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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Achieving Broadband NIR-I to NIR-II Emission in an All-Inorganic Halide Double-Perovskite Cs2NaYCl6:Cr3+ Phosphor for Night Vision Imaging

Fengmei Zhu,Yuan Gao,Chunli Zhao,Jiacheng Pi,Jianbei Qiu

Near-infrared phosphor-converted light-emitting diodes (NIR pc-LEDs) offer numerous advantages, including compact size, tunable emission spectra, energy efficiency, and high integration potential. These features make them highly promising for various applications, such as night vision monitoring, food safety inspection, biomedical imaging, and theragnostics. All-inorganic halide double-perovskite materials, known for their large absorption cross section, excellent defect tolerance, and long carrier diffusion radius, serve as unique matrices for constructing near-infrared fluorescent materials. In this study, we successfully prepared the all-inorganic metal halide double-perovskite Cs2NaYCl6:Cr3+ using a grinding–sintering method. A small fraction of the [YCl6] octahedra within the host material’s lattice was substituted with Cr3+ ions, resulting in the creation of the Cs2NaYCl6:Cr3+ phosphor. When excited with λ = 310 nm UV light, the phosphor exhibited a broad emission range spanning from 800 to 1400 nm, covering the NIR-I and NIR-II regions. It had a broad bandwidth emission of 185 nm and achieved a fluorescence quantum yield of 20.2%. The unique broadband emission of the phosphor originates from the weak crystal field environment provided by the Cs2NaYCl6 host matrix, which enhances the luminescence properties of the Cr3+ ions. To create NIR pc-LEDs, the phosphor was encapsulated onto a commercially available UV LED chip operating at 310 nm. The potential application of these NIR pc-LEDs in night vision imaging was successfully validated.

研究领域: 材料科学 · 光学 · 生物医学工程
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PHYSICAL CHEMISTRY CHEMICAL PHYSICS · 2025 ·Vol. 27 ·期 45 ·24273-24283 · IF 2.9

Highly efficient Cr3+-doped K3Ga2(PO4)3 NIR-I phosphors with exceptional thermal quenching resistance for night vision monitoring and biomedical imaging applications

Jin Zou,Daoyun Zhu,Zhongfei Mu,Song Xu,Nurahmat Wali,Fugen Wu,Huafeng Dong,Xin Zhang,Xiao Wu,Yifei Luo,Yuchun Zhan

Near-infrared (NIR) spectroscopic technology has shown extensive application prospects. However, developing NIR phosphors with tunability and high thermal stability is a huge challenge. In this work, a highly promising phosphate compound, K3Ga2(PO4)3, has been successfully synthesized. When doped with Cr3+ ions, it is particularly noteworthy that Cr3+ exhibits highly efficient and thermally stable broadband NIR luminescence in the tetrahedral coordination environment. This unique property makes K3Ga2(PO4)3:Cr3+ a compelling candidate for advanced photonic applications. Therefore, studying the luminescent properties of Cr3+ rare earth ions doped into tetrahedral sites is of great significance. In the tetrahedral coordination environment of K3Ga2(PO4)3:Cr3+ ions exhibit broadband near-infrared emission spanning from 700 to 1100 nm (λem = 822 nm, FWHM = 124 nm) under 452 nm blue light excitation. Remarkably, the quantum efficiency reaches as high as 70.9%, demonstrating its exceptional potential for advanced photonic applications. In addition, the phosphors demonstrated exceptional thermal stability with near-zero thermal quenching. The NIR luminescence intensity at 373 K and 423 K retained 109.0% and 90.4% of its initial room-temperature value, respectively. This remarkable performance can be attributed to the material's ultra-wide band gap, and minimal electron–phonon coupling. The NIR pc-LED devices, fabricated by integrating the optimized K3Ga1.93(PO4)3:0.07Cr3+ phosphors with a blue LED chip (λex = 455 nm), achieved a near-infrared output power of 274 mW with a conversion efficiency of 5.42% under a driving current of 100 mA. Experimental results demonstrate that the fabricated NIR pc-LED exhibits significant potential for applications in night vision and vein imaging technologies. This study provides a strategic framework for designing high-performance NIR pc-LED devices, utilizing K3Ga2(PO4)3:Cr3+ as an efficient phosphor-converted light source, and offers valuable insights for practical implementation in advanced optical systems.

