Tuning the luminescence properties of blue and far-red dual emitting Gd2MgTiO6: Bi3+, Cr3+ phosphor for LED plant lamp

Blue and far-red light play a key role in plant growth, so it is necessary to develop blue and far-red dual emitting phosphors. However, the match between phosphors and plant pigments is not satisfactory. In this work, we synthesized a series of blue and far-red dual emission Gd₂MgTiO₆: Bi³⁺, Cr³⁺ (GMTO: Bi³⁺, Cr³⁺) phosphors and discussed the luminescence performance. The blue emission at 430 nm is ascribed to ³P₁ → ¹S₀ transition of Bi³⁺ and the far-red emission is ascribed to ⁴T₂ → ⁴A₂ and ²E → ⁴A₂ transitions of Cr³⁺. Notably, because of the energy competition between Cr³⁺ ions and host materials, the luminescence tuning realized with the content of Cr³⁺ doping. In addition, an energy-transfer performance occurred from Bi³⁺ ions to Cr³⁺ ions and the photoluminescence intensity of Cr³⁺ can be enhanced by Bi³⁺. The pc-LEDs devices were synthesized by GMTO: Bi³⁺, Cr³⁺ phosphor, and ultraviolet (UV) chips. Finally, the emission of GMTO: Bi³⁺, Cr³⁺ phosphor matched well with the absorption spectra of plant pigments which indicated the potential applications in LED plant lamp.     

The ultra-wideband near-infrared luminescence properties and applications of K2SrGe8O18:Cr3+ phosphor

The near-infrared (NIR) light sources are fascinating in real-time nondestructive examination applications. Given that chemical bonds in organic substances (such as C–H, O–H and N–H) have extensive absorption and reflection of light in the NIR region, the emission spectrum of the NIR light sources should be as broad as possible. In this work, ultra-wideband K₂SrGe₈O₁₈ (KSGO):Cr³⁺ NIR-emitting phosphors with a 650–1200 nm emission span are developed. Structural analysis combined with electron paramagnetic resonance (EPR), photoluminescence (PL) spectra, time-resolved spectrum (TRES) and temperature-dependent PL spectra confirm that the super broadband emission with full width at half-maximum (FWHM) of 214 nm originates from the double Cr³⁺ luminescence centers occupying different [GeO₆] octahedra. Li⁺ ion as charge compensator is introduced to balance the negative charge induced by the un-equivalent replacement of Cr³⁺ for Ge⁴⁺, and the PL intensity and thermal stability are greatly enhanced. The NIR phosphor-converted luminescent diodes (pc-LEDs) prepared by combining optimized KSGO:0.10Cr³⁺, 0.07Li⁺ samples with 460 nm LED chips demonstrate their application in night vision. The measured absorption spectra of hemoglobin, water, ethyl alcohol and peanut oil illuminated by the as-prepared KSGO:0.10Cr³⁺, 0.07Li⁺ phosphors indicate nondestructive analysis in the areas of food safety.     

Luminescent properties and LED Application of Broadband Near-Infrared Emitting NaInGe2O6: Cr3+ phosphors

A NIR-emitting Cr³⁺-activated phosphors (NaInGe₂O₆: Cr³⁺) covering whole NIR-I region (700–1200 nm) were successfully designed and prepared via solid-state reaction. XRD and Rietveld refinement verified that the octahedral In³⁺ site is the preferred site of Cr³⁺ substitution in NaInGe₂O₆ structure. The synthesized NaInGe₂O₆: Cr³⁺ phosphors exhibit two strong absorption bands at 480 and 700 nm, and show a mountain-like single-band emission at 900 nm with FWHM = 175 nm. The crystal field parameters are calculated using steady-state spectral data, in which a low Dq/B value of 1.89 is obtained and results in this broadband NIR emission. NaInGe₂O₆: Cr³⁺ exhibits good emission thermal stability, i.e. 55 % of room temperature intensity at 373 K. Besides, an efficient NIR pc-LED is fabricated and shows NIR output of 25.2 mW@120 mA. This broadband NaInGe₂O₆: Cr³⁺ NIR phosphor could be merged into pc-LED package for hand-held spectrometers, security cameras and vivo biomarkers.     

