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.     

A broadband near-infrared Sc1−x(PO3)3:XCr3+ phosphor with enhanced thermal stability and quantum yield by Yb3+ codoping

Broadband near-infrared (NIR) phosphors converted light-emitting diodes (pc-LEDs) have attracted tremendous attention for their great potential in NIR spectroscopy applications. Herein, we report on the photoluminescence (PL) properties of Cr³⁺-doped Sc(PO₃)₃, which exhibits a broadband NIR emission centered at 900 nm with a full width at half-maximum (FWHM) of 161 nm upon excitation at 480 nm. In terms of the examination of spectroscopic parameters, we find that Cr³⁺ ions occupy a weak crystal field site (Dq/B = 1.94) in the Sc(PO₃)₃ host with a stronger electron–phonon coupling (Huang-Rhys factor, S = 5.5), which results in a serious thermal quenching and a low internal quantum efficiency (IQE). Thermal stability and IQE of phosphors can be substantially enhanced by the introduction of Yb³⁺ ions. In the light of the analysis of excited-state dynamics, we demonstrate that the enhancement mechanism is ascribed to the efficient Cr³⁺→Yb³⁺ energy transfer from the thermal sensitive Cr³⁺ centers to the thermal stable Yb³⁺ emitters. An NIR pc-LED device has been finally fabricated by the combination of a blue-emitting chip and a Cr³⁺/Yb³⁺ codoped Sc(PO₃)₃ phosphor whose potential application for broadband NIR pc-LEDs is also discussed.     

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.     

Broadband deep-red-to-near-infrared emission from Mn2+ in strong crystal-field of nitride MgAlSiN3

Broadband near-infrared (NIR) phosphors have received increasing attention for fabricating phosphor-converted light-emitting diodes (pc-LEDs) as NIR light source. Most of the reported broadband NIR phosphors originate from Cr³⁺ in weak crystal field environments. Herein, we report a luminescent material, MgAlSiN₃:Mn²⁺ with CaAlSiN₃-type structure, demonstrating that broadband deep-red-to-NIR emission can be achieved via doping Mn²⁺ into crystallographic sites with strong crystal field in inorganic solids. This phosphor is synthesized via easy-handle solid-state reaction, and the optimized sample, (Mg_0.93Mn_0.07) AlSiN₃ shows an emission band with peak at ~754 nm, FWHM of 150 nm, and internal quantum efficiency of 70.1%. The photoluminescence intensity can further be enhanced by co-doping Eu²⁺ as sensitizer. This work provides a new strategy for discovering new broadband NIR phosphors using Mn²⁺ in strong crystal field as luminescence center.     

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.     

Broadband near-infrared double-perovskite phosphor Sr2ScTaO6:Cr3+, Yb3+ for NIR pc-LED applications

The broadband near-infrared (NIR) phosphor converted light emitting diode (NIR pc-LED) has garnered unprecedented attention due to its crucial role in NIR applications. However, there remains a scarcity of efficient broadband NIR luminescence materials capable of emitting NIR light with wavelengths greater than 800 nm. This study reports the synthesis, crystal structure and photoluminescence (PL) properties for double perovskite Sr₂ScTaO₆:Cr³⁺ phosphors which exhibit a broadband NIR emission in the 650–1250 nm range, peaking at∼815 nm with the full width at half maximum (FWHM) of 161 nm. The observed broadband emission arises from two distinct Cr³⁺ centers, namely Sc³⁺ and Ta⁵⁺ octahedral sites within the Sr₂ScTaO₆ structure, as demonstrated by luminescence and decay kinetic analysis. A significant enhancement of the thermal stability and a remarkable broadening of the FWHM (from 161 to 275 nm) are achieved by employing Yb³⁺ co-doping strategy. The efficient energy transfer from Cr³⁺ to Yb³⁺ was confirmed through emission and excitation spectra, as well as luminescence decay measurements. Finally, Sr₂ScTaO₆:Cr³⁺-Yb³⁺ phosphor was integrated with a 470 nm blue LED chip to fabricate a NIR pc-LED device, and its potential application in night vision was evaluated.     

