WO2019062557A1 - 一种氮化物荧光物质及含有该荧光物质的发光装置 - Google Patents

一种氮化物荧光物质及含有该荧光物质的发光装置 Download PDF

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WO2019062557A1
WO2019062557A1 PCT/CN2018/105574 CN2018105574W WO2019062557A1 WO 2019062557 A1 WO2019062557 A1 WO 2019062557A1 CN 2018105574 W CN2018105574 W CN 2018105574W WO 2019062557 A1 WO2019062557 A1 WO 2019062557A1
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fluorescent substance
emitting device
nitride fluorescent
light emitting
nitride
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PCT/CN2018/105574
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French (fr)
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刘荣辉
刘元红
陈磊
江泽
邵冷冷
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有研稀土新材料股份有限公司
国科稀土新材料有限公司
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Priority to DE112018001629.3T priority Critical patent/DE112018001629B4/de
Priority to US16/612,327 priority patent/US11518935B2/en
Priority to JP2019557628A priority patent/JP6997799B6/ja
Priority to KR1020197029174A priority patent/KR102391156B1/ko
Publication of WO2019062557A1 publication Critical patent/WO2019062557A1/zh

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Definitions

  • the invention belongs to the technical field of inorganic luminescent materials, in particular to a nitride fluorescent substance, and further discloses a light-emitting device containing the fluorescent substance.
  • Near-infrared light refers to light with a wavelength ranging from 700 to 1500 nm. This band spectrum has great application prospects in the fields of optical fiber communication, biological imaging, signal conversion amplification, etc., and has become a hot research topic at home and abroad.
  • the existing near-infrared phosphor substrate mainly adopts a rare earth metal oxide having a garnet structure, such as disclosed in Chinese Patent No. CN101063228A, CN105733580A, or an organic complex of electroluminescence (Chem.-Eur. J., 2012, 18, 1961-1968; Adv. Mater., 2009, 21, 111-116; Chem. Commun., 2011, 14, 1833-1837; Adv. Funct. Mater., 2009, 19, 2639-2647).
  • these known fluorescent materials have disadvantages such as poor stability and low luminous efficiency, which limits the application of such devices in the above application fields.
  • the near-infrared illuminating device which is common in the prior art basically adopts an infrared chip, there is also a problem that the excitation efficiency is low and the cost is high.
  • the technical problem to be solved by the present invention is to provide a high-luminance and high-stability nitride fluorescent substance to solve the problem of low luminous efficiency of the fluorescent material in the prior art;
  • a second technical problem to be solved by the present invention is to provide a light-emitting device including the fluorescent material, which solves the problems of poor stability of the light-emitting device and low luminous efficiency in the prior art.
  • a nitride fluorescent substance according to the present invention, the fluorescent substance containing a compound of the formula M m Al x Si y N 3 : aR, bEu, cCe, wherein
  • the M element is selected from the group consisting of Ca elements and/or Sr elements;
  • the R element is selected from at least one of an Er element, an Nd element, a Yb element, a Cr element, and an Fe element;
  • the parameters m, x, y, a, b, and c satisfy the following relationship: 0.8 ⁇ m ⁇ 1.0, 0.9 ⁇ x ⁇ 1.1, 0.9 ⁇ y ⁇ 1.1, 0.001 ⁇ a ⁇ 0.20, 0 ⁇ b ⁇ 0.20, 0 ⁇ c ⁇ 0.1.
  • the fluorescent substance has the same crystal structure as CaAlSiN 3 .
  • the M element is a Ca element and an Sr element, and a molar ratio of the Ca element to the M element is not less than 0.8.
  • the parameters b and c satisfy the following relationship: 0.001 ⁇ b ⁇ 0.10, 0.001 ⁇ c ⁇ 0.05;
  • the parameters x and y satisfy the following relationship: 1 ⁇ y / x ⁇ 1.3.
