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Visible light is a universal and user-friendly excitation source; however, its use to generate persistent luminescence (PersL) in materials remains a huge challenge. Herein, the concept of intermolecular charge transfer (xCT) is applied in typical host-guest molecular systems, which allows for a much lower energy requirement for charge separation, thus enabling efficient charging of near-infrared (NIR) PersL in organics by visible light (425-700 nm). Importantly, NIR PersL in organics occurs via the trapping of electrons from charge-transfer aggregates (CTAs) into constructed trap states with trap depths of 0.63-1.17 eV, followed by the detrapping of these electrons by thermal stimulation, resulting in a unique light-storage effect and long-lasting emission up to 4.6 h at room temperature. The xCT absorption range is modulated by changing the electron-donating ability of a series of acenaphtho[1,2-b]pyrazine-8,9-dicarbonitrile-based CTAs, and the organic PersL is tuned from 681 to 722 nm. This study on xCT interaction-induced NIR PersL in organic materials provides a major step forward in understanding the underlying luminescence mechanism of organic semiconductors and these findings are expected to promote their applications in optoelectronics, energy storage, and medical diagnosis.
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Mechanoluminescence (ML) sensing technologies open up new opportunities for intelligent sensors, self-powered displays and wearable devices. However, the emission efficiency of ML materials reported so far still fails to meet the growing application requirements due to the insufficiently understood mechano-to-photon conversion mechanism. Herein, we propose to quantify the ability of different phases to gain or lose electrons under friction (defined as triboelectric series), and reveal that the inorganic-organic interfacial triboelectricity is a key factor in determining the ML in inorganic-organic composites. A positive correlation between the difference in triboelectric series and the ML intensity is established in a series of composites, and a 20-fold increase in ML intensity is finally obtained by selecting an appropriate inorganic-organic combination. The interfacial triboelectricity-regulated ML is further demonstrated in multi-interface systems that include an inorganic phosphor-organic matrix and organic matrix-force applicator interfaces, and again confirmed by self-oxidization and reduction of emission centers under continuous mechanical stimulus. This work not only gives direct experimental evidences for the underlying mechanism of ML, but also provides guidelines for rationally designing high-efficiency ML materials.
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Proportionally converting the applied mechanical energy into photons by individual mechanoluminescent (ML) micrometer-sized particles opens a new way to develop intelligent electronic skins as it promises high-resolution stress distribution visualization and fast response. However, a big challenge for ML sensing technology is its low sensitivity in detecting stress. In this work, a novel stress distribution sensor with the detection sensitivity enhanced by two orders of magnitude is developed by combining a proposed near-distance ML imaging scheme with an improved mechano-to-photon convertor. The enhanced sensitivity is the main contributor to the realization of a maximum photon harvesting rate of ≈80% in the near-distance ML imaging scheme. The developed near-distance ML sensor shows a high sensitivity with a detection limit down to ≈kPa level, high spatial resolution of 254 dpi, and fast response with an interval of 3.3 ms, which allows for high-resolution and real-time visualization of complex mechanical actions such as irregular solid contacts or fluid impacts, and thus enables use in intelligent electronic skin, structural health monitoring, and human-computer interaction.
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Dispositivos Electrónicos Vestibles , Diagnóstico por Imagen , Humanos , FotonesRESUMEN
The discovery of X-ray-charged persistent luminescence (PersL) in fluoride nanoparticles enables these materials to emit photons without real-time excitation, which provides a great possibility for the development of new luminescent nanotechnologies. In this work, we developed NaLuF4:Mn nanoparticles with intense green PersL and functionalized surfaces and accordingly achieved time-gated imaging of latent fingerprints (LFPs) with Level 3 details. These surface-modified NaLuF4:Mn nanoparticles exhibited near-spherical morphology, long-lasting emission for several hours, appropriate trap depth distribution, and tight chemical bonding with amino acids from fingerprints, thus greatly improving the accuracy of LFP imaging in a variety of environments. The developed NaLuF4:Mn PersL nanoparticles are expected to find broad applications in the fields of LFP imaging and in vivo biological imaging.
