Ultra-broadband Emission Research Articles

Rare‐Metal‐Free Ultrabroadband Near‐Infrared Phosphors

AbstractTrivalent chromium (Cr3+) is an attractive near‐infrared (NIR) emitter, but its ultrabroadband NIR emission is limited to host crystals containing large amounts of rare‐metal elements and usually suffers from low internal quantum efficiency (IQE) and poor thermal stability. Here, a class of high‐performance, rare‐metal‐free ultrabroadband NIR phosphors, are reported by revealing that weak‐field Cr3+ centers featuring broadband NIR emission with near‐unity IQEs are intrinsic, though in trace quantities, to Cr3+ doped MgAl2O4 spinel (MAS) and its derivatives well‐known for their narrowband far‐red emission. It is shown that such weak‐field Cr3+ centers stem from cation inversion ubiquitous in spinel compounds, and their quantity can be increased simply by superstoichiometric Al2O3/Ga2O3. Then SiO2 is introduced into Al2O3‐excess MAS to break the inversion symmetry of Cr3+ centers for greatly improving the probabilities of their otherwise parity‐forbidden 3d–3d transitions. The as‐fabricated phosphor‐converted light‐emitting diodes are capable of emitting ultrabroadband NIR light with high photoelectric efficiency (16.0%) and optical power (180.8 mW), and excellent spectral stability, which apparently outperforms existing state‐of‐the‐art devices.

Ultra-broadband emission from Mg7Ga2GeO12:Ni2+,Cr3+ phosphor spanning the NIR I–III regions for spectroscopy applications

Ultra-broadband near-infrared (NIR) lighting sources covering NIR Ⅰ to III regions are pivotal components for NIR spectroscopy devices. However, achieving ultra-broadband and efficient emission covering the entire NIR Ⅰ to III regions remains a significant challenge. To address this, we selected Mg7Ga2GeO12 as host material to realize ultra-broadband NIR emission. Density functional theory calculations on formation energies confirmed the feasibility of doping both Ni2+ and Cr3+ within Mg7Ga2GeO12. Band structure calculations reveal a significantly reduced band gap upon the doping of Ni2+. Following that, we synthesized Mg7Ga2GeO12:Ni2+ through conventional solid-state-reaction method. This phosphor exhibits broadband NIR emission with a full-width-at-half-maximum of 377 nm in the range of NIR II ∼ III (1100–2100 nm). To further enhance the emission efficiency, we co-doped Mg7Ga2GeO12:Ni2+ phosphor with Cr3+. This co-doping strategy not only dramatically enhances the Ni2+ emission intensity, but also extends the lower limit of emission band to 600 nm. However, a spectral gap around 1150 nm remains between Cr3+ and Ni2+ emission centers. To bridge this spectral gap, we employed LiScSiO4:Cr3+ phosphor alongside Mg7Ga2GeO12:Ni2+,Cr3+ phosphor to fabricate a phosphor converted LED (pc-LED) with ultra-broadband NIR emission covering entire NIR Ⅰ to III regions. By utilizing this pc-LED as the lighting source for NIR spectral detection, multiple organic functional group signals can be identified simultaneously in NIR II and III bands from 1000 to 2100 nm. The performance of such an NIR pc-LED not only confirms the application potential of Mg7Ga2GeO12:Ni2+,Cr3+ phosphor in non-destructive spectral analysis but also underscores the feasibility of combining two phosphors to achieve ultra-broadband NIR pc-LEDs, rendering them suitable to be lighting sources for portable spectrometers.

Ultrabroadband mid-infrared emission and gas sensing of cobalt-doped chalcogenide glass ceramics.

Mid-infrared (MIR) gain materials are of great significance for the development of MIR tunable fiber lasers. Herein, for the first time, to the best of our knowledge, it is found that Ga2Se3 nanocrystals distributed in chalcogenide glass ceramics can provide new tetrahedral-coordinated sites that can be used to activate ultrabroadband MIR emissions of divalent transition metal ions, such as Co2+. Under the excitation of a 1550 nm diode laser, the transparent Ge-Ga-Se glass ceramic embedded with Co2+: Ga2Se3 nanocrystals shows an intense 2.5-5.5 µm ultrabroadband emission. The peak wavelength is located at ∼4.2 µm and the full width at half maximum exceeds 2 µm. Such emission properties, originating from the dual lattice sites of Ga3+ ions, are superior to those of transparent chalcogenide glass ceramics embedded with Co2+: ZnSe nanocrystals. Moreover, the gas detection system built based on the glass ceramic shows a sensitivity of 45.9 ppm for butane gas. Therefore, the chalcogenide glass ceramics embedded with active Co2+: Ga2Se3 nanocrystals have great potential in MIR tunable fiber lasers and gas sensing.