  • the M element is a Ca element
  • the R element is an Er element
  • the nitride fluorescent material provided by the invention can emit near-infrared light under the excitation of a radiation source such as ultraviolet light, blue light chip, etc., and the material has good luminous efficiency, can also greatly reduce the cost, and can be used for optical fiber communication. , bioimaging, signal conversion amplification and component analysis.
  • the present invention provides a light emitting device comprising at least the nitride fluorescent substance and an excitation light source.
  • the excitation light source has an emission wavelength of 360-480 nm.
  • the excitation source is a violet/near-ultraviolet semiconductor chip, or a blue semiconductor chip.
  • the excitation source is a violet/near-violet semiconductor chip having an emission wavelength ranging from 390 to 430 nm, or the excitation source is a blue semiconductor chip having an emission wavelength ranging from 430 to 470 nm.
  • the nitride fluorescent substance of the present invention contains a compound such as M m Al x Si y N 3 : aR, bEu, cCe structure, the fluorescent substance has high physical stability and chemical stability, and the fluorescent substance crystallizes well. Therefore, it has a high external quantum efficiency.
  • the advantages of good stability and high external quantum efficiency can be sufficiently exhibited, and the luminous efficiency and stability of the light-emitting device can be improved.
  • the combination of different rare earth ions or rare earth ions can achieve adjustable and controllable emission peak intensity and position to improve its luminescent properties. Based on the characteristics of the above-mentioned nitride fluorescent substance, the fluorescent substance and the light-emitting device have a good application prospect in the fields of optical fiber communication, biological imaging, signal conversion amplification and composition analysis.
  • Example 1 is an emission spectrum of a fluorescent substance prepared in Example 1 by using a 460 nm blue light source;
  • Example 2 is an excitation spectrum of a fluorescent substance prepared in Example 1 at a monitoring wavelength of 1538 nm.
  • the chemical formula of the fluorescent substance is Ca 0.963 AlSiN 3 : 0.03Er, 0.006Eu.
  • the nitride fluorescent material of the present embodiment uses Ca 3 N 2 , AlN, Si 3 N 4 , EuN, and ErF 3 as raw materials, and has a stoichiometric ratio of Ca 0.963 AlSiN 3 : 0.03Er and 0.006 Eu in accordance with the composition thereof.
  • the raw materials were accurately weighed in the glove box, and the raw materials were placed in a mixing tank for 30 minutes on the mixer, and then taken out and sieved.
  • the mixed raw materials were calcined at 1750 ° C for 10 hours in a nitrogen atmosphere to obtain a calcined product. It is crushed, sieved, washed, coated, and dried to obtain the desired fluorescent substance.
  • the excitation source semiconductor chip has a wavelength of 460 nm, and its emission spectrum is shown in FIG. As can be seen from Figure 1, the highest peak wavelength of the emission spectrum is 1538 nm.
  • the excitation spectrum of the fluorescent substance is shown in FIG. 2, and its monitoring wavelength is 1538 nm, and its relative intensity is 155%.
  • the fluorescent substance can be effectively excited in the range of 250-600 nm, for example, can be near-ultraviolet light. , blue light and red light excitation, have a wide range of uses.
  • the fluorescent substance produced in this example is a near-infrared fluorescent substance which can be excited by visible light.
  • the chemical formula of the fluorescent substance is (Ca 0.15 , Sr 0.81 ) AlSiN 3 : 0.01Er, 0.02Eu.
  • the nitride fluorescent material of the present embodiment is made of Ca 3 N 2 , Sr 2 N, AlN, Si 3 N 4 , EuN, and ErF 3 , and has a composition of (Ca 0.15 , Sr 0.81 ) AlSiN 3 : 0.01Er. , stoichiometric ratio of 0.02Eu, accurately weigh the raw materials in the glove box, and put the raw materials into the mixing tank and mix them on the mixer for 30 minutes, take them out and sieve them, and mix the raw materials at 1800 ° C, nitrogen.
