CN116536044A - A preparation method of broadband deep red-near-infrared pc-LED fluorescent material and near-infrared light source - Google Patents

A preparation method of broadband deep red-near-infrared pc-LED fluorescent material and near-infrared light source Download PDF

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CN116536044A
CN116536044A CN202310336420.6A CN202310336420A CN116536044A CN 116536044 A CN116536044 A CN 116536044A CN 202310336420 A CN202310336420 A CN 202310336420A CN 116536044 A CN116536044 A CN 116536044A
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fluorescent material
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led fluorescent
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孙立忠
袁艳
徐昌富
林民椿
刘太
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Xiangtan University
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    • HELECTRICITY
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    • H10HINORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
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    • HELECTRICITY
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Abstract

The invention discloses a broadband deep red-near infrared pc-LED fluorescent material, a preparation method thereof and a near infrared light source. The fluorescent material comprises a structural general formula A 3 B 2‑y C y D 3 O 12 :xCr 3+ Wherein A is Ca and/or Sr, B is at least one of Al, sc and Lu, C is at least one of Al, sc and Lu, and D is at least one of Ge, si and Sn, hf; the y is more than 0 and less than 2,0<x<0.3. The fluorescent material is prepared by uniformly mixing raw materials including an A source, a B source, a C source and a D source, and sequentially performing mechanical activation and sintering. The fluorescent powder has adjustable spectrum, high internal quantum efficiency and heatThe stability is good, and the manufacturing is simple, the cost is low, and the industrialization is easy to realize.

Description

一种宽带深红-近红外pc-LED荧光材料的制备方法及近红外 光源A preparation method of broadband deep red-near-infrared pc-LED fluorescent material and its near-infrared light source

技术领域technical field

本发明涉及一种pc-LED荧光材料,具体涉及一种宽带深红-近红外pc-LED荧光材料的制备方法及近红外光源,属于荧光材料技术领域。The invention relates to a pc-LED fluorescent material, in particular to a preparation method of a broadband deep red-near-infrared pc-LED fluorescent material and a near-infrared light source, belonging to the technical field of fluorescent materials.

背景技术Background technique

随着白光LED照明技术工艺(成本低)和效率(光电转化效率高达80%)不断成熟和提高,科研工作者开始把目光放到可见光之外的区域宽带深红-近红外光(650-1400nm),发现近红外光源在近红外光谱技术、植物人工补光、夜视照明、虹膜识别、手掌静脉成像、生物医学成像、生物疾病诊断与治疗、发光太阳能聚光器、光通信等众多领域中存在广泛应用。这一重大发现使众多科研工作者对深红及近红外光源展开研究。目前能够产生近红外光源的有卤钨灯、近红外LED阵列、碳化硅加热元件和荧光粉转换的LED等四种主要方式,卤钨灯、近红外LED阵列、碳化硅具有寿命短、发光效率低、成本高、体积大等不足限制其在近红外方面的应用。与传统的近红外光源不同,荧光粉转换的LED作为新型的近红外光源,具有寿命长、体积小、成本低等优势,这为近红外应用提供了一种可用的潜在光源,但其仍然存在这输出功率低、热稳定性查、发射谱带等不足。With the continuous maturity and improvement of white LED lighting technology (low cost) and efficiency (photoelectric conversion efficiency up to 80%), researchers began to focus on areas other than visible light, broadband deep red-near infrared light (650-1400nm ), found that near-infrared light sources are used in many fields such as near-infrared spectroscopy technology, plant artificial light supplement, night vision lighting, iris recognition, palm vein imaging, biomedical imaging, biological disease diagnosis and treatment, luminous solar concentrators, optical communications, etc. There is a wide range of applications. This major discovery has led many researchers to conduct research on deep red and near-infrared light sources. At present, there are four main methods that can produce near-infrared light sources: halogen tungsten lamps, near-infrared LED arrays, silicon carbide heating elements, and phosphor-converted LEDs. The disadvantages of low cost, high cost, and large volume limit its application in near-infrared. Different from traditional near-infrared light sources, phosphor-converted LEDs, as a new type of near-infrared light source, have the advantages of long life, small size, and low cost, which provide a usable potential light source for near-infrared applications, but they still exist This has the disadvantages of low output power, poor thermal stability, and emission bands.

