Efficient Near-infrared Emission Research Articles

Decoupling excitons from high-frequency vibrations in organic molecules

The coupling of excitons in π-conjugated molecules to high-frequency vibrational modes, particularly carbon–carbon stretch modes (1,000–1,600 cm−1) has been thought to be unavoidable1,2. These high-frequency modes accelerate non-radiative losses and limit the performance of light-emitting diodes, fluorescent biomarkers and photovoltaic devices. Here, by combining broadband impulsive vibrational spectroscopy, first-principles modelling and synthetic chemistry, we explore exciton–vibration coupling in a range of π-conjugated molecules. We uncover two design rules that decouple excitons from high-frequency vibrations. First, when the exciton wavefunction has a substantial charge-transfer character with spatially disjoint electron and hole densities, we find that high-frequency modes can be localized to either the donor or acceptor moiety, so that they do not significantly perturb the exciton energy or its spatial distribution. Second, it is possible to select materials such that the participating molecular orbitals have a symmetry-imposed non-bonding character and are, thus, decoupled from the high-frequency vibrational modes that modulate the π-bond order. We exemplify both these design rules by creating a series of spin radical systems that have very efficient near-infrared emission (680–800 nm) from charge-transfer excitons. We show that these systems have substantial coupling to vibrational modes only below 250 cm−1, frequencies that are too low to allow fast non-radiative decay. This enables non-radiative decay rates to be suppressed by nearly two orders of magnitude in comparison to π-conjugated molecules with similar bandgaps. Our results show that losses due to coupling to high-frequency modes need not be a fundamental property of these systems.

Strategies to Realize Efficient and Stable Broadband NIR Emission in Germinate Oxides

AbstractPhosphor‐converted light‐emitting diodes (pc‐LEDs) are efficient and cost‐effective ultrabroadband light sources for miniaturizing various optical systems, but they exhibit poor optical performance due to the lack of efficient near‐infrared (NIR) phosphors with a wide spectral coverage of 700−1100 nm. Although germanate oxides are a promising class of host materials for Cr3+ to generate broadband NIR light, the preferred formation of [CrO4]4− and the high vapor pressure of Ge element cause these Cr3+ activated phosphors to suffer from low internal quantum efficiency (IQE) and poor thermal stability. Here, highly efficient (IQE > 90%) and thermally stable broadband NIR emission of Cr3+ in the germinate garnet Ca2LuMgScGe3O12 (CLMSG) are obtained by exploiting a two‐step sintering method to achieve full reduction of Cr4+ to Cr3+. Further, efficient energy transfer from Cr3+ to Yb3+ is leveraged to significantly improve the emission intensity of CLMSG:Cr3+ in the shortwave infrared range of 900−1100 nm. Finally, an ultrabroadband NIR pc‐LED with a high NIR conversion efficiency (21.5%@10 mA) and high NIR power (116.4 mW@350 mA) is demonstrated to verify the strong capability of CLMSG:Cr3+, Yb3+ in blue‐to‐NIR light conversion. The results open up new ways to realize efficient ultrabroadband NIR‐emitting materials.

Efficient Near‐Infrared Emitting Halide Scintillators with Mitigating External Light Crosstalk for Portable X‐Ray Imaging

AbstractPortable X‐ray imaging technology plays a crucial role in enabling prompt diagnosis and treatment outdoors. Nevertheless, the persistent challenge of external optical signal crosstalk poses a significant bottleneck to its advancement. Herein, a solution utilizing near‐infrared (NIR) light to effectively mitigate optical crosstalk is proposed, thereby demonstrating the feasibility of portable X‐ray imaging even under ambient light. A series of rare earth ions doped Cs2AgxNa1‐xInyBi1‐yCl6 halide scintillators is reported, which possess bright broadband visible and NIR emissions. Taking Cs2Ag0.6Na0.4In0.95Bi0.05Cl6: 5%Tm as an example, it shows decent thermal quenching resistance, high PLQY up to 76.3%, and compelling light yield up to 33500 photons MeV−1. The highly efficient NIR emission is attributed to the energy transfer from the optimized host to lanthanide ions. A flexible scintillation film is prepared by mixing poly(dimethyl‐siloxane) with Cs2Ag0.6Na0.4In0.95Bi0.05Cl6: 5%Tm powder, realizing a low X‐ray detection limit of 55.2 nGyair/s and a high spatial resolution of 11.2 lp mm−1. Due to the efficient NIR emission, the scintillation film enables clear X‐ray imaging under bright LED illumination with the simple addition of filters, avoiding the necessity of a complex imaging apparatus. This work sheds light on NIR emissive scintillator for rapid outdoor response and portable X‐ray imaging.