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Laser & Photonics Reviews · 2023 · IF 11

Achieving Nearly Quantitative (∼100%) IQE and 42.3% EQE Across NIR-I and NIR-II Regions with Cr3+-doped Cs2NaScCl6 under 300 nm Excitation

Chunli Zhao,Yuan Gao,Jing Wang,Jianbei Qiu

Lead-free rare-earth-based perovskites have received widespread attention for their unique optical properties, although achieving efficient broadband near-infrared (NIR) emission with these materials remains a challenge. Here the synthesis of a rare earth-based double perovskite (Cs 2 NaScCl 6 ) by an improved solid phase method is reported. The doping of Cr 3+ led to the formation of [CrCl 6 ] 3− octahedron, which exhibited a broadband NIR emission peaked at 950 nm and a half-peak width of 162 nm. It is worth noting that with the same actual Cr 3+ content, the luminous intensity of Cs 2 NaScCl 6 synthesized by the improved solid-phase synthesis is four times higher than the product synthesized by the hydrothermal method. an efficient Cl − -Cr 3+ charge transfer sensitization facilitated by localized electrons in [CrCl 6 ] 3− octahedron is the mechanism for the strong NIR emission of Cr 3+ is proposed. Calculations based on density functional theory and Bader charge analysis support the notion that electrons in [CrCl 6 ] 3− octahedrons are strongly localized in Cs 2 NaScCl 6 :Cr 3+ , which is conducive to the Cl − –Cr 3+ charge transfer process, resulting the internal quantum efficiency of 100% and external quantum yield as 42.3%. The highly efficient ultra-broadband NIR emission with excellent stability offers many opportunities for applications in the field of NIR night vision and bio-imaging.

CAS / MDL: 10060-12-5 20662-14-0
研究领域: 材料科学 · 光学 · 纳米技术 · 光子学
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Small · 2025 · IF 12.1

A Hydrogen Sulfide-Activated NIR-II Fluorescence/NIR-I Photoacoustic Dual-Ratiometric Nanoprobe With Unique Recognition Reaction for Precise Visual Diagnosis of Hepatitis Disease

Lixian Huang,Fei Lv,Yidong Bin,Jingjin Zhao,Caiying Li,Shulin Zhao,Shengqiang Hu,Liangliang Zhang

Hydrogen sulfide (H 2 S) is a vital gaseous signaling molecule that plays a central role in various physiological and pathological processes. Given the complementary advantages of fluorescence (FL) and photoacoustic (PA) imaging, there is a growing demand for dual-ratiometric probes that enable precise in vivo monitoring of H 2 S levels. In this study, the use of 2-mercapto-1,3,4-thiadiazole (MTD) as a novel recognition group of H 2 S is presented for the first time, following conjugation with cyanine dyes to obtain a new PA probe Cy-MTD. To achieve dual-ratiometric imaging, Cy-MTD is incorporated into down-conversion nanoparticle (DCNP), resulting in the creation of a pioneering NIR-II FL/NIR-I PA dual-ratiometric nanoprobe DCNP@Cy-MTD. Cy-MTD undergoes the blueshift in absorption from 840 to 670 nm after reaction with H 2 S, enabling NIR-I ratiometric PA imaging of H 2 S by measuring the ratio of PA signal at 670 and 840 nm (PA 670 /PA 840 ). In addition, due to the strong absorption of Cy-MTD ≈840 nm and the overlapping between the absorption spectrum of Cy-MTD and 808 nm excitation band of DCNP, the 808 nm-excited FL emission (F 1550 nm,808Ex ) of DCNP in DCNP@Cy-MTD nanoprobe is quenched through the competitive absorption, while it is restored upon the interaction with H 2 S because of the blueshift in absorption of Cy-MTD. Using the stable FL emission of DCNP under 980 nm excitation (F 1550 nm,980Ex ) as the reference signal, NIR-II ratiometric FL imaging (F 1550 nm,808Ex /F 1550 nm,980Ex ) of H 2 S is achieved. The dual-ratiometric response features of the DCNP@Cy-MTD nanoprobe offer a significant advancement over traditional single-signal or single-modality imaging techniques. By providing enhanced accuracy and reliability, this probe allows for the diagnosis of hepatitis by monitoring the H 2 S, surpassing the capabilities of conventional histopathological methods, which provides a new way for more effective diagnostic strategies for liver diseases.