Achieving Ultra-Broadband Sunlight-Like Emission in Single-Phase Phosphors: The Interplay of Structure and Luminescence.

The quest for artificial light sources mimicking sunlight has been a long-standing endeavor, particularly for applications in anticounterfeiting, agriculture, and color hue detection. Conventional sunlight simulators are often cost-prohibitive and bulky. Therefore, the development of a series of single-phase phosphors Ca9LiMg1-xAl2x/3(PO4)7:0.1Eu2+ (x = 0-0.75) with sunlight-like emission represents a welcome step towards compact and economical light source alternatives. The phosphors are obtained by an original heterovalent substitution method and emit a broad spectrum spanning from violet to deep red. Notably, the phosphor with x = 0.5 exhibits an impressive full width at half-maximum of 330nm. A synergistic interplay of experimental investigations and theory unveils the mechanism behind sunlight-like emission due to the local structural perturbations introduced by the heterovalent substitution of Al3+ for Mg2+, leading to a varied distribution of Eu2+ within the lattice. Subsequent characterization of a series of organic dyes combining absorption spectroscopy with convolutional neural network analysis convincingly demonstrates the potential of this phosphor in portable photodetection devices. Broad-spectrum light source testing empowers the model to precisely differentiate dye patterns. This points to the phosphor being ideal for mimicking sunlight. Beyond this demonstrated application, the phosphor's utility is envisioned in other relevant domains, including visible light communication and smart agriculture.

In Situ Self-Assembled 1D/3D Mixed-Dimensional Perovskite Heterostructures for Efficient White Light Emission.

Mixed-dimensional perovskite (MDP) heterostructures are promising optoelectronic semiconductors. Yet, the current preparation methods involve complex experimental procedures and material compatibility constraints, limiting their widespread applications. Here, we present a one-step room temperature solution-based approach to synthesize a range of 1D C4N2H14PbBr4 and 3D APbBr3 (A = Cs+, MA+, FA+) self-assembled MDP heterostructures exhibiting high-efficiency white light-emitting properties. The ultra-broadband emission results from the synergy between the self-captured blue broadband emission from 1D perovskites and the green emission of 3D perovskites, covering the entire visible-light spectrum with a full width at half-maximum exceeding 170 nm and a remarkable photoluminescence quantum yield of 26%. This work establishes a novel prototype for the preparation of highly luminescent MDP heterostructures, offering insights for future research and industrialization in the realm of white light LEDs.

Multi-plane imaging based on cascade spintronic terahertz emitters with curved substrates.

As a novel terahertz (THz) source, a spintronic THz emitter (STE) has become a research hot topic recently due to its ultra-broadband emission, powerful scalability, simple fabrication, and ultrawide pump-wavelength range. To optimize the performance of a STE, its spintronic heterostructure has been extensively investigated and its accessories have been also appropriately improved. In this work, a curved substrate of a STE was proposed and utilized to achieve the modulation of the THz wave front as a new degree of freedom. A STE with a neutral-meniscus substrate was designed and fabricated to attain the focusing function of the emitted THz radiation. Coaxial THz bi-focus with a non-overlapping spatio-temporal distribution were effectively generated and applied in multi-plane imaging by properly using two cascade STEs. Amplitude- and phase-type objects consisting of bilayer structures were measured by the scheme. The focused and defocused regions of the samples were distinguished and analyzed on different cross sections. Furthermore, a STE with a spiral stair substrate was manufactured in this way and the generation of a THz vortex beam was fulfilled. The convenient approach offered more possibilities for developing THz optospintronic devices.

Accessing Ultrafast Spin-Transport Dynamics in Copper Using Broadband Terahertz Spectroscopy.