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Luminiscencia , Nanopartículas , Fluoruros , FotonesRESUMEN
The first carbon dot (CD)-based organic long persistent luminescence (OLPL) system exhibiting more than 1 h of duration was developed. In contrast to the established OLPL systems, herein, the reported CDs-based system (named m-CDs@CA) can be facilely and effectively fabricated using a household microwave oven, and more impressively, its LPL can be observed under ambient conditions and even in aqueous media. XRD and TEM characterizations, afterglow decay, time-resolved spectroscopy, and ESR analysis were performed, showing the successful composition of CDs and CA, the formation of exciplexes and long-lived charged-separated states. Further studies suggest that the production of covalent bonds between CA and CDs plays pivotal roles in activating LPL and preventing its quenching from oxygen and water. To the best of our knowledge, this is a very rare example of an OLPL system that exhibits hour-level afterglow under ambient conditions. Finally, applications of m-CDs@CA in glow-in-the-dark paints for emergency signs and multicolored luminous pearls were preliminarily demonstrated. This work may provide new insights for the development of rare-earth-free and robust OLPL materials.
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NaYF4:Ln3+, due to its outstanding upconversion characteristics, has become one of the most important luminescent nanomaterials in biological imaging, optical information storage, and anticounterfeiting applications. However, the large specific surface area of NaYF4:Ln3+ nanoparticles generally leads to serious nonradiative transitions, which may greatly hinder the discovery of new optical functionality with promising applications. In this paper, we report that monodispersed nanoscale NaYF4:Ln3+, unexpectedly, can also be an excellent persistent luminescent (PersL) material. The NaYF4:Ln3+ nanoparticles with surface-passivated core-shell structures exhibit intense X-ray-charged PersL and narrow-band emissions tunable from 480 to 1060 nm. A mechanism for PersL in NaYF4:Ln3+ is proposed by means of thermoluminescence measurements and host-referred binding energy (HRBE) scheme, which suggests that some lanthanide ions (such as Tb) may also act as effective electron traps to achieve intense PersL. The uniform and spherical NaYF4:Ln3+ nanoparticles are dispersible in solvents, thus enabling many applications that are not accessible for traditional PersL phosphors. A new 3-dimensional (2 dimensions of planar space and 1 dimension of wavelength) optical information-storage application is demonstrated by inkjet-printing multicolor PersL nanoparticles. The multicolor persistent luminescence, as an emerging and promising emissive mode in NaYF4:Ln3+, will provide great opportunities for nanomaterials to be applied to a wider range of fields.
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The emergence of new applications, such as in artificial intelligence, the internet of things, and biotechnology, has driven the evolution of stress sensing technology. For these emerging applications, stretchability, remoteness, stress distribution, a multimodal nature, and biocompatibility are important performance characteristics of stress sensors. Mechanoluminescence (ML)-based stress sensing has attracted widespread attention because of its characteristics of remoteness and having a distributed response to mechanical stimuli as well as its great potential for stretchability, biocompatibility, and self-powering. In the past few decades, great progress has been made in the discovery of ML materials, analysis of mechanisms, design of devices, and exploration of applications. One can find that with this progress, the focus of ML research has shifted from the phenomenon in the earliest stage to materials and recently toward devices. At the present stage, while showing great prospects for advanced stress sensing applications, ML-based sensing still faces major challenges in material optimization, device design, and system integration.
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Stress sensing is the basis of human-machine interface, biomedical engineering, and mechanical structure detection systems. Stress sensing based on mechanoluminescence (ML) shows significant advantages of distributed detection and remote response to mechanical stimuli and is thus expected to be a key technology of next-generation tactile sensors and stress recorders. However, the instantaneous photon emission in ML materials generally requires real-time recording with a photodetector, thus limiting their application fields to real-time stress sensing. In this paper, we report a force-induced charge carrier storage (FICS) effect in deep-trap ML materials, which enables storage of the applied mechanical energy in deep traps and then release of the stored energy as photon emission under thermal stimulation. The FICS effect was confirmed in five ML materials with piezoelectric structures, efficient emission centres and deep trap distributions, and its mechanism was investigated through detailed spectroscopic characterizations. Furthermore, we demonstrated three applications of the FICS effect in electronic signature recording, falling point monitoring and vehicle collision recording, which exhibited outstanding advantages of distributed recording, long-term storage, and no need for a continuous power supply. The FICS effect reported in this paper provides not only a breakthrough for ML materials in the field of stress recording but also a new idea for developing mechanical energy storage and conversion systems.