Cr3+‐activated Li5Zn8Al5Ge9O36: A near‐infrared long‐afterglow phosphor

Near‐infrared long‐afterglow (LAG) materials have attracted considerable attention owing to their high potential for in vivo imaging applications. Here, we present a series of near‐infrared LAG phosphors Li₅Zn₈Al_5?xGe₉O₃₆:xCr³⁺ (LZAG:Cr³⁺), which were synthesized using a solid‐state reaction method. The pure LZAG host exhibits blue photoluminescence and LAG emission. We investigated the effect of the zinc vacancy contents on the photoluminescence and LAG performance by adjusting the zinc content and introducing Ga³⁺ ions to substitute the Zn²⁺ sites in LZAG host. When Cr³⁺ ions were introduced into the LZAG host, LZAG:Cr³⁺ produced a strong, broad blue emission band centered at 456 nm and a near‐infrared emission band at 700 nm caused by the ²E → ⁴A₂ transition of Cr³⁺. The energy transfer processes from the LZAG host to Cr³⁺ were identified in the photoluminescence and LAG process. After irradiation at 258 nm for 10 minutes, the LAG emission of LZAG:0.008Cr³⁺ can last nearly 2.5 hours. Moreover, the LAG intensity and duration of LZAG: 0.008Cr³⁺ were significantly improved by introducing a small dose of Ga³⁺ ions. Finally, the traps and mechanism of LAG in LZAG, LZAG:Ga³⁺, and LZAG:Cr³⁺ were discussed in detail.     

Far-red-emitting YAl3(BO3)4:Cr3+ phosphors with excellent thermal stability and high luminescent yield for plant growth LEDs

Phosphors-converted LEDs (pc-LEDs) are excellent artificial light sources for indoor plant cultivation, in which the far-red-emitting component (700−780 nm) plays an important role in regulating the photomorphogenesis of plants. Accordingly, highly efficient and thermally stable far-red-emitting phosphors are indispensable for developing high-performance plant cultivation pc-LEDs. Herein, far-red-emitting YAl₃(BO₃)₄:Cr³⁺ (YAB:Cr³⁺) phosphors were synthesized by solid-state reaction, and their photoluminescence characteristics, thermal quenching, quantum yield (QY), and application in pc-LEDs were systematically investigated. The YAB:Cr³⁺ phosphor has an intense broadband absorption to the blue light, simultaneously exhibiting the sharp-line ²E emission and the broadband ⁴ T₂ emission of Cr³⁺ with a QY of ~86.7%. The far-red broadband emissions of YAB:Cr³⁺ centered at ~735 nm show a high resemblance to the active-state (P_FR) absorption of plant phytochrome. Moreover, the YAB:Cr³⁺ phosphor shows the thermally enhanced luminescence at temperatures of 303−393 K and the near-zero thermal quenching up to 423 K. The anomalous thermal enhancement is attributed to the temperature-dependent repopulation between ²E and ⁴ T₂ states. Finally, a pc-LED device was fabricated with the YAB:Cr³⁺ phosphor and blue chip, exhibiting the light out power of ~50.6 mW and energy conversion efficiency of ~17.4% at 100 mA drive current, respectively. The exceptional PL features including suitable excitation/emission wavelengths, suppressed thermal quenching and high QY make YAB:Cr³⁺ phosphors very promising for applications in plant growth pc-LEDs.     

Efficient near-infrared pyroxene phosphor LiInGe2O6:Cr3+ for NIR spectroscopy application

Broadband near-infrared phosphors are essential to realize nondestructive analysis in food industry and biomedical areas. Efficient long-wavelength (>830 nm) phosphors are strongly desired for practical applications. Herein, we demonstrate an efficient broadband NIR phosphor LiInGe₂O₆:Cr³⁺, which exhibits a broad NIR emission peaking at ~880 nm with a full width at half maximum of 172 nm upon 460 nm excitation. The internal/external quantum efficiencies of LiInGe₂O₆:Cr³⁺ are measured to be 81.2% and 39.8%, respectively. The absorption of the phosphor matches well with commercial blue LEDs. Using the fabricated phosphor converted LED illuminating human palm, distribution of blood vessels can be clearly recognized under a NIR camera. These results indicate that LiInGe₂O₆:Cr³⁺ is a promising candidate to be used in future non-destructive biological applications.     