荧光粉转换的LED的发光性能取决于近红外荧光粉的发光性质,这些年来众多科研工作者已经开发了许多可用蓝光激发的Cr3+掺杂的高效宽带深红-近红外荧光粉,但是面对实用大功率的高效率、优异稳定性、良好器件性能等要求,近红外荧光粉仍然有许多的路要走。当前,优异高效、热稳定性好的近红外荧光粉的制备难点主要存在三点:一是Cr3+的3d-3d跃迁是奇偶跃迁禁阻,导致较低的电子吸收率和外量子效率。二是弱晶体场的4T2能级位置较低,激发态的电子更加容易通过多声子发射等无辐射跃迁回到基态,导致荧光粉的内量子效率低。三是随着温度的升高,Cr3+的电子发生无辐射跃迁的几率会增大,荧光粉的发光强度显著下降,热猝灭加剧。The luminous performance of phosphor-converted LEDs depends on the luminescent properties of near-infrared phosphors. Over the years, many researchers have developed many high-efficiency broadband deep-red-near-infrared phosphors doped with Cr 3+ that can be excited by blue light. For practical high-power requirements such as high efficiency, excellent stability, and good device performance, near-infrared phosphors still have a long way to go. At present, there are three main difficulties in the preparation of near-infrared phosphors with excellent efficiency and good thermal stability: First, the 3d-3d transition of Cr 3+ is forbidden by even and odd transitions, resulting in lower electron absorption rate and external quantum efficiency. The second is that the 4 T 2 energy level of the weak crystal field is lower, and the electrons in the excited state are more likely to return to the ground state through non-radiative transitions such as multi-phonon emission, resulting in low internal quantum efficiency of the phosphor. The third is that as the temperature increases, the probability of non-radiative transition of Cr 3+ electrons will increase, the luminous intensity of the phosphor will decrease significantly, and the thermal quenching will intensify.

为了克服现存的Cr3+掺杂宽带近红外面临的问题,依据Cr3+的发光性能深受晶体场强影响的性质来调控基质晶格的晶体场强。一般情况下,当外来离子掺杂进宿主晶格时,局部晶格会发生扭曲,由于晶格中不同格位的扭曲程度是不一样的,造成宏观上的扭曲分布现象,引起荧光粉的发射带发生拓宽和发光效率下降。但是,也存在外来离子的掺杂会引入奇对称场,打破Cr3+的3d-3d电子跃迁禁阻,增加Cr3+对光子的吸收度,从而提高发光强度、内量子效率、外量子效率等发光性能。In order to overcome the existing problems faced by Cr 3+ doped broadband near-infrared, the crystal field strength of the host lattice is regulated according to the property that the luminescence performance of Cr 3+ is deeply affected by the crystal field strength. Under normal circumstances, when foreign ions are doped into the host lattice, the local lattice will be distorted, because the degree of distortion of different sites in the lattice is different, resulting in a macroscopic distorted distribution phenomenon, causing the emission of the phosphor The band widens and the luminous efficiency decreases. However, there are also foreign ion doping that will introduce an odd symmetry field, break the 3d-3d electronic transition barrier of Cr 3+ , increase the absorption of Cr 3+ to photons, thereby improving the luminous intensity, internal quantum efficiency, and external quantum efficiency. and other luminescent properties.