Antimony doping in A2ZnCl4 (A= Rb, Cs) metal halides enabling tunable near-infrared emission

Lead-free metal halides with stable and tunable emission have shown great promise for broad application prospects in the visible light range. However, it remains a fundamental challenge to realize tunable near-infrared (NIR) luminescence in these metal halide materials. Herein, a cation regulation strategy in zero-dimension organic metal halides A2ZnCl4:Sb3+ (A = Rb, Cs) to achieve tunable NIR luminescence is reported. The prepared A2ZnCl4:Sb3+ (A = Rb, Cs) halides exhibited efficient broadband NIR emission, which originates from self-trapped excitons of the [SbCl4]− polyhedron. Based on the regulation of cation, the [SbCl4]− tetrahedral distortion capacity changes, exciton–phonon coupling is enhanced, leading to a red shift of the emission wavelength. The results provide inspiration for the regulation of the self-trapped excitons luminescence of halides and demonstrate potential as a non-visible light source for night vision.

Highly efficient broadband near-infrared luminescence phosphors Ca3MgSn0.5Zr0.5Ge3O12:Pr3+,Cr3+ for multifunctional applications in pc-LEDs field

Exploring high-performance broadband near-infrared (NIR) emitting materials is crucial for the development of NIR devices. In this study, Ca3MgSn0.5Zr0.5Ge3O12:Cr3+ and rare earth ion Pr3+ co-doped Ca3MgSn0.5Zr0.5Ge3O12:Pr3+,Cr3+ phosphors were successfully synthesized. By utilizing time-resolved emission spectroscopy (TRES), photoluminescence (PL) spectra, and fluorescence decay curve, the Ca3MgSn0.5Zr0.5Ge3O12:Cr3+ phosphor is determined to exhibit a broadband emission (650–1150 nm) with a peak at 795 nm due to Cr3+ occupying multiple cationic sites. Ca3MgSn0.5Zr0.5Ge3O12:0.1Cr3+ has excellent thermal stability (86%@425 K), and co-doping Pr3+ ions into Ca3MgSn0.5Zr0.5Ge3O12:0.1Cr3+ obtains highly efficient NIR emission. The Ca3MgSn0.5Zr0.5Ge3O12:0.01Pr3+,0.1Cr3+ phosphor has quantum yield of 89.4% thanks to the energy transfer effect from Pr3+ to Cr3+. The fabricated NIR phosphor-converted light emitting diodes (pc-LEDs) by integrating the blue chip with Ca3MgSn0.5Zr0.5Ge3O12:0.01Pr3+,0.1Cr3+ has diverse applications including night vision, non-destructive testing, and medical imaging.

Efficient near-infrared emission at 1070 nm in (Eu3+/Nd3+) ions pair activated NAFBT glasses by CET process for improving the silicon solar cell efficiency

Present work reveals the luminescent downconversion (LDC) process in a series of new sodium-aluminumfluoro borotellurite (NAFBT) glasses by co-doping Nd3+ concentrations (0.1, 0.5, 1.5, and 2.0 mol%) with a constant (2.0 mol%) Eu3+ content. The X-ray diffractogram and IR spectral studies have shown the amorphous like structure and functional groups of the fabricated NAFBT glasses. The fabricated glasses’ physical properties like density and molar volume, and their absorption in the 300–780 nm (UV-Visible) and 800–2300 nm (NIR) ranges were studied. The LDC effect via co-operative type energy transfer (CET) in NAFBT:(Eu3+/Nd3+) glasses was tested with the stimulation at 463 nm of Eu3+, showing a prominent 614 nm (visible) photon of Eu3+ and 907, 1070, and 1339 nm photons (NIR) of Nd3+ ions. The variation in percentage (%) of the integrated intensity at 1070 nm (Nd3+) and 614 nm (Eu3+) was studied as a function of Nd3+ concentration at a fixed Eu3+ content. The multipolar interactions between Nd3+ and Eu3+ ions in NAFBT glasses were studied by Reisfeld and Dexter energy transfer (ET) process. The decline of PL decay from 1.91 to 0.38 ms was represented by dipole-quadrupole interaction in NAFBT glasses. Asymmetric ratio and photometric parameters such as correlated color temperatures (∼1020 K), and (x, y) color coordinates nearly (0.65, 0.34) of red emission were also evaluated for NAFBT glasses. The intense NIR (1070 nm) emission matches well with the silicon solar spectrum and an increase of conversion efficiency (ηQE) from 125% to 199% demonstrate the potential application of NAFBT glass materials in crystalline silicon (c-Si) solar cells.