We study the spatiotemporal dynamics of ultrafast electron spin transport across nanometer-thick copper layers using ultrabroadband terahertz emission spectroscopy. Our analysis of temporal delays, broadening, and attenuation of the spin-current pulse reveals ballisticlike propagation of the pulse peak, approaching the Fermi velocity, and diffusive features including a significant velocity dispersion. A comparison to the frequency-dependent Fick's law identifies the diffusion-dominated transport regime for distances >2 nm. These findings lay the groundwork for designing future broadband spintronic devices.

Ultra-broadband near-infrared emission of Cr3+-containing oxy-fluoride glass-ceramics

Broadband near-infrared (NIR) light sources cover unique optical wavelengths and are valuable in the fields of bioimaging and photodynamic therapy, night vision lighting and security monitoring. NIR phosphor converted light-emitting diode (NIR pc-LED) devices have attractive features such as tunable emission peak, low cost of production, compact in sizes and high luminous efficiency. However, heat accumulation during operation due to poor thermal conductivity of the organic resin used in packaging often causes serious reduction in luminous efficiency and accelerated degradation of the device. In present work, we developed a Cr3+-doped transparent CaF2-based oxy-fluoride glass-ceramic (GC) that showed a broadband emission of 700∼1400 nm under 470 nm excitation. The emission peaked at ∼880 nm, the full-width at half maximum was about ∼297 nm, and the photoluminescence quantum yield reached ∼31.19 %. The emission was derived from the electronic transition of Cr3+ ions from the 4T2(F) to 4A2(F). Through structural analysis and numerical simulation, we showed that during the heat treatment process, Cr3+ ions were enriched into the CaF2 crystal phase and replaced the Ca2+ in the GC host with occupied the center position of the polyhedrons, which provided a weak crystal field and led to NIR emission. We built NIR pc-LED devices using optimized GC and commercial blue LED chips, and we demonstrated the application of this NIR pc-LED in night-vision lighting. Our approaches to prepare simple and stable inorganic NIR luminous materials sealed in bulk in a transparent CaF2-based oxy-fluoride GC and to construct pc-LED devices could provide new concept to the field and have practical implications to applications in related fields.

Multi-sites induced ultra-broadband luminescence based on Eu2+ doped whitlockite-type phosphor for full-spectrum WLEDs

Ultra-broadband-emitting phosphors are crucial for achieving high-quality full-spectrum WLEDs. However, it is difficult to achieve ultra-broadband emission by doping a single luminescent center. In this work, we propose a strategy to achieve ultra-broadband orange-red emission through utilizing Eu2+ selective occupation in multi-cation sites whitlockite-type phosphate Sr8Mg2Na(PO4)7. The result indicates that Eu2+ can occupy Sr1Mg1, Sr2Mg2, and Sr3Mg3 sites, and generate an ultra-broadband emission ranging from 400 to 800 nm with dominant emission at 620 nm and a FWHM of 220 nm upon 385 nm excitation. Interestingly, a new emission shoulder at 430 nm is obtained, which is demonstrated to ascribed to Eu2+ occupying the Mg4Na1 site in a weak crystal field. As an ultra-broadband-emitting and red-light abundant phosphor, the full-spectrum WLEDs shows much higher color index than that of YAG: Ce3+. Moreover, an ultraviolet light pumped full-spectrum WLED with a high Ra (∼92) and low CCT (∼4275 K) is fabricated by mixing the Sr8Mg2Na(PO4)7: Eu2+ and commercial phosphors BAM: Eu2+, Mn2+. In summary, this work deeply investigated the luminescence properties of Eu2+ in whitlockite-type phosphor Sr8Mg2Na(PO4)7 and is expected to guide the design of novel broadband-emitting phosphors with multi cationic sites for emerging full-spectrum WLED applications.

Two-Site Occupation for Constructing Double Perovskite BaLaMgNbO6:Cr3+ Ultrabroadband NIR Phosphors.