中国发明专利(CN114292646B)公开了一种近红外发光材料和制备方法以及使用其的近红外光源,所述近红外发光材料的化学通式为AB2M2-xCrxV3O12,其中,A为Li、Na、K和Ag元素中的一种,B为Ca、Sr和Ba元素中的一种或多种,M为Ca、Mg和Zn元素中的一种或多种;x为Cr元素的摩尔分数,其中0≤x≤0.1。本发明提供的近红外发光材料,可被300~400nm的紫外、近紫外光激发,发射出光谱范围在400~700nm可见光和700~1100nm的近红外光,可同时用于近红外LED光源和提高太阳能电池转换效率;本发明采用固相法,制备方法简单,绿色无污染,适合规模化生产。然而该专利主要在于调节荧光材料的发射带宽,其光效和对于激发光的适配性仍存在很大的不足,难以满足使用大功率LED器件的性能要求。Chinese invention patent (CN114292646B) discloses a near-infrared luminescent material and its preparation method and a near-infrared light source using it. The general chemical formula of the near-infrared luminescent material is AB 2 M 2-x Cr x V 3 O 12 , wherein , A is one of Li, Na, K and Ag elements, B is one or more of Ca, Sr and Ba elements, M is one or more of Ca, Mg and Zn elements; x is Mole fraction of Cr element, where 0≤x≤0.1. The near-infrared luminescent material provided by the present invention can be excited by 300-400nm ultraviolet and near-ultraviolet light, emit visible light in the spectral range of 400-700nm and near-infrared light in the range of 700-1100nm, and can be used for near-infrared LED light sources and improving Solar cell conversion efficiency; the invention adopts a solid-phase method, the preparation method is simple, green and pollution-free, and suitable for large-scale production. However, this patent mainly focuses on adjusting the emission bandwidth of the fluorescent material, and its luminous efficiency and adaptability to excitation light still have great deficiencies, making it difficult to meet the performance requirements of using high-power LED devices.

发明内容Contents of the invention

针对现有技术存在的问题,本发明的第一个目的在于提供一种宽带深红-近红外pc-LED荧光材料,该荧光材料基于各组成元素间的协同作用,通过严格控制各组成元素的添加比例,调控发射光波长,为不同场合中的近红外应用提供多种最优的光源材料。Aiming at the problems existing in the prior art, the first object of the present invention is to provide a broadband deep red-near infrared pc-LED fluorescent material, which is based on the synergistic effect of each constituent element, and by strictly controlling the Adding proportions, regulating the wavelength of emitted light, and providing a variety of optimal light source materials for near-infrared applications in different occasions.

本发明的第二个目的在于提供一种宽带深红-近红外pc-LED荧光材料的制备方法,该方法采用一锅法固相烧结工艺,通过机械活化提高原料表面的活化能,便于后期烧结成型。该方法具有工艺简单、成本低廉等有点,适合大规模工业化生产。The second object of the present invention is to provide a preparation method of broadband deep red-near infrared pc-LED fluorescent material, the method adopts a one-pot solid-phase sintering process, and the activation energy of the raw material surface is improved through mechanical activation, which is convenient for later sintering forming. The method has the advantages of simple process and low cost, and is suitable for large-scale industrial production.

本发明的第三个目的就是在于提供一种高效耐热宽带深红近红外光源,该光源采用蓝光芯片作为激发光源,利用硅胶或树脂可以将这种荧光粉与蓝光芯片进行封装,并加装滤波片,最终得到采集波段为650~1200nm的近红外发光光源。The third purpose of the present invention is to provide a high-efficiency heat-resistant broadband deep red near-infrared light source. The light source uses a blue light chip as an excitation light source. The fluorescent powder and the blue light chip can be packaged with silica gel or resin, and installed filters to finally obtain a near-infrared luminescent light source with an acquisition band of 650-1200nm.

为实现上述技术目的,本发明提供了一种宽带深红-近红外pc-LED荧光材料,所述荧光材料为包含结构通式A3B2-yCyD3O12:xCr3+的氧化物,其中,A为Ca和/或Sr,B为Al、和Lu中的至少一种,C为Al、和Lu中的至少一种,D为Ge、Si、Sn和Hf中的至少一种;所述0<y<2,0<x<0.3。In order to achieve the above technical purpose, the present invention provides a broadband deep red-near-infrared pc-LED fluorescent material, the fluorescent material is containing the general structural formula A 3 B 2-y C y D 3 O 12 :xCr 3+ Oxide, wherein, A is Ca and/or Sr, B is at least one of Al and Lu, C is at least one of Al and Lu, and D is at least one of Ge, Si, Sn and Hf species; said 0<y<2, 0<x<0.3.