The co-optimization of efficiency and emission bandwidth in GSAGG:Cr3+ NIR ceramic phosphors

The NIR phosphor-converted light-emitting diode (NIR pc-LED) is a new near-infrared light source that has been widely studied. Among various NIR phosphors, Cr³⁺ doped gadolinium aluminum gallium garnet (GAGG:Cr³⁺) ceramic phosphor has shown great potential due to its ultra-high efficiency and thermal stability. Despite its capabilities, its detection range may be limited due to a relatively narrow emission bandwidth. To make the GAGG:Cr³⁺ ceramic phosphors achieve both high efficiency and broadband emission, a series of Gd₃Al_2-x-ySc_xGa₃O₁₂:yCr³⁺ (GASGG:Cr³⁺) ceramic phosphors were prepared. Thanks to the decrease of crystal field strength with the doping of Sc³⁺, the full width at half maximum (FWHM) of GASGG:Cr³⁺ ceramic phosphors were extended from 84 nm to 117 nm, and the emission peak exhibited a red-shift of 46 nm. Meanwhile, it still retained extremely high external quantum efficiency (EQE = 47%) and excellent thermal stability (90.7%@150 °C). Then, a NIR pc-LED prototype device was fabricated by combining GASGG:Cr³⁺ ceramic phosphor with a blue LED chip. The NIR light output power and the photoelectric conversion efficiency of this device achieved 646 mW and 19.2%, respectively. Finally, the application effect in night vision and venography of this prototype device was demonstrated.     

Luminescence of MgAl2O4 and ZnAl2O4 spinel ceramics containing some 3d ions

The luminescence properties of ceramic phosphors based on two spinel hosts MgAl₂O₄ and ZnAl₂O₄ doped with manganese ions have been studied. It has been found that the spectral properties of these phosphors can be strongly varied by changing synthesis conditions. Both types of doped ceramic spinel can serve as efficient Mn²⁺ green-emitting phosphors having peak emissions at 525 and 510 nm, respectively. Mn-doped MgAl₂O₄ spinel can also be prepared as an efficient Mn⁴⁺ red-emitting phosphor having peak emission at ~651 nm by using specific temperatures of heat treatment in air. It has also been shown that the conversion of Mn²⁺ to Mn⁴⁺ and viсe versa, as well as the coexistence of Mn²⁺ green and Mn⁴⁺ red emissions, can be accomplished by properly chosen annealing conditions of the same initially synthesized MgAl₂O₄:Mn sample. Manganese doped MgAl₂O₄ spinel with an optimal intensity ratio of green and red emissions can be a promising single-phase bicolor phosphor suitable for the development of warm white phosphor-converted LED lamps. On the other hand, it has been determined that perfectly normal ZnAl₂O₄ spinel cannot be doped with Mn⁴⁺ ions in contrast to partially inverse MgAl₂O₄ spinel. However, ZnAl₂O₄ samples unintentionally doped with impurity Cr³⁺ ions show emission spectra in the far-red region with well pronounced R, N and vibronic lines of Cr³⁺ luminescence due to the perfect normal spinel structure of synthesized ZnAl₂O₄ ceramics. Also, by partially substituting Al³⁺ cations for Mg²⁺ in ZnAl₂O₄ there is an opportunity to obtain Mn⁴⁺ doped or Mn⁴⁺/Cr³⁺ codoped far-red emitting phosphors which can be suitable for indoor plant growth lighting sources.     