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In this paper, we have designed long afterglow luminescent MgGeO3:Mn2+,Yb3+,Li+ (MGO) nanoparticles in the first (NIR-I) and second (NIR-II) biological windows. Yb3+ ions served not only as the trap center to enhance the NIR-I long afterglow emission of Mn2+ at 680 nm, but also as an emitting center to produce a NIR-II long afterglow emission at â¼1000 nm. Furthermore, we have found the addition of Li+ can greatly increase the NIR-II afterglow emission of Yb3+ and the optimal amount of Mn2+, Yb3+ and Li+ was found to be 0.1, 0.5 and 0.5 mol%, respectively. The MGO nanoparticles synthesized using sol-gel methods showed a uniform morphology with a diameter of 50-100 nm, which were suitable for applications in bioimaging. More importantly, we have found MGO nanoparticles can be effectively excited to produce long persistent NIR-I and II luminescence using soft X-rays, suggesting that low dosage soft X-rays can also serve as a more powerful and deep tissue excitation source to recharge MGO nanoparticles. Furthermore, the MGO nanoparticles can also be re-excited to produce photo-stimulated emission under the irradiation of 650 and 808 nm NIR lasers. The in vivo imaging results have shown that MGO nanoparticles modified with folic acid (FA) can effectively realize super long-term targeted in vivo imaging of inflammation with a high sensitivity via recharging using soft X-rays and NIR lasers, which can provide not only an accurate diagnosis of inflammation, but also long-term monitoring of possible changes in the focus of inflammation in real time.
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Luminiscencia , Nanopartículas , Iones , Radiografía , Rayos XRESUMEN
Red emitters based on CaAl12O19:Mn4+ have been attracting extensive attention due to their advantages of being rare-earth-free and chemically stable. However, their relatively low luminescence efficiencies will seriously hinder their application in light-emitting diodes (LEDs). In this regard, the promising red phosphors of CaAl12O19:Mn4+ were synthesized with enhanced luminous efficiency by introducing the coexisting phase of MgAl2O4. Importantly, an approximately 5 times enhancement of integrated intensity in the emission spectrum was observed for the phosphor with the coexisting phase compared to that with a single phase. Their crystal structures, morphologies and photoluminescence properties and the mechanism of improved luminescence were systematically investigated. Upon exciting them by using near-ultraviolet or blue LEDs, an efficient red emission was achieved with a maximum peak at â¼658 nm. In order to evaluate their potential application, a warm white LED and a plant growth LED were fabricated by using the prepared phosphors in combination with YAG:Ce3+ and InGaN-based blue chips.
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The use of gold nanoparticles as radiosensitizers is an effective way to boost the killing efficacy of radiotherapy while drastically limiting the received dose and reducing the possible damage to normal tissues. Herein, we designed aggregation-induced emission gold clustoluminogens (AIE-Au) to achieve efficient low-dose X-ray-induced photodynamic therapy (X-PDT) with negligible side effects. The aggregates of glutathione-protected gold clusters (GCs) assembled through a cationic polymer enhanced the X-ray-excited luminescence by 5.2-fold. Under low-dose X-ray irradiation, AIE-Au strongly absorbed X-rays and efficiently generated hydroxyl radicals, which enhanced the radiotherapy effect. Additionally, X-ray-induced luminescence excited the conjugated photosensitizers, resulting in a PDT effect. The inâ vitro and inâ vivo experiments demonstrated that AIE-Au effectively triggered the generation of reactive oxygen species with an order-of-magnitude reduction in the X-ray dose, enabling highly effective cancer treatment.
