In2BP3O12:Cr3+宽带近红外荧光粉的发光性能及应用研究※

doi:10.6023/A21120598

化学学报 ›› 2022, Vol. 80 ›› Issue (4): 453-459.DOI: 10.6023/A21120598 上一篇下一篇

所属专题：中国科学院青年创新促进会合辑

研究论文

In₂BP₃O₁₂:Cr³⁺宽带近红外荧光粉的发光性能及应用研究^※

张景荣^a^,^b^,^c, 黄得财^b^,^c^,^*(), 黄聪聪^b^,^c, 梁思思^b^,^c, 朱浩淼^a^,^b^,^c^,^d^,^*()

a 福建师范大学化学与材料学院福州 350003
b 中国科学院福建物质结构研究所中国科学院功能纳米结构设计与组装重点实验室福建省纳米材料重点实验室福州 350002
c 厦门稀土材料研究所厦门市稀土光电功能材料重点实验室厦门 361021
d 中国科学院赣江创新研究院赣州 341000

投稿日期:2021-12-30 发布日期:2022-04-28
通讯作者: 黄得财, 朱浩淼
作者简介:
^※ 庆祝中国科学院青年创新促进会十年华诞.
基金资助:
国家重点研发计划项目(2021YFB3500400); 国家自然科学基金(11904363); 以及中科院重点部署项目(ZDRW-CN-2021-3)

Investigation on the Luminescent Property and Application of In₂BP₃O₁₂:Cr³⁺ Broadband Near-Infrared Phosphor^※

Jingrong Zhang^a^,^b^,^c, Decai Huang^b^,^c(), Congcong Huang^b^,^c, Sisi Liang^b^,^c, Haomiao Zhu^a^,^b^,^c^,^d()

a College of Chemistry and Materials, Fujian Normal University, Fuzhou 350003, China
b CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Key Laboratory of Nanomaterials, Fujian Institute of Research on The Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
c Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials, Xiamen Institute of Rare Earth Materials, Xiamen 361021, China
d Ganjiang Innovation Academy, Chinese Academy of Sciences, Ganzhou 341000, China

Received:2021-12-30 Published:2022-04-28
Contact: Decai Huang, Haomiao Zhu
About author:
^※ Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Key R&D Program of China(2021YFB3500400); National Natural Science Foundation of China(11904363); Key Research Program of the Chinese Academy of Sciences(ZDRW-CN-2021-3)

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摘要/Abstract

近红外光谱技术在安防监控、食品检测、生物成像、农业等领域具有重要应用价值, 而开发出紧凑高效的近红外光源是其大规模商业应用的前提. 荧光粉转换型近红外发光二极管(light emitting diodes, LED)光源具有结构紧凑、成本低、使用寿命长、发射光谱可调等优点, 因此近些年受到广泛关注, 其关键就在于开发出能被蓝光有效激发的高性能近红外荧光粉. 本工作利用高温固相法制备了一种新型宽带近红外荧光粉In₂BP₃O₁₂:Cr³⁺, 在480 nm激发下, 荧光粉发射峰值位于950 nm, 光谱覆盖了750~1350 nm范围, 半峰宽达到210 nm. 采用该荧光粉与商用蓝光InGaN LED芯片封装, 获得了具有宽带发射的近红外LED光源, 在60 mA的驱动电流下, 近红外光辐射功率为5 mW. 当采用该光源照射人的手掌, 用近红外电感耦合器(charge coupled device, CCD)相机能够对手掌中的血管进行清晰的成像. 上述结果表明该近红外荧光粉可用于制备基于蓝光芯片的宽带近红外LED光源, 并在生物医学等领域具有潜在应用前景.

关键词: 近红外荧光粉, In₂BP₃O₁₂, LEDs, 发光材料, 宽带发射

Near-infrared (NIR) spectroscopy technique plays an important role in night-vision surveillance, food analysis, bioimaging and agriculture fields, and the development of compact and efficient NIR light source is a precondition for their massive commercial applications. Phosphor-converted light emitting diodes (pc-LED) have the advantages of compactness, low-cost, and long operating lifetime, thus have attracted considerable attentions in recent years. The key point is to exploit high performance NIR phosphors which can be excited efficiently by blue diode chips. A number of Cr³⁺-activated phosphors have been investigated aiming at NIR pc-LED applications. Nevertheless, most of the NIR phosphors show relatively short peak wavelength and narrow full width at half maximum (FWHM), resulting in spectral deficiency in the range 900~1100 nm. The phosphors with ultrabroad bandwidth are more desirable for spectroscopic applications. In this work, a novel broadband NIR light emitting phosphor In₂BP₃O₁₂:Cr³⁺ is synthesized by solid state reaction method. The structure, concentration and temperature dependent luminescence properties, electron-phonon coupling as well as the NIR LED performances and applications of the In₂BP₃O₁₂:Cr³⁺ have been investigated. Upon 480 nm excitation, the In₂BP₃O₁₂:Cr³⁺ phosphor shows a broad emission band peaked at 950 nm and covering 750~1350 nm (bandwidth of ~210 nm), which is owing to the ⁴T₂ → ⁴A₂ transition of Cr³⁺ ions. It is found that the emission intensity of the phosphor at 373 K keep 40% of that at room temperature. A NIR pc-LED is packaged by combining the In₂BP₃O₁₂:Cr³⁺ phosphor and a commercial blue InGaN chip, which generates broad NIR light emissions with an output power of ~5 mW at 60 mA drive current. When this NIR pc-LED is used to illuminate the human palm, the blood vessels in the palm are clearly imaged by a NIR charge coupled device (CCD) camera. These results suggest that the In₂BP₃O₁₂:Cr³⁺ is a promising phosphor for fabricating NIR pc-LEDs, which are potential for non-destructive analysis in the fields of biology and medicine.