Given the escalating significance of near-infrared (NIR) spectroscopy across industries, agriculture, and various domains, there is an imminent need to address the development of a novel generation of intelligent NIR light sources. Here, a series of Cr3+-doped BaLaMgNbO6 (BLMN) ultrabroadband NIR phosphor with a coverage range of 650-1300 nm were developed. The emission peak locates at 830 nm with a full width at half maximum of 210 nm. This ultrabroadband emission originates from the 4T2→4A2 transition of Cr3+ and the simultaneous occupation of [MgO6] and [NbO6] octahedral sites confirmed by low photoluminescence spectra (77-250 K), time-resolved photoluminescence spectra, and electron paramagnetic resonance spectra. The fluxing strategy improves the luminescence intensity and thermal stability of BLMN:0.02Cr3+ phosphors. The internal quantum efficiency (IQE) is 51%, external quantum efficiency (EQE) can reach 33%, and thermal stability can be maintained at 60%@100 °C. Finally, we successfully demonstrated the application of BLMN:Cr3+ ultrabroadband in the qualitative analysis of organic matter and food freshness detection.

Cr3+ and Yb3+ co-doped perovskite-like phosphor with improved thermal stability by efficient energy transfer

With the development of white light-emitting diode (LED) technology, near-infrared (NIR) phosphor-converted (pc) LED is becoming a new emerging light source. However, due to the lack of long wavelength components of the phosphors, the application of NIR pc-LED is restricted. In this work, a continuous ultra-broadband NIR emission without the emission gap in the 850–950 nm region has been realized in the Mg4Nb2O9 (MNO):Cr3+, Yb3+ phosphor. Meanwhile, when compared to MNO:Cr3+, an improved internal quantum efficiency (from 55.4% to 72.6%) and thermal stability (from 39% to 63% at 100 °C) have been obtained for MNO:Cr3+, Yb3+, which is attributed to the combined effect of the efficient energy transfer from Cr3+ to its nearest Yb3+ and the unique energy levels of Yb3+. The performances of the fabricated pc-LED devices by combining MNO:Cr3+, Yb3+ with 460 nm LED chips were also given, and the results demonstrate that the MNO:Cr3+, Yb3+ phosphor may have potential for practical application in the NIR pc-LED.

LaMg6Ga6S16: a chemical stable divalent lanthanide chalcogenide

Divalent lanthanide inorganic compounds can exhibit unique electronic configurations and physicochemical properties, yet their synthesis remains a great challenge because of the weak chemical stability. To the best of our knowledge, although several lanthanide monoxides epitaxial thin films have been reported, there is no chemically stable crystalline divalent lanthanide chalcogenide synthesized up to now. Herein, by using octahedra coupling tetrahedra single/double chains to construct an octahedral crystal field, we synthesized the stable crystalline La(II)-chalcogenide, LaMg6Ga6S16. The nature of the divalent La2+ cations can be identified by X-ray photoelectron spectroscopy, X-ray absorption near-edge structure and electron paramagnetic resonance, while the stability is confirmed by the differential thermal scanning, in-situ variable-temperature powder X-ray diffraction and a series of solid-state reactions. Owing to the particular electronic characteristics of La2+(5d1), LaMg6Ga6S16 displays an ultrabroad-band green emission at 500 nm, which is the inaugural instance of La(II)-based compounds demonstrating luminescent properties. Furthermore, as LaMg6Ga6S16 crystallizes in the non-centrosymmetric space group, P−6, it is the second-harmonic generation (SHG) active, possessing a comparable SHG response with classical AgGaS2. In consideration of its wider band gap (Eg = 3.0 eV) and higher laser-induced damage threshold (5×AgGaS2), LaMg6Ga6S16 is also a promising nonlinear optical material.

Ultra-broadband triple-peak white light-emitting carbonized polymer dots materials based on Förster resonance energy transfer

Carbonized polymer dots (CPDs) with white-light-emitting property have greatly promising application in next generation of lighting and display technologies. However, most of the reported CPD materials exhibit single peak emission and narrow emission band, resulting in difficulty to obtain white-light emission. In this work, the ultra-broadband triple-peak emission (red, green, and blue) CD-based materials with high-efficiency white light-emitting property are realized for the first time by the Förster resonance energy transfer (FRET). Blue and green emissions are derived from the fluorescence and phosphorescence of donor CPDs, while the red light is derived from receptor by FRET. Remarkably, the fabricated CPD materials show bright pure white-light emission with high overall quantum yield (QY) of 36% and the full width at half maximum of 235 nm. Besides, afterglow colors of CPD-based materials can be tuned from green to red by adjusting the ratio of donor and acceptor. Based on the high-efficiency and wide-spectrum pure white light emission characteristics of CPD-based composites, white light emitting diodes were fabricated and they exhibit bright warm white light with CIE and CCT of (0.35, 0.31) and 4041 K.