An efficient and thermally stable source with Cr3+ near-infrared luminescence for non-destructive testing applications

The quest for efficient and heat-resistant near-infrared (NIR) phosphors to create advanced smart NIR lighting sources continues to pose a significant challenge. This study introduces a new fluoride phosphor, Cr3+-doped Cs2NaScF6, wherein the Cs2NaScF6 host provides a weak crystal field suitable for Cr3+ doping. This arrangement allows the production of a broad NIR emission peaking at 797 nm, coupled with a notable internal quantum efficiency of 90.8 % when excited by 446 nm blue light. Meanwhile, due to the relatively mild electron-phonon coupling effect and a high activation energy within this phosphor, the overall NIR emission intensity at 150 °C sustains 81.8 % of its level at room temperature. This highlights exceptional thermal stability in photoluminescence performance. Combining the Cs2NaScF6:Cr3+ phosphor with a commercially available blue InGaN chip to construct a NIR light-emitting diode (LED) device, which exhibits efficient and stable NIR emission, making it suitable for non-destructive testing applications. These findings affirm that the Cs2NaScF6:Cr3+ phosphor can function as a promising candidate to fabricate high-performance device for NIR spectroscopy application.

Realizing efficient broadband near-infrared emission and multimode photoluminescence switching via coordination structure modulation in Sb3+-doped 0D organic metal chlorides.

Recently, organic Sb(III)-based metal halides have achieved significant results in the visible light region due to their efficient emission. However, realizing efficient broadband near-infrared (NIR) emission in such materials is a great challenge. Herein, we developed three different NIR emitters via a coordination structure modulation strategy in Sb3+-doped zero-dimensional organic metal chlorides of (C20H20P)2MnCl4, (C20H20P)2ZnCl4, and (C20H20P)2CdCl4 with tetrahedral structure. More specifically, after the dopant Sb3+ is inserted into the host lattice, the coordination structures of Sb3+ ions can change from [SbCl5]2- square-pyramidal configuration to [SbCl4]- clusters, which will bring a larger lattice distortion degree to the excited state compared to the ground state, resulting in a larger Stokes shift. Thus, efficient NIR emission with near-unity photoluminescence quantum yield (PLQY) can be obtained in Sb3+-doped compounds under 365 nm excitation. Moreover, Sb3+-doped NIR emitters also show remarkable stabilities, which prompts us to fabricate NIR phosphor conversion light-emitting diodes (pc-LEDs) and demonstrate their application in night vision. More interestingly, the Sb3+-doped (C20H20P)2MnCl4 shows tunable emission characteristics, which can be tuned from green to greenish-yellow, orange, red, and NIR emission under different external stimuli, and thus we can demonstrate the applications of this compound in quintuple-mode fluorescence anti-counterfeiting and information encryption.

Thermal stability and quantum efficiency improvement of Cr3+-activated garnet phosphors via regulating A/B sites for near-infrared LED applications.