研究领域: 生物医学工程 · 分子影像学 · 肝脏疾病研究
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Inorganic Chemistry Frontiers · 2024 ·Vol. 11 ·期 20 ·7098-7109 · IF 6.1

High performance NIR-I to NIR-II emission of a Cr3+-doped Cs2NaLuCl6 phosphor with an IQE and EQE of up to 92.9% and 60.75%

Fengmei Zhu,Yuan Gao,Jianbei Qiu

Presently, there is a need to expand the near-infrared (NIR) emission range, especially in the bio-transparent window, to improve the internal quantum efficiency and external quantum efficiency, and to minimize the shortcomings of luminescence properties. In this work, an ultra-broadband NIR emission Cr3+-doped Cs2NaLuCl6 all-inorganic metal halide perovskite phosphor was synthesized by a grinding–sintering method. Under 300 nm excitation, Cs2NaLuCl6:Cr3+ phosphors exhibited ultra-broadband NIR emission of 800–1400 nm, which covers nearly the entire NIR-I (700–1000 nm) and NIR-II (1000–1400 nm) regions; the emission peaked at around 960 nm, with a full width at half maximum of ∼182 nm. Noticeably, the internal- and external-quantum efficiencies of the optimized Cs2NaLuCl6:Cr3+ phosphor were as high as ∼92.9% and ∼60.75%, respectively. We showed through analysis and simulation that the weak crystal field strength is conducive to increasing the odd term of the crystal field, and therefore it partially released the restriction imposed by the parity prohibition law and improved the energy absorption efficiency of Cr3+. As the size of the phosphor approaches the wavelength of NIR luminescence, the apparent Mie scattering effect starts to take effect, which enhances the light extraction of NIR luminescence in the radial direction.

研究领域: 材料科学 · 光学 · 生物医学工程
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Advanced Optical Materials · 2024 ·Vol. 12 ·期 22 ·2300413 · IF 8

Ultra-Broadband Near-Infrared Luminescence from a Vanadium-Activated Phosphate Glass

Weirong Wang,Zhi Chen,Guanliang Yu,Yeming Zhang,Chun Jiang,Jianrong Qiu

Broadband near-infrared (NIR) emitting materials have gained considerable attention for their applications in lighting, displays, sensing, bio-imaging, and optical amplification. Recently, numerous excellent broadband NIR emitting materials are developed by introducing Cr 3+ , Bi + , or Ni 2+ ions to various hosts. However, there is a notable absence of reports on ultra-broadband NIR emitters spanning the entire telecommunication window as well as the NIR-I (700–1000 nm) and NIR-II (1000–1700 nm) biological windows activated by vanadium ions. Herein, the study presents, for the first time to the best of the knowledge, ultra-broadband NIR emission ranging from 850 to 1600 nm (peaking at ≈1000 nm) at room temperature in vanadium-doped phosphate glass. Detailed spectra and microscopic structure analysis reveal that two V 3+ -emitting centers predominantly contribute to the ultra-broadband emission, corresponding to 3 T 2 ( 3 F)→ 3 A 2 ( 3 F) spin-allowed and 3 T 2 ( 3 F)→ 1 E( 1 D) spin-forbidden electron transitions of tetrahedrally coordinated V 3+ ions. Notably, the tunability of NIR emission peak is demonstrated by adjusting the local glass structure or the vanadium doping content. Moreover, glass-converted light-emitting diodes (gc-LEDs) are fabricated from vanadium-doped glass, and the potential applications are demonstrated. The work opens new avenues for the design and fabrication of broadband NIR-emitting materials and opto-electronic devices.

CAS / MDL: 1314-56-3
研究领域: 材料科学 · 光学 · 光子学 · 生物医学工程
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DYES AND PIGMENTS · 2022 · IF 5.122

Fabrication of semiconducting polymer-blend dots with strong near-infrared fluorescence and afterglow luminescence for bioimaging

Feng Lu,Lili Li,Ting Zhao,Bingqiang Ding,Jiawei Liu,Qi Wang,Chen Xie,Quli Fan,Wei Huang

Fluorescence imaging at longer wavelength and autofluorescence-free imaging were two main strategies to improve the optical imaging performance of traditional near-infrared (NIR) fluorescence imaging, and the design of corresponding imaging agents were heavily explored recently. Herein, polymer-blend dots (PBdots) with strong fluorescence and afterglow luminescence in both NIR-I (700–900 nm) and NIR-II (900–1700 nm) windows were successfully fabricated by encapsulating two functional semiconducting polymers into one nanoparticle . With efficient intra-particle interactions, the PBdots exhibited an afterglow lifetime of 181 s after 730 nm NIR laser activation, which can be activated in vivo. The obtained PBdots with similar emission intensities in NIR-I and NIR-II regions enable fair comparison between different optical imaging modalities , which provides a clear guidance for the choice of suitable imaging modality for different purpose. As the first imaging agents which integrate NIR-II fluorescence imaging and NIR-I afterglow imaging, the PBdots also provide both high resolution and large signal-to-background ratio for blood vessel, lymph node and tumor imaging in living mice.

CAS / MDL: 109-99-9
研究领域: 材料科学 · 生物医学工程 · 光学 · 纳米技术 · 成像科学
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