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Oro/química , Neoplasias/radioterapia , Fotoquimioterapia/métodos , Fármacos Sensibilizantes a Radiaciones/química , Animales , Radical Hidroxilo , Luminiscencia , Ratones , Ratones Endogámicos BALB C , Nanopartículas , Fármacos Fotosensibilizantes , Dosis de Radiación , Rayos X , Ensayos Antitumor por Modelo de XenoinjertoRESUMEN
X-ray-induced photodynamic therapy (X-PDT) combines both the advantages of radiotherapy (RT) and PDT, and has considerable potential applications in clinical deep-penetrating cancer therapy. However, it is still a major challenge to prepare monodisperse nanoscintillators with uniform size and high light yield. In this study, a general and rapid synthesis method is presented that can achieve large-scale preparation of monodisperse and uniform silicate nanoscintillators. By simply adjusting the metal dopants, silicate nanoscintillators with controllable size and X-ray-excited optical luminescence (450-900 nm) are synthesized by employing a general ion-incorporated silica-templating method. To make full use of external radiation, the silicate nanoscintillators are conjugated with photosensitizer rose bengal and arginylglycylaspartic acid (RGD) peptide, making them intrinsically dual-modal targeted imaging probes. Both in vitro and in vivo experiments demonstrate that the silicate nanosensitizers can accumulate effectively in tumors and achieve significant inhibitory effect on tumor progression under low-dose X-ray irradiation, while minimally affecting normal tissues. The insights gained in this study may provide an attractive route to synthesize nanosensitizers to overcome some of the limitations of RT and PDT in cancer treatment.
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Nanopartículas/química , Fotoquimioterapia/métodos , Fármacos Fotosensibilizantes/síntesis química , Silicatos/química , Animales , Línea Celular Tumoral , Supervivencia Celular/efectos de los fármacos , Colorantes Fluorescentes/química , Xenoinjertos , Humanos , Ratones , Ratones Endogámicos BALB C , Oligopéptidos/química , Imagen Óptica , Permeabilidad , Fármacos Fotosensibilizantes/administración & dosificación , Rosa Bengala/química , Rayos XRESUMEN
Carbon dots (CDs) with tunable emission colors and multiple emission modes are highly desirable in advanced optical anti-counterfeiting. Some pioneering efforts to trigger additional long-lived emission modes, nevertheless, did not perfectly solve the issue of printability and color-tunability in practical applications. Herein, we developed an encapsulating-dissolving-recrystallization route for the synthesis of CD-based anti-counterfeiting inks, and accordingly realized blue, green, and red full-color afterglow emissions from these CD-based inks when printed on paper. The printed inks simultaneously possessed triple emission modes including fluorescence (FL), delayed fluorescence (DF), and room-temperature phosphorescence (RTP), among which the long-lived emissions (DF and RTP) could be selectively activated by using different excitation wavelengths. We believe that the proposed synthetic route in this work may promote the development of multicolor-encoded and multiple-mode-integrated optical anti-counterfeiting systems, and will expand the application of CD-based materials to the fields of sensing, photodynamic therapy and bio-imaging.
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Multifunctional theranostic nanoplatforms greatly improve the accuracy and effectiveness in tumor treatments. Much effort has been made in developing advanced optical imaging-based tumor theranostic nanoplatforms. However, autofluorescence and irradiation damage of the conventional fluorescence imaging technologies as well as unsatisfied curative effects of the nanoplatforms remain great challenges against their wide applications. Herein, we constructed a novel core-shell multifunctional nanoplatform, that is, chromium-doped zinc gallogermanate (ZGGO) near-infrared (NIR) persistent luminescent nanoparticles (PLNPs) as a core and zeolitic imidazolate framework-8 (ZIF-8) as a shell (namely ZGGO@ZIF-8). The ZGGO@ZIF-8 nanoplatform possessed dual functionalities of the autofluorescence-free NIR PersL imaging as well as the pH-responsive drug delivery, thus it has high potential in tumor theranostics. Notably, the loading content of doxorubicin (DOX) in ZGGO@ZIF-8 (LC = 93.2%) was quite high, and the drug release of DOX-loaded ZGGO@ZIF-8 was accelerated in an acidic microenvironment such as tumor cells. The ZGGO@ZIF-8 opens up a new material system in the combination of PLNPs with metal-organic frameworks and may offer new opportunities for the development of advanced multifunctional nanoplatforms for tumor theranostics, chemical sensing, and optical information storage.