The discovery of phosphors with highly efficient broadband near-infrared emission is urgent for constructing NIR sources for various applications. Herein, we synthesized a series of near-infrared emitting garnet-type (A3B2C3O12) Lu2-xCaAl3.99Cr0.01SiO12:xGd/La and Lu2CaAl3.99-yCr0.01SiO12:ySc/Ga phosphors and systematically investigated the effect of A/B-site substitution on the crystal structure and luminescence properties. Structural and optical analyses revealed that the A/B-site substitution weakened the crystal field strength, further enhancing the broadband emission of the allowed 4T2 → 4A2transition and diminishing the narrow-peak emission of the forbidden 2E → 4A2 transition. As expected, NIR phosphors, exemplified by Lu1.7CaAl3.99Cr0.01SiO12:0.3Gd and Lu2CaAl3.49Cr0.01SiO12:0.5Sc, showed outstanding thermal stabilities at 423 K (150 °C) registering values of 103.02% and 94.91%, with high quantum efficiencies of 80.48% and 85.01%, respectively. In addition, pc-LEDs with broadband NIR output and good optoelectronic properties have been realized, demonstrating the great potential of broadband NIR pc-LEDs for applications. This work not only provides a series of high-efficiency phosphors for NIR pc-LED applications, but also provides a systematic idea and an efficient method to improve the luminescence performance of garnet-type phosphors.

Efficient tunable visible and near-infrared emission in Sb3+/Sm3+-codoped Cs2NaLuCl6 for near-infrared light-emitting diode, triple-mode fluorescence anti-counterfeiting and information encryption

Efficient tunable visible and near-infrared emission in Sb3+/Sm3+-codoped Cs2NaLuCl6 for near-infrared light-emitting diode, triple-mode fluorescence anti-counterfeiting and information encryption

Purely organic near-infrared afterglow systems based on a triplet excimer donor

A kind of NIR afterglow with a lifetime of 0.16 s at 808 nm was prepared using triplet excimer (PVB@PVA) as the donor. PYB2@PVA containing more excimers is beneficial to improve luminescence of Cy7 acceptor via a triplet-to-singlet energy transfer.

Efficient near-infrared emission benefits from slowing down the internal conversion process.

Organic deep-red (DR) and near-infrared (NIR) emitters with high photoluminescence quantum yield (PLQY) are rare due to the strong non-radiative (knr) decay. Here, we report two DR/NIR emitters with high PLQY, TPANZPyPI and TPANZ3PI. Interestingly, the TPANZPyPI film exhibits 46.5% PLQY at 699 nm. Theoretical calculations indicate that TPANZPyPI can achieve this high PLQY in the near-infrared emission region due to its small S1 to S0 internal conversion (IC) rate. Meanwhile, research has found that, compared to TPANZ3PI, TPANZPyPI with a more rigid structure can effectively suppress the T2 to T1 IC process, which is conducive to higher exciton utilization efficiency (EUE). TPANZPyPI's non-doped OLED shows NIR emission with 4.6% @ 684 nm maximum external quantum efficiency (EQEmax). Its doped OLEDs radiate DR with an EQEmax of 6.9% @ 666 nm. These EQEs are among the highest values for hybridized local charge transfer state materials emitting more than 640 nm. This work demonstrates for the first time, based on a combination of theory and experiment, that increasing the molecular rigidity can inhibit the excited state IC process in addition to the S1 to S0 IC, realizing efficient electroluminescence.

Multi-site occupancy high-efficient Mg2LaTaO6:Cr3+ phosphor for application in broadband NIR pc-LEDs

As a new generation of near-infrared (NIR) light source, phosphor-converted NIR light emitting diodes (NIR pc-LEDs) have broad application prospects in biological tissue imaging, night vision and chemical composition analysis. However, most NIR emitting phosphors are still limited to short-wavelength, narrow-band emission and low efficiency. Here, based on the multi-site occupation strategy, the NIR phosphor Mg2LaTaO6:Cr3+ (MLT:Cr3+) achieves an efficient broadband NIR emission with the full width at half maximum (FWHM) of 203 nm in the range of 600–1300 nm under the excitation of 468 nm blue light. The phosphor MLT:0.01Cr3+ not only exhibits an excellent internal quantum efficiency (IQE) of 85.6 %, but also has good thermal stability and remains about 64.2 % photoluminescence (PL) intensity of room temperature at 423 K. Furthermore, the MLT:0.01Cr3+ phosphor was combined with a blue LED chip to fabricate the NIR pc-LED device, and its potential applications were successfully realized in information encryption, bioimaging and the qualitative or quantitative analysis of mixture of ethanol and water.

Broadband Near-Infrared Emission from 0D Hybrid Copper Halides.