Ultrawide near-infrared SrHfO3:Cr3+ phosphor with dual emission bands

Near-infrared phosphor-converted light-emitting diodes (NIR-pc-LEDs) are superior to traditional NIR-LEDs in spectral modulation, volume, and cost, and their optoelectronic properties are dominantly controlled by the NIR phosphors, which thus boosts the search for high efficiency and broadband NIR phosphors. In this work, we attempt to realize ultra-broadband NIR phosphors by doping Cr³⁺ in self-emitting SrHfO₃ with a weak crystal field. Dual emission bands centered at 770 (host) and 1000 nm (Cr³⁺) are observed, leading to a wide spectral range of 700–1400 nm. The Cr³⁺ ions enter the HfO₆ octahedron and thus produce an NIR emission with a full width at half maximum of 190 nm and an internal quantum efficiency of 24% under 460 nm excitation. A prototype NIR-pc-LED surface light is demonstrated for machine vision by using NIR-pc-LEDs that combine the blue LED with SrHfO₃:Cr. The work paves an avenue for designing super-broadband NIR phosphors by doping Cr³⁺ or other ions into hosts with self-trapped exciton emission (e.g., halide perovskites).     

Low-temperature microwave synthesis and luminescence properties of far-red emission ZnGa2O4:Cr3+ phosphor for plant cultivation

In this work, microwave (MW) sintering method is employed to synthesize far-red (FR) emission ZnGa₂O₄:Cr³⁺ phosphor at a lower sintering temperature (900 °C), comparing with the conventional high temperature solid-state sintering (SS) method. Micrometer-size phosphor particles with smooth morphology are obtained due to the MW-induced small temperature gradient between the constituent particles upon the local dielectric volumetric heating. The MW sintering ZnGa₂O₄:Cr³⁺ phosphor exhibited excitable properties at the wavelengths of 260 nm, 410 nm and 550 nm, and the intensity of photoluminescence excitation (PLE) at 260 nm showed a dramatic enhancement, which is 2–3 times higher than that of SS sintering sample due to MW “non-thermal effect” in reducing the defect amount in the ZnGa₂O₄ host latices. These results together with decay time, thermal quenching and color coordinate evaluations showed that synthesis of FR emission ZnGa₂O₄:Cr³⁺ by MW-sintering method has advantages of high efficiency, energy saving and least environmental threats.     

Li2ZnTi3O8@α-Fe2O3 composite anode material for Li-ion batteries

Li₂ZnTi₃O₈@α-Fe₂O₃ composites have been successfully prepared by a facile hydrothermal process. Li₂ZnTi₃O₈/α-Fe₂O₃ composites show similar irregular spherical morphologies like Li₂ZnTi₃O₈ and relatively smaller particle sizes than pristine Li₂ZnTi₃O₈. Among all Li₂ZnTi₃O₈/α-Fe₂O₃ composites, Li₂ZnTi₃O₈/α-Fe₂O₃ composite (5 wt%) exhibits the best electrochemical properties. Li₂ZnTi₃O₈/α-Fe₂O₃ composite (5 wt%) delivers a reversible charge capacity of 184.8 mAh g^?1 even at 1000 mA g^?1 after 500 cycles, while pristine Li₂ZnTi₃O₈ only delivers a reversible charge capacity of 110.7 mAh g^?1. The strong covalent bonds between Li₂ZnTi₃O₈ and α-Fe₂O₃ will be formed, which is beneficial for the reduction of interfacial energy and thus helpful for the stabilization of the composite. Because of the special synergistic effect of the multi-phase interface, Li₂ZnTi₃O₈/α-Fe₂O₃ composites not only possess the advantages of single components but also show novel and attractive performances, such as the enhanced ionic conductivity, reduced interfacial charge transfer impedance, improved migration rate of lithium ions, and the enhancement of the rate performance and reversible capacity. The as-prepared Li₂ZnTi₃O₈/α-Fe₂O₃ composites reveal important potentials as anode materials for next-generation rechargeable Li-ion batteries, and this work also offers an effective strategy to design high performance lithium storage materials for advanced lithium-ion batteries.     

