounts of Pb ions into Ag2Se quantum dots, which to the best of our knowledge has not been realized for continuous tunable dual NIR emission in Ag-based QDs. The fabricated broadband NIR mini light-emitting diodes based on the Pb-doped Ag2Se QDs exhibit potential applications for highly sensitive and multispectral non-invasive imaging and NIR lighting.

Monitoring cardiovascular disease severity using near-infrared mechanoluminescent materials as a built-in indicator.

Artificial vascular grafts (AVGs) are widely used to treat cardiovascular diseases (CVDs). But none of the reported AVGs can also monitor the CVD severity. Because CVDs affect the blood pressure, we proposed to employ a force-sensing material that emits near-infrared (NIR) light upon force loading, a NIR mechanoluminescent (ML) material (CaZnOS:Nd3+), as an indicator in AVGs to tackle this challenge. Specifically, we used a polydimethylsiloxane AVG modified with this ML material, termed ML-AVG, to achieve the rapid and convenient monitoring of two CVD models (vascular occlusion and hypertension) in real time. The NIR ML material showed good blood and tissue compatibility without causing an inflammatory response. By implanting the ML-AVGs into the common carotid artery (CCA) of rats, we observed the NIR ML signals emitted from the AVGs by a thermal camera, a NIR spectrometer, and a NIR camera. The NIR ML signal was linearly correlated with the degree of vascular opening (in the vascular occlusion model) or the degree of hypertension (in the hypertension model). Our work suggests that NIR ML materials can monitor the severity of diseases with force or pressure as biomarkers.

Visible and Near-Infrared Emission in Ba3Sc4O9:Bi Phosphor: An Investigation on Bismuth Valence Modification.

Bismuth (Bi)-activated luminescence materials have attracted much attention for their tunable broad emissions ranging from a visible to near-infrared (NIR) region. However, it remains a challenge to regulate the Bi valence state and achieve NIR emission via a facile way. Here, we report the design and preparation of Ba3Sc4O9:Bi phosphors, which emit visible and NIR emissions simultaneously even prepared in the air condition. The self-reduction mechanism of Bi3+ species in Ba3Sc4O9 with a rigid crystal structure is illustrated based on the charge compensation model, and the coexistence of different Bi-active centers, Bi3+ for visible emission, while Bi+ and Bi0 for NIR emission, is confirmed by the spectroscopic data and X-ray photoelectron spectroscopy (XPS) analysis. The enhanced NIR emission was further achieved through controlled reducing treatment and the related mechanism has also been clarified. This work paves a new way to control bismuth valence and tune the emission of Bi-based luminescence materials for emerging photonics applications.

Near-infrared mechanoluminescence crystals: a review.

Due to the in situ, real-time, and non-destructive properties, mechanoluminescence (ML) crystals have been considered as intelligent stress sensors, which demonstrate potential applications such as in inner crack visualization, light source, and ultrasonic powder recording. Thereinto, it is highly expected that near-infrared (NIR) MLs can realize the visualization of inner biological stress because mechanically induced signals from them can penetrate biological tissues. However, such an energy conversion technique fails to work in biomechanical monitoring due to the limited advances of NIR ML materials. Based on those, some research groups have begun to focus on this field and initially realized this idea in vitro while related advances are still at the early stage. To advance this field, it is highly desirable to review recent advances in NIR ML crystals. In this review, to our knowledge, all the NIR ML crystals have been included in two main groups: oxysulfides and oxides. Besides, the present and emerging trends in investigation of such crystals were discussed. In all, the aim is to advance NIR ML crystals to more practical applications, especially for that of biomechanical visualization in vivo.

Recent Advances in Super Broad Infrared Luminescence Bismuth-Doped Crystals.

Bismuth (Bi)-doped materials are capable of exhibiting broadband near-infrared (NIR) luminescence in 1,000-1,700 nm; driven by the potential use in lasers and broadband optical amplifiers for modern fiber communication systems, Bi-activated NIR luminescencent glasses and related devices have attracted much attention. Compared with glass systems, Bi-doped crystals as gain media usually have more regular crystal structures to produce stronger NIR signals, and developing such materials is highly desirable. Regarding the recent advances in Bi-doped NIR crystals, here, for the first time, we summarized such crystals listed as two main categories of halogen and oxide compounds. Then, by comparing the substitution site, coordination environment, emission and excitation luminescence peaks, emitting center species, and decay times of these known Bibased NIR crystals, discussion on how to design Bi-doped NIR crystals is included. Finally, the key challenges and perspectives of Bi-doped NIR crystals are also presented. It is hoped that this review could offer inspiration for the further development of Bi-doped NIR luminescent crystals and exploit its potential applications.

Ultraviolet-A Persistent Luminescence of a Bi3+-Activated LiScGeO4 Material.

Long persistent phosphors (LPPs) with ultraviolet (UV) luminescence have great potential for application in the fields of biomedicine, environmental, and catalysis. However, it is currently limited by the design and development of remarkable UV LPPs with a suitable spectral region and an ultralong afterglow decay time. Herein, we develop a new type of Bi3+-activated LiScGeO4 LPP, which exhibits bright ultraviolet-A (UVA) persistent luminescence (PersL). Because of the existence of numerous stabilized effective traps, the as-synthesized phosphors can undergo an ultralong PersL decay time far longer than 12 h. The PersL properties, effective trap depths, distributions, and types, as well as the possible mechanism for the PersL behavior of LiScGeO4:Bi3+, are comprehensively surveyed utilizing PersL excitation spectra, PersL decay analyses, thermoluminescence experiments, and X-ray photoelectron spectroscopy. This work can cover the shortage of LPPs in the UV region and also can lay the foundation for the development of more excellent UV LPPs toward versatile novel applications.