Full-Spectrum White-Light Emission from Triple Self-Trapped Excitons in Hybrid Mixed-Metal Halides.

Low-dimensional metal halides with broadband emissions are expected to serve as downconversion luminescent materials for solid-state lighting (SSL). However, efficiently generating full-spectrum white-light emission with a high color-rendering index (CRI) in single-phase emitters remains a challenge. Here, we report a novel zero-dimensional (0D) hybrid mixed-metal halide (TPA)2CuAgI4 (TPA = tetrapropylammonium), in which individual [CuAgI4]2- dimers are completely isolated and surrounded by the organic cations TPA+. Cu+ and Ag+ share the same crystallographic site in [CuAgI4]2- dimers with the same statistical probability. Upon photoexcitation, single crystals exhibit a full-spectrum white-light emission with a full width at half-maximum (fwhm) of up to 314 nm and a high quantum efficiency of 46.8%. Detailed photophysical studies and theoretical calculations reveal that the ultra-broadband emission of (TPA)2CuAgI4 originates from the radiative recombination of red-, green-, and blue-emitting self-trapped excitons in [CuAgI4]2- dimers. In addition, (TPA)2CuAgI4 nanocrystals were successfully synthesized and exhibited optical properties similar to those of single-crystal counterparts. Finally, a prototype ultraviolet (UV)-pumped white-light-emitting diode (WLED) and a composite thin film employing this new white-light emitter produces a well-distributed full-spectrum white light with a high CRI of 91.4 and a warm correlated color temperature (CCT) of 4135 K, indicating the potential application of this white-light emitter in SSL. These results provide a new perspective for designing superior single-phase white-light emitters.

Tunable ultra-broadband multi-band NIR emission in Bi-doped aluminogermanate glasses and fibers via controllable Al2O3 content for broadband amplifiers

The tunable ultra-broadband multi-band NIR emission of Bi-doped germanate glass and fiber can be achieved via constructing various glass local network environments with steerable Al2O3 content and show potential applications in broadband amplifiers.

Ultra-broadband bright light emission from a one-dimensional inorganic van der Waals material

One-dimensional (1D) van der Waals materials have emerged as an intriguing playground to explore novel electronic and optical effects. We report on inorganic one-dimensional SbPS4 nanotube bundles obtained via mechanical exfoliation from bulk crystals. The ability to mechanically exfoliate SbPS4 nanobundles offers the possibility of applying modern 2D material fabrication techniques to create mixed-dimensional van der Waals heterostructures. We find that SbPS4 can readily be exfoliated to yield long (>10 μm) nanobundles with thicknesses that range from 1.3 to 200 nm. We investigated the optical response of semiconducting SbPS4 nanobundles and discovered that upon excitation with blue light, they emit bright and ultra-broadband red light with a quantum yield similar to that of hBN-encapsulated MoSe2. We discovered that the ultra-broadband red light emission is a result of a large ∼1 eV exciton binding energy and a ∼200 meV exciton self-trapping energy, unprecedented in previous material studies. Due to the bright and ultra-broadband light emission, we believe that this class of inorganic 1D van der Waals semiconductors has numerous potential applications, including on-chip tunable nanolasers, and applications that require ultraviolet to visible light conversion, such as lighting and sensing. Overall, our findings open avenues for harnessing the unique characteristics of these nanomaterials, advancing both fundamental research and practical optoelectronic applications.

A NIR phosphor with ultra-broadband emission enabled by dual energy transfer within two Cr3+ emitters and Cr3+ → Yb3+

The NIR phosphor Sr3SiAl10O20, which realizes ultra-broadband emission via dual energy transfer within two Cr3+ emitters and Cr3+ → Yb3+, can be used for NIR pc-LEDs, showing great potential in the fields of night-vision illumination, nondestructive surveillance, and information encryption.