  • the calcined product was obtained by calcination for 15 h in an atmosphere, and the calcined product was crushed, sieved, washed with water, coated, and dried to obtain a desired fluorescent substance.
  • the obtained fluorescent substance was excited at 405 nm, and its emission spectrum was measured to have a peak wavelength of 1538 nm and a relative intensity of 117%.
  • the chemical formula of the fluorescent substance is Ca 0.953 AlSiN 3 : 0.007Eu, 0.03Er, 0.01Ce.
  • the nitride fluorescent substance of the present embodiment is made of Ca 3 N 2 , Sr 2 N, AlN, Si 3 N 4 , EuN, ErF 3 , CeO 2 , and has a composition of Ca 0.953 AlSiN 3 : 0.007Eu, 0.03. Er, 0.01Ce stoichiometric ratio, accurately weigh the raw materials in the glove box, and put the raw materials into the mixing tank and mix them on the mixer for 50 minutes, take them out and sieve them, and mix the raw materials at 1700 ° C, nitrogen.
  • the calcined product was obtained by firing in an atmosphere for 24 hours, and the calcined product was crushed, sieved, washed with water, coated, and dried to obtain a desired fluorescent substance.
  • the fluorescent material was excited by a 405 nm semiconductor chip, and the highest peak wavelength of the emission spectrum was 1538 nm, and the relative intensity was 160%.
  • the chemical formula of the fluorescent substance is Ca 0.899 AlSiN 3 : 0.05Yb, 0.06Cr.
  • the nitride fluorescent material of the present embodiment uses Ca 3 N 2 , AlN, Si 3 N 4 , Yb 2 O 3 , and Cr 2 O 3 as raw materials, and has a composition of Ca 0.899 AlSiN 3 : 0.05Yb, 0.06Cr.
  • the raw materials were accurately weighed in a glove box, and the raw materials were placed in a mixing tank and mixed on a mixer for 30 minutes, taken out and sieved, and the mixed raw materials were calcined at 1750 ° C for 10 hours in a nitrogen atmosphere to obtain roasting.
  • the product, the calcined product is crushed, sieved, washed with water, coated, and dried to obtain a desired fluorescent substance.
  • the emission of the fluorescent material was broad-band emission under the excitation of a 455 nm semiconductor chip, and the emission peaks were at 994 nm and 1278 nm, corresponding to the emission peaks of Cr 3+ and Yb 3+ , respectively.
  • the highest peak wavelength of the emission was 1278 nm, and the relative intensity was 109%. .
  • EuN, CeO 2 , Nd 2 O 3 and Fe 2 O 3 are accurately weighed in the glove box, and the above raw materials are put into the mixing tank and mixed on the mixer for 5 hours, taken out and sieved, and the mixed raw materials are
  • the calcined product was obtained by calcination at 1800 ° C for 13 h in a nitrogen atmosphere.
  • the calcined product was crushed, sieved, washed with water, coated, and dried to obtain a sample having the chemical formula of Examples 5-22.
  • the nitride fluorescent materials of Examples 1-22 were respectively tested for optical properties.
  • the infrared regions of Examples 5-22 were exposed to the infrared region at 460 nm.
  • the relative intensities of the infrared regions are shown in Table 1, which is Y 2.92 Al 5 in the prior art.
  • O 12 0.04 Ce, and the luminous intensity of 0.04 Nd was calculated as 100.
  • the nitride fluorescent substance of the present invention has higher luminous intensity and luminescent properties.