Metal halides have attracted increasing attention owing to their outstanding optoelectronic properties and tunable emission characteristics. Among these, low-dimensional metal halides have emerged as a novel and efficient luminescent material, primarily attributed to their broad spectral emission induced by self-trapped excitons (STEs). However, achieving highly efficient deep red and near-infrared (NIR) emission in metal halides remains a challenge. In this study, we report a novel zero-dimensional (0D) copper-based metal halide [Na2(DMSO)8]Cu4Br6 as the NIR light source, which exhibits a full width at half-maximum (FWHM) of 195 nm peaking at 685 nm, an impressive quantum efficiency of 68% and a large Stokes shift of 299 nm. Through comprehensive spectral analysis and meticulous data calculations, we substantiate that the emission originates from STEs formed within the 0D structure. Furthermore, we demonstrate the potential application of [Na2(DMSO)8]Cu4Br6 as an invisible light source in night vision by combining it with a commercially available 365 nm ultraviolet (UV) chip. This work not only enriches the family of low-dimensional metal halide materials but also inspires the potential of low-dimensional metal halides in night vision applications.

Efficient and ultra-broadband near-infrared emission in perovskite-like Mg4Sb2O9:Cr3+ phosphor

Near-infrared (NIR) spectroscopy based on phosphor-converted NIR light-emitting-diode (LED) has extensive applications in modern life, stimulating the exploration of ultra-broadband NIR phosphors with high efficiency. Herein, Cr3+-doped perovskite-like Mg4Sb2O9 phosphor was synthesized, which exhibits a NIR emission with peak wavelength of 855 nm, and a full width at half maximum (FWHM) of about 207 nm. Upon 442 nm excitation, the quantum efficiency (QY) and absorption efficiency (AE) were determined to be 59.1 % and 48.3 %, respectively; while the luminescence intensity remained 61.5 % of room temperature at 373 K, indicating an excellent efficient and a moderate thermal stability of this material. The fabricated NIR pc-LED through combining the optimized phosphor with a 455 nm LED chip presents an output power of 20.1 mW and a photoelectronic conversion efficiency of 3.6 % under a driving current of 175 mA. These results suggest that Mg4Sb2O9:Cr3+ phosphor with excellent luminescent performance may have good potential for applications in NIR pc-LEDs.

Creating an efficient and tunable near-infrared emission by using [Mg2+-Sn4+] chemical unit co-substitution in Ga2O3:Cr3+ phosphor

NIR phosphor-converted light-emitting diode (NIR pc-LED) has attracted many attentions for its promising applications in biomedical imaging, night vision, spectroscopy, and many other fields, while the discovery of broadband NIR phosphors with high external quantum efficiency (EQE) remains a challenge. Herein, a series of efficient and tunable broadband NIR-emitting Ga1.97-2xMgxSnxO3:0.03Cr3+ phosphors were synthesized via [Mg2+-Sn4+] substituting [Ga3+-Ga3+] in Ga2O3:Cr3+ system. As increase of substituting ratio x, a significant red-shift in the emission spectra from 726 to 793 nm with a full width at half maximum (FWHM) extended from 121 to 167 nm can be observed. All the samples have an EQE above 40% under 450 nm excitation; and the excitation peak in the blue light region remains unchanged, enabling these materials to be efficiently excited by blue LEDs. Finally, a NIR pc-LED device was fabricated by integrating the optimized Ga1.77Mg0·1Sn0·1O3:0.03Cr3+ phosphor on a blue LED chip, which exhibits a high NIR output power of 33.41 mW with a photoelectric conversion efficiency of 12.01% under a drive current of 100 mA. These results indicate that the obtained NIR phosphors may have potential in NIR pc-LEDs applications.

Highly Efficient Broadband Near‐Infrared Emission from Sn2+ Alloyed Lead‐Free Cesium Zinc Halides