本发明所提供的荧光材料,基于原料各组分之间的协同作用,依据Cr3+的发光性能深受晶体场强影响的性质来调控基质晶格的晶体场强,通过晶体工程调控理论采用Al3+取代Lu3+格位来进一步提高其发光性能。The fluorescent material provided by the present invention is based on the synergistic effect between the various components of the raw materials, and the crystal field strength of the matrix lattice is regulated according to the property that the luminescent performance of Cr 3+ is deeply affected by the crystal field strength, and the crystal engineering control theory adopts Al 3+ replaces Lu 3+ sites to further improve its luminescent properties.

A3B2-yCyD3O12:xCr3+是一种石榴石结构的基质材料,本身是不发光的,A与O八配位形成十二面体,B/C与O六配位形成八面体,D与O四配位形成四面体,该基质结构中八面体为Cr3+提供可占据或者可替代的格点,起到一个固定Cr3+的作用,Cr3+作为有一种激活离子,当掺杂Cr3+时,Cr3+与配体周围的局部环境发生相互作用从而产生发射带。A 3 B 2-y C y D 3 O 12 :xCr 3+ is a garnet-structured host material, which is non-luminescent. A and O are eight-coordinated to form a dodecahedron, and B/C and O are six-coordinated. D and O form tetrahedrons, and D and O form tetrahedrons. In this matrix structure, octahedrons provide Cr 3+ with occupiable or replaceable lattice sites, and play a role in fixing Cr 3+ . Cr 3+ acts as a An active ion, when doped with Cr 3+ , Cr 3+ interacts with the local environment around the ligand to generate an emission band.

作为一项优选的方案,所述荧光材料的空间群为I-3ad。As a preferred solution, the space group of the fluorescent material is I-3ad.

作为一项优选的方案,所述荧光材料中的A为Ca,B和C为Lu和Al,D为Ge。As a preferred solution, A in the fluorescent material is Ca, B and C are Lu and Al, and D is Ge.

作为一项优选的方案,所述Al和Lu的摩尔比为1.2~1.9:0.1~0.8。Al和Lu的添加量要严格按照上述要求执行,当掺杂少量Al3+时,样品的内量子效率会逐渐增加至100%左右,当Al3+的掺杂含量超过1.4时,内量子效率开始显著下降。As a preferred solution, the molar ratio of Al and Lu is 1.2-1.9:0.1-0.8. The amount of Al and Lu to be added should be strictly in accordance with the above requirements. When a small amount of Al 3+ is doped, the internal quantum efficiency of the sample will gradually increase to about 100%. When the doping content of Al 3+ exceeds 1.4, the internal quantum efficiency began to decline significantly.

本发明还提供了一种宽带深红-近红外pc-LED荧光材料的制备方法,将包含A源、B源和C源在内的原料混合均匀,依次经机械活化和烧结,即得。The invention also provides a preparation method of a broadband deep red-near infrared pc-LED fluorescent material, comprising uniformly mixing raw materials including source A, source B and source C, followed by mechanical activation and sintering to obtain the finished product.

作为一项优选的方案,所述A源为氧化钙、氢氧化钙、氧化锶和氢氧化锶中的至少一种。As a preferred solution, the source of A is at least one of calcium oxide, calcium hydroxide, strontium oxide and strontium hydroxide.

作为一项优选的方案,所述B源为氧化铝、和氧化镥中的至少一种。As a preferred solution, the B source is at least one of alumina and lutetium oxide.

作为一项优选的方案,所述C源为为氧化铝、和氧化镥中的至少一种。As a preferred solution, the C source is at least one of alumina and lutetium oxide.

作为一项优选的方案,所述D源为氧化锗。As a preferred solution, the D source is germanium oxide.