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Abstract

一种氮化物荧光物质及含有该荧光物质的发光装置，属于无机发光材料技术领域。所述氮化物荧光物质含有如MmAl xSi yN3：aR，bEu，cCe结构的化合物，该荧光物质具有很高的物理稳定性和化学稳定性，同时该荧光物质结晶较好，因此，具有较高的外量子效率。该荧光物质应用至发光装置中时，能够充分发挥稳定性好、外量子效率高的优势，进而提高发光装置的发光效率和稳定性。

Description

一种氮化物荧光物质及含有该荧光物质的发光装置 技术领域
本发明属于无机发光材料技术领域，具体涉及一种氮化物荧光物质，并进一步公开一种含有该荧光物质的发光装置。
背景技术
近红外光指的是波长范围从700-1500nm的光，该波段波谱在光纤通讯、生物成像、信号转换放大等领域有着巨大应用前景，已成为国内外研究的热点。
现有近红外荧光物质基质主要采用具有石榴石结构的稀土金属氧化物，如中国专利CN101063228A、CN105733580A等公开的，或电致发光的有机配合物(Chem.-Eur.J.，2012，18，1961-1968；Adv.Mater.，2009，21，111-116；Chem.Commun.，2011，14，1833-1837；Adv.Funct.Mater.，2009，19，2639-2647)。但是由于这些已知荧光物质具有稳定性差、发光效率低等缺点，限制了该类器件在以上应用领域的应用。此外，现有技术中常见的近红外发光装置由于基本采用红外芯片，也存在着激发效率低且成本较高的问题。
因此，有必要研究开发新的荧光物质，以克服上述缺陷。
发明内容
为此，本发明所要解决的技术问题在于提供一种高亮度和高稳定性的氮化物荧光物质，以解决现有技术中荧光材料发光效率低的问题；
本发明所要解决的第二个技术问题在于提供一种含有该荧光物质的发光装置，以解决现有技术中发光装置稳定性差、发光效率低的问题。
为解决上述技术问题，本发明所述的一种氮化物荧光物质，所述荧光 物质含有化学式为M mAl xSi yN 3：aR，bEu，cCe的化合物，其中，
所述M元素选自Ca元素和/或Sr元素；
所述R元素选自Er元素、Nd元素、Yb元素、Cr元素、Fe元素中的至少一种；
所述参数m、x、y、a、b、c满足如下关系：0.8≤m≤1.0，0.9≤x≤1.1，0.9≤y≤1.1，0.001≤a≤0.20，0≤b≤0.20，0≤c≤0.1。
优选的，所述荧光物质具有与CaAlSiN 3相同的晶体结构。
更优的，所述氮化物荧光物质中，所述M元素为Ca元素和Sr元素，且所述Ca元素占所述M元素的摩尔比不低于0.8。
作为优选，上述荧光物质的化学式中，所述参数b、c满足如下关系：0.001≤b≤0.10，0.001≤c≤0.05；
作为优选，上述荧光物质的化学式中，3≤b/c≤6。
作为优选，上述荧光物质的化学式中，所述参数x、y满足如下关系：1≤y/x≤1.3。
最优的，所述的氮化物荧光物质中，所述M元素为Ca元素，所述R元素为Er元素。
本发明所提供的氮化物荧光物质在辐射源如紫外光、蓝光芯片等的激发下，能够发出近红外光，且这种物质具有较好的发光效率，还可以大大降低成本，可用于光纤通讯、生物成像、信号转换放大和成分分析领域。
本发明提供了一种发光装置，所述发光装置至少包括所述的氮化物荧光物质以及激发光源。
优选的，所述激发光源的发射波长为360-480nm。
作为优选，所述激发光源为紫光/近紫外光半导体芯片，或蓝光半导体芯片。
更优的，所述激发光源为发射波长范围介于390-430nm的紫光/近紫 外光半导体芯片，或者，所述激发光源为发射波长范围介于430-470nm的蓝光半导体芯片。