AbstractLuminescent metal halides have attracted increasing attention because of their tunable emission and superior photoelectric properties. However, it is still challenging to achieve near‐infrared (NIR) emission from metal halides, which is important in applications such as food quality analysis and night vision. In this work, the broadband NIR emission is achieved by alloying Sn2+ into zero‐dimensional (0D) Cs2ZnBr4. The incorporating of Sn2+ cations enables the originally weakly luminescent Cs2ZnBr4 to exhibit an efficient broadband NIR emission. Upon photoexication, the optimized Sn2+ alloyed Cs2ZnBr4 (Cs2Zn0.875Sn0.125Br4) exhibits a highly efficient broadband NIR emission peaked around 700 nm, with a large Stokes shift of 323 nm, a full width at maximum of 177 nm, and a high quantum efficiency of around 41%. Spectroscopic and theoretical calculations unveil that the efficient NIR emission originates from the self‐trapping emission introduced by the Sn alloying. In addition to the high efficient broadband emission, the Sn2+ alloyed Cs2ZnBr4 also exhibits high thermal stability, retaining 78% of its initial intensity at 150 °C. The night vision application is demonstrated by using a light source fabricated by combining Sn2+ alloyed Cs2ZnBr4 phosphor with a 365 nm LED chip in the dark.

Realize intelligent anti-counterfeiting and efficient near-infrared emission of indium-based perovskite through crystal phase and energy band engineering

The crystal phase and energy band adjustment of halide perovskites have become the focus of research. Sb3+ doped lead-free indium-based perovskites A2InX5·H2O:Sb3+ (A=Cs+, Rb+; X = Cl-, Br-) are synthesized at room temperature. Through changing the crystal phase structure, an intelligent anti-counterfeiting material is used to monitor water vapor and high temperature. Moreover, the Rb2InBr5·H2O:Sb3+ achieves broadband near-infrared (NIR) emission with a high photoluminescence quantum efficiency (PLQY) of 54.3%. The NIR light-emitting diode shows that the device can effectively achieve NIR imaging. Theoretical calculations further clarified that the regular changes in luminescence originate from energy band modulation. This work provides a broader sight for the synthesis, luminescence mechanism and application of indium-based perovskite.

Wide-coverage and Efficient NIR Emission from Single-component Nanophosphors through Shaping Multiple Metal-halide Packages.

Wide-coverage near infrared (NIR) phosphor-converted LEDs possess promising potential for practical applications, but little is developed towards the efficient and wide-coverage NIR phosphors. Here, we report the single-component lanthanide (Ln3+ ) ions doped Cs2 M(In0.95 Sb0.05 )Cl6 (M=alkali metal) nanocrystals (NCs), exhibiting emission from 850 to 1650 nm with high photoluminescence quantum yield of 20.3 %, which is accomplished by shaping the multiple metal halide octahedra of double perovskite via the simple alkali metal substitution. From Judd-Ofelt theoretical calculation and spectroscopic investigations, the shaping of metal halide octahedra in Cs2 M(In1-x Sbx )Cl6 NCs can break the forbidden of f-f transition of Ln3+ , thus increasing their radiative transition rates and simultaneously boosting the energy transfer efficiency from host to Ln3+ . Finally, the wide-coverage NIR LEDs based on Sm3+ , Nd3+ , Er3+ -tridoped Cs2 K0.5 Rb0.5 (In0.95 Sb0.05 )Cl6 NCs are fabricated and employed in the multiplex gas sensing and night-vision application.

Wide‐coverage and Efficient NIR Emission from Single‐component Nanophosphors through Shaping Multiple Metal‐halide Packages

AbstractWide‐coverage near infrared (NIR) phosphor‐converted LEDs possess promising potential for practical applications, but little is developed towards the efficient and wide‐coverage NIR phosphors. Here, we report the single‐component lanthanide (Ln3+) ions doped Cs2M(In0.95Sb0.05)Cl6 (M=alkali metal) nanocrystals (NCs), exhibiting emission from 850 to 1650 nm with high photoluminescence quantum yield of 20.3 %, which is accomplished by shaping the multiple metal halide octahedra of double perovskite via the simple alkali metal substitution. From Judd‐Ofelt theoretical calculation and spectroscopic investigations, the shaping of metal halide octahedra in Cs2M(In1−xSbx)Cl6 NCs can break the forbidden of f‐f transition of Ln3+, thus increasing their radiative transition rates and simultaneously boosting the energy transfer efficiency from host to Ln3+. Finally, the wide‐coverage NIR LEDs based on Sm3+, Nd3+, Er3+‐tridoped Cs2K0.5Rb0.5(In0.95Sb0.05)Cl6 NCs are fabricated and employed in the multiplex gas sensing and night‐vision application.