作为一项优选的方案,所述机械活化的方式为高能球磨或机械研磨。As a preferred solution, the mechanical activation method is high-energy ball milling or mechanical grinding.

作为一项优选的方案,所述原料混合的方式为球磨或机械研磨;所述球磨的条件为:时间为20~30min,转速为150~300r/min。As a preferred solution, the mixing method of the raw materials is ball milling or mechanical grinding; the conditions of the ball milling are: the time is 20-30 min, and the rotation speed is 150-300 r/min.

作为一项优选的方案,所述烧结的方式为高温烧结,其条件为:以8~12℃/min从室温升温至1300~1400℃,保温5~8h,随炉冷却至室温。As a preferred solution, the sintering method is high-temperature sintering, and the conditions are as follows: the temperature is raised from room temperature to 1300-1400 °C at 8-12 °C/min, kept for 5-8 hours, and cooled to room temperature with the furnace.

本发明还提供了一种高效耐热宽带深红近红外光源,包括上述优选方案中任意一项所述的近红外pc-LED荧光材料、蓝光LED芯片和滤光片;所述蓝色LED芯片与荧光材料之间通过封装胶封装,所述滤光片固定覆盖在封装胶上。The present invention also provides a high-efficiency heat-resistant broadband deep red near-infrared light source, including the near-infrared pc-LED fluorescent material, blue LED chip and optical filter described in any one of the above-mentioned preferred solutions; the blue LED chip The fluorescent material is encapsulated by encapsulating glue, and the optical filter is fixedly covered on the encapsulating glue.

作为一项优选的方案,所述光源的发光中心为700~900nm。As a preferred solution, the luminescence center of the light source is 700-900 nm.

作为一项优选的方案,所述封装胶为硅胶或环氧树脂,所述滤波片的传输波长≥500nm。As a preferred solution, the packaging glue is silica gel or epoxy resin, and the transmission wavelength of the filter is ≥500nm.

相对现有技术,本发明的具有以下有益效果:Compared with the prior art, the present invention has the following beneficial effects:

1)本发明所提供近红外pc-LED荧光材料基于各组成元素间的协同作用,通过严格控制各组成元素的添加比例,调控激发光波长,从而实现最有利于虹膜图像采集波段的最优化选择。1) The near-infrared pc-LED fluorescent material provided by the present invention is based on the synergy between the constituent elements, and by strictly controlling the addition ratio of each constituent element, the wavelength of the excitation light is regulated, so as to realize the optimal selection of the band that is most conducive to iris image acquisition .

2)本发明所提供的制备方法中,采用一锅法固相烧结工艺,通过机械活化提高原料表面的活化能,使得各元素能够均一化互相嵌合,通过高温烧结成型,赋予材料优异的中熵效应。该方法具有工艺简单、成本低廉等有点,适合大规模工业化生产。2) In the preparation method provided by the present invention, a one-pot solid-phase sintering process is adopted to increase the activation energy of the raw material surface through mechanical activation, so that each element can be uniformly embedded with each other, and through high-temperature sintering molding, the material is endowed with excellent neutrality. entropy effect. The method has the advantages of simple process and low cost, and is suitable for large-scale industrial production.

3)本发明所提供的技术方案中,利用本法发明所提供的荧光材料所制备的光源具有优异的光学性能,该光源采用蓝光芯片作为激发光源,利用硅胶或树脂可以将这种荧光粉与蓝光芯片进行封装,并加装传输波长≥500nm的滤波片,最终得到650~1200nm的宽带深红-近红外发光光源。3) In the technical scheme provided by the present invention, the light source prepared by utilizing the fluorescent material provided by the present invention has excellent optical performance, and the light source adopts a blue light chip as an excitation light source, and the phosphor powder can be combined with silica gel or resin. The blue-ray chip is packaged, and a filter with a transmission wavelength ≥ 500nm is installed, and finally a broadband deep red-near-infrared light source of 650-1200nm is obtained.