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.     

Broadband emission of single-phase Ca3Sc2Si3O12:Cr3+/Ln3+ (Ln = Nd,Yb, Ce) phosphors for novel solid-state light sources with visible to near-infrared light output

Novel single-component phosphors Ca₃Sc₂Si₃O₁₂:Cr³⁺/Ln³⁺ (CSS:Cr³⁺/Ln³⁺, Ln = Nd, Yb, Ce) with broadband near-infrared (NIR) emissions are synthesized. Their phase structure, photoluminescence properties and energy transfer between Cr³⁺ and Ln³⁺ ions are investigated. In the CSS host, Cr³⁺ ions occupy Sc³⁺ sites with low-field octahedral coordination, and thus show a broadband emission in 700–900 nm under the blue light excitation. Nd³⁺, Yb³⁺ and Ce³⁺ ions substitute Ca²⁺ sites in CSS, where Nd³⁺ and Yb³⁺ ions emit the NIR light in 900–1100 nm and their excitation efficiencies at ∼450 nm are greatly enhanced by utilizing the energy transfer from Cr³⁺ to Nd³⁺/Yb³⁺ ions. Ce³⁺ ions can further enhance the absorption of CSS:Cr³⁺/Ln³⁺ phosphors to the blue light, and at the same time contribute to the visible emission in 480–650 nm. Furthermore, CSS:Cr³⁺/Ln³⁺ phosphors show good thermal stability, and approximately 79% of the initial emission intensity is sustained at 150 °C. A phosphor-converted LED (pc-LED) prototype is fabricated by integrating the as-prepared phosphor CSS:Cr³⁺/Ln³⁺ and the commercial phosphor CaAlSiN₃:Eu²⁺ with the blue LED chip, showing a super broadband emission ranging from 450 to 1100 nm. This finding shows the potential application of CSS:Cr³⁺/Ln³⁺ phosphors in broadband NIR pc-LEDs or super broadband LED sources with visible to NIR light output.     

Site occupancy and enhanced luminescence of broadband NIR gallogermanate phosphors by energy transfer

Super broadband near-infrared (NIR) La₃Ga₅GeO₁₄(LGGO): Cr³⁺ phosphor is in urgent needs for food testing. Unfortunately, it suffers from poor luminescence intensity in applications. Herein, the enhanced NIR luminescence performance can be realized in LGGO: Pr³⁺, Cr³⁺. The preferential crystallographic site of Cr³⁺ is validated on the basis of EPR spectrum, Rietveld refinement, and the first-principles DFT calculations. It is of great importance that the as-prepared phosphors can be excited by blue light (460 nm), which is beneficial to the application of blue-pumped LEDs. The critical distance of Pr³⁺ in LGGO host has been calculated by concentration-quenching method. For co-doped sample, it is observed that Cr³⁺ luminescence intensity enhancement by a factor of 3 can be achieved by doping Pr³⁺ owing to the energy transfer from Pr³⁺ to Cr³⁺. In addition, the introduction of Pr³⁺ can also improve the Cr³⁺ luminescence intensity at elevated temperature. Furthermore, using the optimized phosphor, a blue-based NIR phosphor-converted LEDs (NIR pc- LEDs) is fabricated, the forward voltage and the intensity of LED hardly change after thermal aging for 500 hours under high temperature/ high humidity condition, indicating its great reliability for NIR pc-LEDs. Therefore, LGGO:Pr³⁺, Cr³⁺ has great potential to serve as an attractive candidate in the application of blue light-excited NIR pc-LEDs in view of its capability for blue to enhanced broadband NIR conversion.     