Red,green and blue-violet emission coexistence in white-light-emitting Ca3SiO4Cl2:Bi3+, Li+, Eu2+, Eu3+ phosphor

A series of emission-tunable Ca₃SiO₄Cl₂:Bi³⁺, Li⁺, Euⁿ⁺(n =2, 3) (CSC:Bi³⁺, Li⁺, Euⁿ⁺) phosphors have been synthesized via sol-gel method. The X-ray diffraction results indicate that the as-synthesized phosphors crystallize in a low temperature phase with the space group of P21/c. Energy transfer from Bi³⁺ to Eu³⁺/Eu²⁺ exists in CSC:Bi³⁺, Li⁺, Euⁿ⁺ phosphors. Under the excitation of 327 or 365 nm, the Ca_2.98−ySiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, yEuⁿ⁺(y=0.0001–0.002) phosphors show an intense green emission band around 505 nm, while under the excitation of 264 nm, three emission bands centered around 396 nm (Bi³⁺), 505 nm (Eu²⁺) and 614 nm (Eu³⁺) are observed and tunable colors from blue-violet to green or white are achieved in these phosphors by varying the content of Eu. White-light emission with the color coordinate (0.312, 0.328) is obtained in Ca_2.978SiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, 0.002Euⁿ⁺(n =2, 3). Based on these results, the as-prepared CSC:Bi³⁺, Li⁺, Eu²⁺, Eu³⁺ phosphors can act as color-tunable and single-phase white emission phosphors for potential applications in UV-excited white LEDs.     

Up-conversion luminescence and temperature-sensing properties of Li+, K+ doped Na2Zn3Si2O8: Er3+ phosphors

In this work we detail the preparation of new luminescent Li⁺ and K⁺ doped Na₂Zn₃Si₂O₈: Er³⁺ up-conversion phosphors using the high-temperature solid-phase method. We investigate the phosphors phase structure, elemental distribution, up-conversion luminescence characteristics and temperature sensing properties. Our fabricated samples were found to be homogeneous and when excited using 980 nm light, they emitted wavelengths in the green and red visible wavelength bands, which correspond to two major emission bands of Er³⁺. Doping with Li⁺ and K⁺ increased the luminescence intensity of the Na₂Zn₃Si₂O₈: Er³⁺ phosphor at 661 nm by 36 and 21 times respectively. The highest relative temperature sensitivity (Sa) of the fabricated phosphor reached a value of 19.69% K^?1 and the highest absolute temperature sensitivity (Sr) reached 1.20% K^?1. These values are superior to other materials which utilize up-conversion by Er³⁺ ions as a tool for temperature sensing. We anticipate that these new phosphors will find significant application as components in optical temperature measurement systems.     

Promoting the Li storage performances of Li2ZnTi3O8@Na2WO4 composite anode for Li-ion battery

In this work, a reasonable strategy for the construction of Li₂ZnTi₃O₈@Na₂WO₄ composite was employed to promote the Li storage performances of Li₂ZnTi₃O₈. The Li₂ZnTi₃O₈@Na₂WO₄ composites (5, 10, and 15 wt%) were then prepared by a solution dispersion method. The introduction of Na₂WO₄ does not change the structures of the samples and they show similar morphologies with particle sizes from 100 to 200 nm. Suitable amount of Na₂WO₄ modification effectively improves the electrochemical performance of Li₂ZnTi₃O₈. Li₂ZnTi₃O₈@Na₂WO₄ composites (0, 5, 10, and 15 wt%) deliver the discharge/charge capacities of 137.4/136.4, 164.2/162.3, 189.2/188.1, and 154.5/153.3 mAh g^?1 at 0.5 A g^?1 after 100 cycles, respectively. Li₂ZnTi₃O₈@Na₂WO₄ composites (10 wt%) has the highest reversible capacities among all samples. The Na₂WO₄ shell with an excellent electronic conductivity can reduce electrode polarization, decrease the charge transfer resistance, enhance the Li-ion diffusion coefficient of Li₂ZnTi₃O₈, and then improve the electrochemical kinetics of composites. In addition, the formation of Ti–O bonds at the interface can be helpful for the stabilization of the composite, being beneficial for the improvement of their cycling stabilities. These results reveal that Na₂WO₄ coating is a facile and effective strategy to promote the Li storage performance of Li₂ZnTi₃O₈.     