附图说明Description of drawings

图1为实施例1~6所得荧光材料的XRD图;Fig. 1 is the XRD figure of embodiment 1~6 obtained fluorescent material;

图2为对比例1所得荧光材料制备的近红外光源的光谱图;Fig. 2 is the spectrogram of the near-infrared light source prepared by the fluorescent material obtained in Comparative Example 1;

图3为实施例1~6所得荧光材料制备的近红外光源的光谱图;Fig. 3 is the spectrogram of the near-infrared light source prepared by the fluorescent material obtained in Examples 1-6;

图4为本发明实施例1~6所得荧光材料制备的近红外光源的结构示意图;4 is a schematic structural view of a near-infrared light source prepared from fluorescent materials obtained in Examples 1 to 6 of the present invention;

图5为利用本发明实施例2提供的荧光材料所制备的红外光源的内量子产率图。Fig. 5 is a diagram of the internal quantum yield of the infrared light source prepared by using the fluorescent material provided in Example 2 of the present invention.

具体实施方式Detailed ways

在以下的说明过程中,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。In the following description, it is obvious that the described embodiments are only some of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

以下实施例所采用的原料为CaCO3、Lu2O3、Al2O3、GeO2和Cr2O3,制备所得荧光材料的结构式为Ca3Lu1.94-yAlyGe3O12:xCr3+The raw materials used in the following examples are CaCO 3 , Lu 2 O 3 , Al 2 O 3 , GeO 2 and Cr 2 O 3 , and the structural formula of the prepared fluorescent material is Ca 3 Lu 1.94-y Aly Ge 3 O 12 :xCr 3+ .

实施例1Example 1

本实施例中的y为0.5,x为0.06,根据化学计量数称取原料,于玛瑙研钵中充分研磨后装入刚玉坩埚,以升温速率为10摄氏度/分钟从室温升温至1350℃,保温6h,随炉冷却至室温,即得。In this example, y is 0.5, and x is 0.06. The raw materials are weighed according to the stoichiometric number, fully ground in an agate mortar and put into a corundum crucible, and the temperature is raised from room temperature to 1350°C at a heating rate of 10°C/min, and kept warm 6h, cooled to room temperature with the furnace, that is.

实施例2Example 2

本实施例中的y为0.7,x为0.06,根据化学计量数称取原料,于玛瑙研钵中充分研磨后装入刚玉坩埚,以升温速率为10摄氏度/分钟从室温升温至1350℃,保温6h,随炉冷却至室温,即得。In this example, y is 0.7, and x is 0.06. The raw materials are weighed according to the stoichiometric number, fully ground in an agate mortar and put into a corundum crucible, and the temperature is raised from room temperature to 1350°C at a heating rate of 10°C/min, and kept warm 6h, cooled to room temperature with the furnace, that is.

实施例3Example 3

本实施例中的y为1.0,x为0.06,根据化学计量数称取原料,于玛瑙研钵中充分研磨后装入刚玉坩埚,以升温速率为10摄氏度/分钟从室温升温至1350℃,保温6h,随炉冷却至室温,即得。In this example, y is 1.0, and x is 0.06. The raw materials are weighed according to the stoichiometric number, fully ground in an agate mortar and put into a corundum crucible, and the temperature is raised from room temperature to 1350°C at a heating rate of 10°C/min, and kept warm 6h, cooled to room temperature with the furnace, that is.

实施例4Example 4

本实施例中的y为1.2,x为0.06,根据化学计量数称取原料,于玛瑙研钵中充分研磨后装入刚玉坩埚,以升温速率为10摄氏度/分钟从室温升温至1350℃,保温6h,随炉冷却至室温,即得。In this example, y is 1.2, and x is 0.06. The raw materials are weighed according to the stoichiometric number, fully ground in an agate mortar and put into a corundum crucible, and the temperature is raised from room temperature to 1350°C at a heating rate of 10°C/min, and kept warm 6h, cooled to room temperature with the furnace, that is.