Ultra-broadband emission up to 181 nm of VO4-activated yellow phosphor for white light-emitting diodes with high color rendering index

Exploring broadband yellow phosphors capable of covering the cyan to red region is an effective approach to achieve high-performance phosphor-converted white light-emitting diodes (pc-WLEDs). Herein, we synthesized a series of VO4-activated ultra-broadband KSrP1−xVxO4 (0.1 ≤ x ≤ 1) yellow phosphors via high temperature solid-state reaction. Successive substitution of P5+ with V5+ causes a slight expansion of the lattice constant and induces several highly localized energy-levels within the forbidden band. Density functional theory calculations confirm that these newly appeared sharp-line energy-levels are attributed to the constructed VO4 anionic groups. With the optimized V5+ content, the KSrP0.7V0.3O4 phosphor exhibits an ultra-broadband yellow emission centered at 537 nm under 355 nm excitation. Impressively, its full width at half maximum is up to 181 nm, exceeding that of most reported counterparts. At 105 °C, the KSrP0.7V0.3O4 sample experiences an emission loss of 53%. A WLED device is fabricated by using phosphor blend of KSrP0.7V0.3O4 yellow phosphor and the commercial BaMgAl10O17: Eu2+ blue phosphor and a 355 nm NUV LED chip, demonstrating bright white emission with high color rendering index (CRI) of 90 and suitable correlated color temperature of 5953 K. These findings indicate that this phosphor has great potential for achieving high CRI WLEDs.

Unity emission in organic phosphonium antimony halide for high color rendering white LED

Metal halides have attracted increasing attention in luminescent applications because of their fantastic properties in optoelectronics and easy solution processability. However, toxicity of Pb element and low photoluminescence quantum yield (PLQY) hamper their practical application. Herein, we report a lead-free zero-dimensional antimony (Ⅲ) hybrid halide (EPP)2SbCl5 ⋅CH2Cl2 (EPP = Ethyltriphenylphosphonium), in which inorganic luminescent center [SbCl5]2- are surrounded by organic ligands, forming a perfect host-guest system and exhibiting unprecedented photophysical properties. The (EPP)2SbCl5⋅CH2Cl2 exhibits a bright orange-red emission located at 623 nm, a near-unity PLQY of 97.09 %, and a large Stokes shift of 253 nm. The characterization of photophysical properties shows that broadband emission with microsecond decay lifetime (6.98 μs) is derived from self-trapped exciton emission. Together highly efficient and ultra-stable luminescence performance enable (EPP)2SbCl5⋅CH2Cl2 as excellent down-conversion phosphor to successfully fabricate white light-emitting diodes (LEDs) device with a color rendering index of 95. It is proved that the prepared 0D antimony hybrid halide with ultrabroad-band emission and near-unity PLQY is a promising solid-state lighting luminescent material.

Ni2+-doped MgTa2O6 phosphors capable of near-infrared II and III emission under blue-light excitation

Presently, Ni2+-activated near-infrared (NIR) phosphors still have disadvantages such as relatively short emission wavelength and narrow half-peak width, mismatched excitation wavelength to that of commercially available high-efficiency blue chips. Here, Ni2+-doped tetragonal MgTa2O6 NIR phosphor was successfully prepared by high-temperature solid phase method. The matrix material provided an octahedral lattice for Ni2+ to replace Ta5+ in the [TaO6] octahedron of the crystal lattice. Under the excitation of 470 nm blue light, Ni2+ was excited through 3T2(F)→3A2(F) spin-allowed transition and emitted an ultra-broadband NIR light that was 1300–2000 nm in wavelength, peaked ∼ 1620 nm, covered the NIR-II and NIR-III regions, had a full width at half maximum reached 297 nm, and a PLQY of 25.62 %. The unique ultra-broadband and long wavelength NIR emission by this phosphor was derived from Ni2+ which is situated in a weak crystal field environment due to space asymmetric distortion caused by a high charge polarization surrounding the center of the [TaO6] octahedron in a MgTa2O6 matrix. A NIR pc-LED was constructed using Ni2+-doped near-infrared phosphors packaged with a commercial high-efficiency blue LED chip (@ 470 nm), and its application prospect was demonstrated by NIR night vision monitoring and nondestructive imaging of venous in human fingers.