A novel extra-broadband visible-NIR phosphor doped with Ce3+ and Cr3+ towards multifunctional advanced applications

Phosphors that can emit broadband light from visible to near infrared (NIR) may have applications in the fields like white-light illumination and NIR vessel visualization, the investigation on single phase extra-broadband visible-NIR emitting phosphor is of great significance. Herein, an extra-broadband phosphor with tunable visible-NIR emission from 500 nm to longer than 900 nm (bandwidth >400 nm) was successfully prepared, which originates from the emission of Ce³⁺ (peaking at 573 nm), Cr³⁺ (peaking at 750 nm) and energy transfer from Ce³⁺ to Cr³⁺ in Y₃MgAl₃SiO₁₂ garnet. The influences of Ce³⁺/Cr³⁺ doping concentration and working temperature were discussed systematically by luminescence spectra and decay curves. A visible-NIR full-spectrum phosphor-converted light emitting diode (pc-LED) fabricated with a 460 nm LED chip and Y₃MgAl₃SiO₁₂:0.03Ce³⁺, 0.01Cr³⁺ can generate bright white light and broadband NIR light simultaneously. The co-doping of Ce³⁺ can perfectly compensate for the missing spectrum of Cr³⁺ in the visible region, thanks to the extra-broadband emission of Ce³⁺ in visible region and Cr³⁺ in NIR region, multifunctional advanced applications may be realized for the prepared phosphors.     

Energy transfer realizes efficient NIR emitting Ca2ScTaO6:Cr3+, Yb3+ perovskite-structured phosphors

Stable and efficient broadband near-infrared (NIR) emitting phosphors are vital for the next-generation NIR sources. However, it still remains challenging to construct such phosphors, particularly those with a NIR-II window. In this work, using the Cr³⁺-Yb³⁺ energy transfer (ET) strategy, the as-synthesized Ca₂ScTaO₆:Cr³⁺, Yb³⁺ phosphor retains 86.2% of the initial luminescence intensity of Yb³⁺ at 373 K with characteristic emissions of both activators ranging from 700 nm to 1200 nm. The occupation of Cr³⁺ into both Ta⁵⁺ and Sc³⁺ sites is confirmed by X-ray diffraction, time-resolved emission spectrum, and crystal structure. The efficient ET from Cr³⁺ to Yb³⁺ is revealed by the diffuse reflection spectrum, steady-state and transient fluorescence. As a result, it contributes to the excellent performance of the phosphor. Based on the optimized phosphor, a NIR light-emitting diode is fabricated and demonstrated its advantage in imaging and potential application in information encryption. The result highlights ET as a robust strategy to construct efficient NIR phosphor.     

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.     

Dopant and compositional modulation triggered long-wavelength ultra-broadband and tunable NIR emission in MgO: Cr3+ phosphor for NIR spectroscopy applications

Efficient ultra-broadband near-infrared (NIR) phosphors with long-wavelength (λ_max > 850 nm) and wide full width at half-maximum (FWHM, >200 nm) have sparked tremendous interest, demonstrating their immense potential in NIR spectroscopy technology. Nevertheless, the development of NIR spectroscopy technology suffers from the restricted capability to efficiently emit the ultra-broadband NIR light. Herein, the synergetic enhancement strategy of heterogeneous substitution and compositional modulation was applied to create a novel Cr³⁺ doped long-wavelength ultra-broadband MgO: Cr³⁺, Ga³⁺ phosphor, which exhibited a long-wavelength ultra-broadband NIR emission (λ_max = 850 nm) covering the range of 650–1300 nm on the electromagnetic spectrum with the FWHM of more than 200 nm under the excitation of 468 nm light. Furthermore, the tunable NIR emission from 818 nm to 862 nm with an optimized quantum efficiency of 30% was accomplished by the Ga³⁺ ions substitution and Cr³⁺ ions modulation. The phosphor exhibited remarkable thermal stability up to 100 °C, remaining 83% of the integrated emission intensity at room temperature. A prototype of the NIR phosphor-converted LED (pc-LED) demonstrated that the novel MgO: Cr³⁺, Ga³⁺ phosphor possessed a relatively strong NIR output power (15.05 mW at 100 mA driven current) with a photoelectric conversion efficiency of 5.53%, which is impressive compared with other Cr³⁺-doped long-wavelength ultra-broadband phosphors. This work not only proposes a novel long-wavelength ultra-broadband NIR phosphors with industrialization and great application prospect in night vision but highlights a synergetic enhancement strategy to effectively boost the performance of long-wavelength ultra-broadband NIR pc-LED light sources.     