实施例5Example 5

本实施例中的y为1.4,x为0.06,根据化学计量数称取原料,于玛瑙研钵中充分研磨后装入刚玉坩埚,以升温速率为10摄氏度/分钟从室温升温至1350℃,保温6h,随炉冷却至室温,即得。In this example, y is 1.4, and x is 0.06. The raw materials are weighed according to the stoichiometric number, fully ground in an agate mortar and put into a corundum crucible, and the temperature is raised from room temperature to 1350 °C at a heating rate of 10 °C/min. 6h, cooled to room temperature with the furnace, that is.

实施例6Example 6

本实施例中的y为1.6,x为0.06,根据化学计量数称取原料,于玛瑙研钵中充分研磨后装入刚玉坩埚,以升温速率为10摄氏度/分钟从室温升温至1350℃,保温6h,随炉冷却至室温,即得。In this example, y is 1.6, and x is 0.06. The raw materials are weighed according to the stoichiometric number, fully ground in an agate mortar and put into a corundum crucible, and the temperature is raised from room temperature to 1350°C at a heating rate of 10°C/min, and kept warm 6h, cooled to room temperature with the furnace, that is.

将实施例1~6所得荧光材料按照下列的过程制备近红外光源:采用蓝色LED作为激发光源,将荧光材料与硅胶按质量比1:1混合均匀后覆盖于蓝色LED芯片上,放入干燥箱中于100℃下干燥12h,并加装传输波长≥700nm的滤波片,即得。Prepare the near-infrared light source from the fluorescent materials obtained in Examples 1 to 6 according to the following process: use blue LED as the excitation light source, mix the fluorescent material and silica gel evenly at a mass ratio of 1:1, cover the blue LED chip, put Dry in a drying oven at 100°C for 12 hours, and add a filter with a transmission wavelength ≥ 700nm to obtain the product.

以实施例1~6所得荧光材料制备的近红外光源的发光特征见表1。Table 1 shows the luminescent characteristics of the near-infrared light source prepared with the fluorescent materials obtained in Examples 1-6.

表1以实施例1~6所得荧光材料制备的近红外光源的发光特征Table 1 The luminous characteristics of the near-infrared light source prepared with the fluorescent material obtained in Examples 1-6

通过实施例1~6可知,随着Lu含量的增加,所得荧光材料的内量子效率呈现先增加后减小的现象,而过量的Lu不仅不能带来效果更佳的内量子效率,反而会带来成本的增加和性能的下降。From Examples 1 to 6, it can be seen that with the increase of Lu content, the internal quantum efficiency of the fluorescent material obtained first increases and then decreases, and excessive Lu not only cannot bring better internal quantum efficiency, but will bring Come cost increases and performance degradation.

选择最优化发光波长的样品测试得到的激发图和发射图,所有光谱图都是提供材料测试得到的。Select the excitation diagram and emission diagram obtained from the sample test with the optimal luminescence wavelength, and all the spectrum diagrams are obtained from the material test.

Claims (9)