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Doxorrubicina , Estructuras Metalorgánicas , Nanopartículas , Neoplasias , Zeolitas , Cromo/química , Cromo/farmacocinética , Cromo/farmacología , Preparaciones de Acción Retardada/química , Preparaciones de Acción Retardada/farmacocinética , Preparaciones de Acción Retardada/farmacología , Doxorrubicina/química , Doxorrubicina/farmacocinética , Doxorrubicina/farmacología , Humanos , Concentración de Iones de Hidrógeno , Células MCF-7 , Estructuras Metalorgánicas/química , Estructuras Metalorgánicas/farmacocinética , Estructuras Metalorgánicas/farmacología , Nanopartículas/química , Nanopartículas/uso terapéutico , Neoplasias/tratamiento farmacológico , Neoplasias/metabolismo , Neoplasias/patología , Zeolitas/química , Zeolitas/farmacocinética , Zeolitas/farmacología , Zinc/química , Zinc/farmacocinética , Zinc/farmacologíaRESUMEN
Deep-trap persistent luminescent materials, due to their exceptional ability of energy storage and controllable photon release under external stimulation, have attracted considerable attention in the field of optical information storage. Currently, the lack of suitable materials is still the bottleneck that restrains their practical applications. Herein, we successfully synthesized a series of deep-trap persistent luminescent materials Y3Al5- xGa xO12:Ce3+,V3+ ( x = 0-3) with a garnet structure and developed novel phosphor-in-glass (PiG) films containing these phosphors. The synthesized PiG films exhibited sufficiently deep traps, narrow trap depth distributions, high trap density, high quantum efficiency, and excellent chemical stability, which solved the problem of chemical stability at high temperatures in the reported phosphor-in-silicone films. Moreover, the trap depth in the phosphors and PiG films could be tailored from 1.2 to 1.6 eV, thanks to the bandgap engineering effect, and the emission color was simultaneously changed from green to yellow due to the variation of crystal field strength. Image information was recorded on the PiG films by using a 450 nm blue-light laser in a laser direct writing mode and the recorded information was retrieved under high-temperature thermal stimulation or photostimulation. The Y3Al5- xGa xO12:Ce3+,V3+ PiG films as presented in this work are very promising in the applications of multidimensional and rewritable optical information storage.
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Luminescent metal-organic frameworks (MOFs) (typically dye-encapsulated MOFs) are considered as one kind of interesting downconversion materials for white-light-emitting diodes (LEDs), but their quantum efficiency (QE) is not sufficient and thus needs to be significantly enhanced for practical applications. In this study, we successfully synthesized a series of Rh@bio-MOF-1 (Rh = rhodamine) with an internal QE as high as â¼79% via a solvothermal reaction followed by cation exchanges. The high efficiency of the Rh@bio-MOF-1 composites was attributable to the high intrinsic luminescent efficiency of the selected Rh dyes, the confinement effect in the bio-MOF-1 host, and the uniform particle morphology. The emission maximum could be continuously tuned from 550 to 610 nm by controlling the species and concentration of encapsulated dye molecules, showing great color tunability of the dye-encapsulated MOFs. The emission lifetime of â¼7 ns was 1 or 2 magnitude orders shorter than that of Ce3+- or Eu2+-doped inorganic phosphors, allowing for visible light communication (VLC). White LEDs, fabricated by using the synthesized Rh@bio-MOF-1 composite and inorganic phosphors of green (Ba,Sr)2SiO4:Eu2+ and red CaAlSiN3:Eu2+, exhibited a high color rendering index of 80-94, a luminous efficacy of 94-156 lm/W, and an excellent stability in color point against drive current. The Rh@bio-MOF-1 composites with tunable colors, short emission lifetime, and high QE are expected to be used for smart white LEDs with multifunctions of both lighting and VLC.