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.     

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.     

Mid-infrared luminesce of ZnS:Cr2+-glass composite and fiber

Cr²⁺-doped materials with mid-infrared (Mid-IR) broadband luminescence are of fundamental importance for various applications, such as solid-state lasers technology, biolabeling, optical telecommunication, and solar energy management. Especially, Cr²⁺-doped glass has been considered as one of important material candidates. The major challenge is the precipitation of crystals doped with Cr²⁺ ions in glass. So, “crystals in glass composite” is an effective method to solve this issue. Here, we describe a ZnS:Cr²⁺ in borophosphate glass composite (CZPB) which exhibits Mid-IR luminescence in the region from 1700 to 2900 nm with the full width at half maximum (FWHM) of about 690 nm. In addition, the materials can also be fabricated into fiber without obvious change in the characteristic luminescence band. The results provide new opportunities for the construction of the broadband fiber light source operating at Mid-IR waveband region.     

The hydrothermally synthesis of K3AlF6:Cr3+ NIR phosphor and its performance optimization based on phase control

Phosphor-convert (pc) near-infrared (NIR) LED is the next-generation smart NIR light sources. Thus, NIR phosphors are quickly developed. The K₃Al_1−xF₆:xCr³⁺ (KAF:Cr³⁺) NIR phosphor shows broadband emission from 650 to 900 nm under 430 nm and can be used to fabricate NIR LEDs. In this work, KAF:Cr³⁺ phosphors were prepared by a hydrothermal method for the first time. Morphologies and NIR properties are tuned by controlling the hydrothermal processes. Different from the cubic KAF:Cr³⁺ synthesized by a coprecipitation method, KAF:Cr³⁺ synthesized by the hydrothermal method shows the tetragonal phase. The optimized KAF:3%Cr³⁺ shows an internal quantum efficiency of about 31.4%. A NIR pc-LED device was fabricated by integrating the KAF:3%Cr³⁺ phosphor with a blue LED chip (~450 nm). The output power of NIR light is about 5.5 mW driven at 150 mA.     

Luminescence enhancement of Cr3+ doped garnet phosphor for high-performance LED towards smart NIR light source

Cr³⁺ doped phosphor shows great potential for near-infrared (NIR) light-emitting diodes (LED), but it suffers from low quantum efficiency and poor thermal stability. Herein, a novel Cr³⁺ doped broadband NIR garnet Ca₃Sc₂Ge₃O₁₂ phosphor was developed. The multisite structure of the emission band is investigated by site-selective spectroscopy and is attributed to the octahedral Cr³⁺ perturbed by defects. Moreover, we propose different strategies to enhance the luminescence of the phosphor, including enhancement of crystallinity and elimination of defects. Compared with the initial sample, the emission intensity of the optimized phosphor is improved for 8.6 times. The optimal Ca₃Sc₂Ge₃O₁₂: 0.06Cr³⁺ phosphor exhibits excellent thermal stability. At 423 K, the integral emission intensity of the optimal sample remains 94.7% of that at room temperature. Finally, high-performance NIR LED was fabricated using a blue LED and the title phosphor. The packaged LED lamp has high radiance (109.3 mW@300 mA) and photoelectric efficiency (15.96%@40 mA). Our study not only provides a boulevard for enhancing the luminescence of Cr doped NIR phosphor, but also gives a new perspective for understanding the multisite luminescence of Cr³⁺ in garnet host.     

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.     

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).