1.一种宽带深红-近红外pc-LED荧光材料,其特征在于:所述荧光材料为包含结构通式A3B2-yCyD3O12:xCr3+的氧化物,其中,A为Ca和/或Sr,B为Al和Lu中的至少一种,C为Al和Lu中的至少一种,D为Ge、Si、Sn和Hf中的至少一种;所述0<y<2,0<x<0.3。1. A broadband deep red-near-infrared pc-LED fluorescent material, characterized in that: said fluorescent material is an oxide comprising general structural formula A 3 B 2-y C y D 3 O 12 : xCr 3+ , wherein , A is Ca and/or Sr, B is at least one of Al and Lu, C is at least one of Al and Lu, D is at least one of Ge, Si, Sn and Hf; said 0<y<2,0<x<0.3. 2.根据权利要求1所述的一种宽带深红-近红外pc-LED荧光材料,其特征在于:所述荧光材料的空间群为I-3ad;所述荧光材料中的A为Ca,B为Lu,C为Al,D为Ge。2. a kind of broadband deep red-near infrared pc-LED fluorescent material according to claim 1 is characterized in that: the space group of described fluorescent material is I-3ad; A in described fluorescent material is Ca, B is Lu, C is Al, and D is Ge. 3.根据权利要求2所述的一种宽带深红-近红外pc-LED荧光材料,其特征在于:所述Al和Lu的摩尔比为1.2~1.9:0.1~0.8。3. A broadband deep red-near infrared pc-LED fluorescent material according to claim 2, characterized in that: the molar ratio of Al to Lu is 1.2-1.9:0.1-0.8. 4.权利要求1~3任意一项所述的一种宽带深红-近红外pc-LED荧光材料的制备方法,其特征在于:将包含A源、B源、C源和D源在内的原料混合均匀,依次经机械活化和烧结,即得。4. A method for preparing a broadband deep red-near-infrared pc-LED fluorescent material according to any one of claims 1 to 3, characterized in that: the A source, the B source, the C source and the D source The raw materials are mixed evenly, followed by mechanical activation and sintering to obtain the product. 5.根据权利要求4所述的一种宽带深红-近红外pc-LED荧光材料的制备方法,其特征在于:所述A源为氧化钙、氢氧化钙、氧化锶和氢氧化锶中的至少一种;所述B源为氧化铝和氧化镥中的至少一种;所述C源为为氧化铝和氧化镥中的至少一种;所述D源为氧化锗。5. the preparation method of a kind of broadband deep red-near infrared pc-LED fluorescent material according to claim 4 is characterized in that: described A source is calcium oxide, calcium hydroxide, strontium oxide and strontium hydroxide At least one; the B source is at least one of aluminum oxide and lutetium oxide; the C source is at least one of aluminum oxide and lutetium oxide; the D source is germanium oxide. 6.根据权利要求4所述的一种宽带深红-近红外pc-LED荧光材料的制备方法,其特征在于:所述原料混合的方式为球磨或机械研磨;所述球磨的条件为:时间为20~30min,转速为150~300r/min。6. the preparation method of a kind of broadband dark red-near infrared pc-LED fluorescent material according to claim 4 is characterized in that: the mode of described raw material mixing is ball milling or mechanical grinding; The condition of described ball milling is: time 20~30min, the speed is 150~300r/min. 7.根据权利要求4所述的一种宽带深红-近红外pc-LED荧光材料的制备方法,其特征在于:所述烧结的方式为高温烧结,其条件为:以8~12℃/min从室温升温至1300~1400℃,保温5~8h,随炉冷却至室温。7. A method for preparing a broadband deep red-near-infrared pc-LED fluorescent material according to claim 4, characterized in that: the sintering method is high temperature sintering, and the conditions are: 8-12°C/min Raise the temperature from room temperature to 1300-1400°C, keep it warm for 5-8 hours, and cool down to room temperature with the furnace. 8.一种高效耐热宽带深红近红外光源,其特征在于:包括权利要求1~3任意一项所述的深红近红外pc-LED荧光材料、蓝光LED芯片和滤光片;所述蓝色LED芯片与荧光材料之间通过封装胶封装,所述滤光片固定覆盖在封装胶上。8. A high-efficiency heat-resistant broadband deep red near-infrared light source, characterized in that: comprising the deep red near-infrared pc-LED fluorescent material, blue LED chip and optical filter according to any one of claims 1 to 3; The blue LED chip and the fluorescent material are encapsulated by encapsulation glue, and the optical filter is fixedly covered on the encapsulation glue. 9.根据权利要求8所述的一种高效耐热宽带深红近红外光源,其特征在于:所述封装胶为硅胶或环氧树脂。9. A high-efficiency heat-resistant broadband deep red near-infrared light source according to claim 8, characterized in that: the packaging glue is silica gel or epoxy resin.
CN202310336420.6A 2023-03-31 2023-03-31 A preparation method of broadband deep red-near-infrared pc-LED fluorescent material and near-infrared light source Pending CN116536044A (en)

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