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Deep-trap persistent luminescence materials exhibit unique properties of energy storage and controllable photon release under additional stimulation, allowing for both wavelength and intensity multiplexing to realize high-capacity storage in the next-generation information storage system. However, the lack of suitable persistent luminescence materials with deep traps is the bottleneck of such storage technologies. In this study, we successfully developed a series of novel deep-trap persistent luminescence materials in the Ln2+/Ln3+-doped SrSi2O2N2 system (Ln2+ = Yb, Eu; Ln3+ = Dy, Ho, Er) by applying the strategy of trap depth engineering. Interestingly, the trap depth can be tailored by selecting different codopants, and it monotonically increases from 0.90 to 1.18 eV in the order of Er, Ho, and Dy. This is well explained by the energy levels indicated in the host-referred binding energy scheme. The orange-red-emitting SrSi2O2N2:Yb,Dy and green-emitting SrSi2O2N2:Eu,Dy phosphors are demonstrated to be good candidates of information storage materials, which are attributed to their deep traps, narrow thermoluminescence glow bands, high emission efficiency, and excellent chemical stability. This work not only validates the suitability of deep-trap persistent luminescence materials in the information storage applications, but also broadens the avenue to explore such kinds of new materials for applications in anticounterfeiting and advanced displays.
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Long-lived luminescent metal-organic frameworks (MOFs) have attracted much attention due to their structural tunability and potential applications in sensing, biological imaging, security systems, and logical gates. Currently, the long-lived luminescence emission of such inorganic-organic hybrids is dominantly confined to short-wavelength regions. The long-wavelength long-lived luminescence emission, however, has been rarely reported for MOFs. In this work, a series of structurally stable long-wavelength long-lived luminescent MOFs have been successfully synthesized by encapsulating different dyes into the green phosphorescent MOFs Cd(m-BDC)(BIM). The multicolor long-wavelength long-lived luminescence emissions (ranging from green to red) in dye-encapsulated MOFs are achieved by the MOF-to-dye phosphorescence energy transfer. Furthermore, the promising optical properties of these novel long-lived luminescent MOFs allow them to be used as ink pads for advanced anticounterfeiting stamps. Therefore, this work not only offers a facile way to develop new types of multicolor long-lived luminescent materials but also provides a reference for the development of advanced long-lived luminescent anticounterfeiting materials.
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We investigated the effect of trivalent lanthanide substitution on a novel oxynitride persistent phosphor SrSi2AlO2N3:Eu2+,Ln3+, which shows green persistent luminescence for more than 2 h. First, an energy level diagram by using the host-referred binding energy (HRBE) scheme was constructed. The location of the energy levels of all divalent and trivalent lanthanides referred to the energy band of the host SrSi2AlO2N3 was estimated. Then, thermoluminescence (TL) measurements in the target persistent phosphors were performed to obtain direct experimental results on the trap depth. We found that the trap levels based on the TL measurements coincided well with the 4f ground states of divalent lanthanide codopants in SrSi2AlO2N3:Eu2+,Ln3+. The result strongly suggests the effective traps for persistent luminescence in SrSi2AlO2N3:Eu2+,Ln3+ could be due to the aliovalent substitution of Ln3+ for Sr2+, which can be controlled by selecting suitable codopant Ln3+. The work shows the HRBE scheme may offer a way to understand the nature of defects in the persistent phosphor as well as a possible guideline to design new persistent phosphors with required trap depths.
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We demonstrated an effective way to broaden the bandwidth of near-infrared (NIR) emission from Bi/Ni codoped 58SiO2â21ZnO-13Al2âO3â5TiO2â3Ga2O3 glass through nanocrystallization. The nanocrystallized glass shows ultra-wide NIR luminescence with a full width at half maximum (FWHM) of 350 nm and long lifetime up to 476 µs. The observed broadband NIR emission, attributed to energy transfer suppression between Ni and Bi active centers, was realized by a separation process with Ni²âº ions selectively incorporated into nanocrystals. This bandwidth engineering through nanocrystallization inside glass suggests a promising approach for enhancement of glass functionality and construction of broadband light sources.