Improvement the near-infrared luminescence properties of double perovskite phosphor La(Mg0.5Sn0.5In0.5Sc0.5)0.5O3:Cr3+ via co-doping Yb3+

In recent years, the broadband near-infrared (NIR) spectroscopy technology has been widely used in the field of nondestructive testing. However, these existing NIR phosphors showed relatively short emission wavelengths, narrower half-maximum full-width (FWHM), and narrower half-peak widths, importantly, few phosphors presented the emission from 950 nm to 1100 nm. In order to solve these problems, the Yb³⁺/Cr³⁺ ions codoped La(Mg_0.5Sn_0.5In_0.5Sc_0.5)_0.5O₃ (LMSIS) was synthesized by the solid-state method, and the emission spectrum of LMSIS:Cr³⁺ can be extended to the NIR long-wave region due to the energy transfer of Yb³⁺ and Cr³⁺, and the thermal stability of the phosphor can be improved due to the inherent temperature stability of the Yb³⁺ f-f transition. The NIR phosphor converted light emitting diodes (pc-LEDs) were fabricated by combining the LMSIS:0.003Cr³⁺, 0.0015Yb³⁺ with blue LED chip, which can be expected to be used in the field of broadband near-infrared non-destructive detection.     

Deep-red emission of Mn4+ and Cr3+ in (Li1−xAx)2MgTiO4 (A=Na and K) phosphor: Potential application as W-LED and compact spectrometer

Mn⁴⁺ doped and Mn⁴⁺/Cr³⁺ co-doped alkali metal titanate phosphors have been prepared by solid state reaction method. A part of Li⁺ ions in the Li₂MgTiO₄: Mn⁴⁺ are substituted with Na⁺ and K⁺ ions and consequently the intensity of Mn⁴⁺ emission at 678 nm is enhanced by 1.7 and 2.5 times, respectively. In the Mn⁴⁺/Cr³⁺ co-doped (Li_0.95K_0.05)₂MgTi_0.999O₄, both emission of Cr³⁺at 726 nm and emission of Mn⁴⁺ at 678 nm of Mn⁴⁺ are observed. It is interesting to find that the intensity ratio of 726–678 nm emissions in the Mn⁴⁺/Cr³⁺ phosphor continually increases with excitation wavelength increasing from 290 nm to 455 nm, which means that the intensity ratio in turn can be used to identify the excitation light wavelength. This refers a possible approach to design novel compact light-wavelength detector or spectrometer based on the phosphor. The mechanism of Na⁺ or K⁺ substitution induced luminescence enhancement in the Mn⁴⁺ phosphor and the competition between the Cr³⁺ and Mn⁴⁺ emissions in the Mn⁴⁺/Cr³⁺ co-doped has been discussed.     

Ultra-broadband of up to 200 nm near-infrared phosphors based on one-site occupation strategy for multipurpose applications in light-emitting diodes

Portable near-infrared (NIR) lighting source stimulates great efforts to exploit NIR phosphor-converted LEDs (pc-LEDs) that push the rapid development of broadband NIR-emitting phosphors. Although Cr³⁺-activated NIR phosphors designed by multisites occupation strategy show significant potential in emission bandwidth, poor spectral stability caused by different thermal quenching behaviors is a brake on practical application due to different local structure around Cr centers. One-site-based NIR phosphors seem to be an effective method to solve aforementioned problem. Herein, we report a type of new ultra-broadband one-site-based NIR-emitting phosphors NaSc_1-xP₂O₇:xCr³⁺ (NSP:xCr³⁺) with emission at 910 nm and full width at half maximum (FWHM) of up to ～200 nm. Their FWHM value exceeds all one-site-based Cr³⁺-activated phosphors and some multiple-sites ones. Structural analysis and low-temperature spectra demonstrate that such impressive broadband NIR emission originates from Cr³⁺ occupying at single octahedral Sc site. At 425 K, integrated emission intensity of NSP:0.04Cr³⁺ phosphor maintains 53.8% of room temperature. A NIR pc-LED prototype is fabricated by using NSP:0.04Cr³⁺ phosphor with a blue LED chip, and its multipurpose applications in non-destructive detection, night vision and analysis of foodstuff are demonstrated. These findings indicate that broadband NSP:0.04Cr³⁺ NIR phosphor enabled by one-site occupation strategy has potential prospect for multipurpose NIR pc-LEDs applications.     