Key words: near infrared phosphor, In₂BP₃O₁₂, LEDs, luminescent materials, broadband emission

引用此文

张景荣, 黄得财, 黄聪聪, 梁思思, 朱浩淼. In₂BP₃O₁₂:Cr³⁺宽带近红外荧光粉的发光性能及应用研究^※[J]. 化学学报, 2022, 80(4): 453-459.

Jingrong Zhang, Decai Huang, Congcong Huang, Sisi Liang, Haomiao Zhu. Investigation on the Luminescent Property and Application of In₂BP₃O₁₂:Cr³⁺ Broadband Near-Infrared Phosphor^※[J]. Acta Chimica Sinica, 2022, 80(4): 453-459.

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图/表 4

图1. (a) In2BP3O12晶体的结构示意图; (b) In2BP3O12:xCr3+ (x=2%~12%)样品的XRD图; (c) In2BP3O12:10%Cr3+样品的Rietveld结构精修图; (d) In2BP3O12:10%Cr3+样品的扫描电子显微图(SEM)及元素mapping图

Figure 1. (a) Crystal structure of In2BP3O12 crystal. (b) XRD patterns of In2BP3O12:xCr3+ (x=2%~12%) samples. (c) Rietveld refinement of the XRD pattern for In2BP3O12:10%Cr3+ sample. (d) Scanning electron microscope (SEM) and elemental mapping images of In2BP3O12:10%Cr3+ sample

图2. (a) In2BP3O12:xCr3+ (x=0 %~12%)的漫反射光谱; (b) In2BP3O12:10%Cr3+样品的激发和发射光谱; (c) Cr3+ (3d3)离子在八面体配位晶体场环境中的能级图; (d) In2BP3O12:xCr3+ (x=2%~12%)的发射光谱; (e) In2BP3O12:xCr3+ (x=2%~12%)发射强度归一化后的发射光谱; (f) In2BP3O12: xCr3+(x=4%~12%)样品的荧光衰减曲线

Figure 2. (a) Diffuse reflection spectra of In2BP3O12:xCr3+ (x=0%~12%) samples. (b) Excitation and emission spectra of the In2BP3O12:10%Cr3+ sample. (c) Energy level diagram for Cr3+ (3d3) ions in an octahedral crystal field. (d) Emission spectra of In2BP3O12:xCr3+(x=2%~12%) samples. (e) Normalized emission spectra of In2BP3O12:xCr3+ (x=2%~12%) samples. (f) PL decay curves of In2BP3O12:xCr3+ (x=4%~12%) samples

图3. (a) In2BP3O12:10%Cr3+的二维变温光谱; (b) 归一化发光积分强度变化图 (298~523 K); (c) In2BP3O12:10%Cr3+样品在298~473 K范围内的荧光衰减曲线; (d) In2BP3O12:10%Cr3+样品In[(I0/IT)–1]与1/kT的线性关系

Figure 3. (a) PL/temperature correlation map of the In2BP3O12:10%Cr3+ sample. (b) The integrated PL intensity of the In2BP3O12:10%Cr3+ as a function of temperature at 298~523 K. (c) PL decay curves of the In2BP3O12:10%Cr3+ sample at 298~473 K. (d) The linear relationship of In[(I0/IT)–1] versus 1/kT for the In2BP3O12:10%Cr3+ sample

图4. (a) 采用In2BP3O12:10%Cr3+荧光粉与蓝光芯片封装得到的近红外pc-LED的电致发光光谱(插图为pc-LED器件照片); (b) 近红外pc-LED照明下手掌的影像

Figure 4. (a) Electroluminescence spectra of the pc-LED fabricated with the In2BP3O12:10%Cr3+ phosphor and a blue diode chip (the inset is the photograph of the fabricated pc-LED). (b) Image of the palm under the illumination of the fabricated NIR pc-LED

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In₂BP₃O₁₂:Cr³⁺宽带近红外荧光粉的发光性能及应用研究^※

Investigation on the Luminescent Property and Application of In₂BP₃O₁₂:Cr³⁺ Broadband Near-Infrared Phosphor^※

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