Near infrared persistent luminescence of transparent Zn-Ga-Ge-O:Cr3+ glass ceramic for optical information storage

Cr³⁺-doped near-infrared (NIR) afterglow phosphors have received wide recognition in the optical storage field because of the high signal-to-noise ratio and broad excitation spectra. In this article, the high-temperature TL intensity of ZnGa₂O₄:Cr³⁺ afterglow glass ceramic (ZGO:Cr³⁺ GC) was enhanced via partial hetero-valence substitution of Ge for Ga, demonstrating the tunability of the trapped electron levels in ZGO:Cr³⁺ GC. The persistent luminescence phosphor ZGO:Cr³⁺ GC exhibits a zero-phonon lines emission peaking at 698 nm, attributing to the ²E→⁴A_2g transition of Cr³⁺ ions. Moreover, the trap levels in Zn-Ga-Ge-O:Cr³⁺ glass ceramic (ZGGO:Cr³⁺ GC) are deeper than those of the Ge-free one and the captured electrons in deeper levels cannot be released only by the ambient thermal energy, thus the optical storage capacity of ZGGO:Cr³⁺ GC is much larger. By means of an additional 980 nm laser photostimulation, an intense NIR emission could be obtained. In consequence, ZGGO:Cr³⁺ GC has a promising application prospect in optical information storage field.     

Synthesis,Crystal Structure,and Enhanced Luminescence of Garnet‐Type Ca3Ga2Ge3O12:Cr3+ by Codoping Bi3+

Garnet‐type compound Ca₃Ga₂Ge₃O₁₂ and Cr³⁺‐doped or Cr³⁺/Bi³⁺ codped Ca₃Ga₂Ge₃O₁₂ phosphors were prepared by a solid‐state reaction. The crystal structure of Ca₃Ga₂Ge₃O₁₂ host was studied by X‐ray diffraction (XRD) analysis and further determined by the Rietveld refinement. Near‐infrared (NIR) photoluminescence (PL) and long‐lasting phosphorescence (LLP) emission can be observed from the Cr³⁺‐doped Ca₃Ga₂Ge₃O₁₂ sample, and the enhanced NIR PL emission intensity and LLP decay time can be realized in Cr³⁺/Bi³⁺ codped samples. The optimum concentration of Cr³⁺ in Ca₃Ga₂Ge₃O₁₂ phosphor was about 6 mol%, and optimum Bi³⁺ concentration induced the energy‐transfer (ET) process between Bi³⁺ and Cr³⁺ ions was about 30 mol%. Under different excitation wavelength from 280 to 453 nm, all the samples exhibit a broadband emission peaking at 739 nm and the intensity of NIR emission increases owing to the ET behavior from Bi³⁺ to Cr³⁺ ions. The critical ET distance has been calculated by the concentration‐quenching method. The thermally stable luminescence properties were also studied and the introduction of Bi³⁺ can also improve the thermal stability of the NIR emission.     

Near-infrared long-lasting phosphorescence in transparent glass ceramics embedding Cr3+-doped LiGa5O8 nanocrystals

Cr³⁺ doped transparent glass ceramics of SiO₂–Ga₂O₃–Li₂O were fabricated by melt-quenching and subsequent crystallization. X-ray diffraction and transmission electron microscopy analyses evidenced that cubic LiGa₅O₈ nanocrystals were homogeneously precipitated among the silicate glass matrix. The incorporation of Cr³⁺ ions into LiGa₅O₈ nanocrystals was evidenced by absorption, emission and time-resolved luminescence spectra. Impressively, the present Cr³⁺ doped glass ceramics were demonstrated to be a new near-infrared (∼720 nm) long-lasting bulk phosphor whose luminescence can last for more than 2 h after stoppage of UV (250–350 nm) irradiation. The occurring of Cr³⁺ long-lasting phosphorescence in the glass ceramics was confirmed to be mainly due to the precipitation of Cr³⁺:LiGa₅O₈ nanocrystals from glass matrix. The filling/releasing of electrons into/from the intrinsic traps of LiGa₅O₈ nanocrystals through the conduction band of host were proposed to be responsible for the realization of the long-lasting phosphorescence of the investigated Cr³⁺ doped glass ceramics.