本发明所述氮化物荧光物质含有如M mAl xSi yN 3：aR，bEu，cCe结构的化合物，该荧光物质具有很高的物理稳定性和化学稳定性，同时该荧光物质结晶较好，因此，具有较高的外量子效率。该荧光物质应用至发光装置中时，能够充分发挥稳定性好、外量子效率高的优势，进而提高发光装置的发光效率和稳定性。另外，选用不同稀土离子或稀土离子组合可以实现发射峰强度以及位置的可调可控，以改善其发光性能。基于上述氮化物荧光物质的特性，该荧光物质及发光装置在光纤通讯、生物成像、信号转换放大和成分分析领域具有很好的应用前景。
附图说明
为了使本发明的内容更容易被清楚的理解，下面根据本发明的具体实施例并结合附图，对本发明作进一步详细的说明，其中，
图1为采用460nm蓝光光源激发下实施例1制得的荧光物质的发射光谱图；
图2为监控波长为1538nm下实施例1制得的荧光物质的激发光谱。
具体实施方式
实施例1
以下为本发明的实施例和实施方式，只是为了说明本发明涉及的氮化物荧光物质及其发光装置，但是本发明并不局限于该实施例和实施方式。
实施例1
本实施例所述氮化物荧光物质，经过分析该荧光物质的化学式为Ca 0.963AlSiN 3：0.03Er，0.006Eu。
本实施例所述氮化物荧光物质，以Ca 3N 2、AlN、Si 3N 4、EuN、ErF 3为原 料，按照其成分为Ca 0.963AlSiN 3：0.03Er，0.006Eu的化学计量比，在手套箱内准确称取所述原料，并将原料放入混料罐在混料器上混合30min，取出后过筛，混合后的原料在1750℃、氮气气氛焙烧10h获得焙烧产物，焙烧产物经破碎、过筛、水洗、包膜、烘干得到所需要的荧光物质。
利用该荧光物质封装的发光装置，激发源半导体芯片波长为460nm，其发射光谱见图1所示。从图1可以看出，该发射光谱最高峰值波长为1538nm。
该荧光物质的激发光谱如图2所示，其监控波长为1538nm，其相对强度155％，从图2可以看出，该荧光物质在250-600nm范围内能够有效激发，例如可以被近紫外光、蓝光及红光激发，具有广泛的用途。
从图1和图2结果可以看出，本实施例制得荧光物质是可在可见光激发的近红外荧光物质。
实施例2
本实施例所述氮化物荧光物质，经过分析该荧光物质的化学式为(Ca 0.15，Sr 0.81)AlSiN 3：0.01Er，0.02Eu。
本实施例所述氮化物荧光物质，以Ca 3N 2、Sr 2N、AlN、Si 3N 4、EuN、ErF 3为原料，按照其成分为(Ca 0.15，Sr 0.81)AlSiN 3：0.01Er，0.02Eu的化学计量比，在手套箱内准确称取所述原料，并将原料放入混料罐在混料器上混合30分钟，取出后过筛，混合后的原料在1800℃、氮气气氛焙烧15h获得焙烧产物，焙烧产物经破碎、过筛、水洗、包膜、烘干得到所需要的荧光物质。将所制得荧光物质在405nm激发下，测定其发射光谱最高峰值波长为1538nm，相对强度117％。
实施例3
本实施例所述氮化物荧光物质，经过分析该荧光物质的化学式为Ca 0.953AlSiN 3：0.007Eu，0.03Er，0.01Ce。
本实施例所述氮化物荧光物质，以Ca 3N 2、Sr 2N、AlN、Si 3N 4、EuN、ErF 3、CeO 2为原料，按照其成分为Ca 0.953AlSiN 3：0.007Eu，0.03Er，0.01Ce的化学 计量比，在手套箱内准确称取所述原料，并将原料放入混料罐在混料器上混合50min，取出后过筛，混合后的原料在1700℃、氮气气氛焙烧24h获得焙烧产物，焙烧产物经破碎、过筛、水洗、包膜、烘干得到所需要的荧光物质。
经测定，该荧光物质在405nm半导体芯片激发下，发射光谱最高峰值波长为1538nm，相对强度160％。
实施例4
本实施例所述氮化物荧光物质，经过分析该荧光物质的化学式为Ca 0.899AlSiN 3：0.05Yb，0.06Cr。
本实施例所述氮化物荧光物质，以Ca 3N 2、AlN、Si 3N 4、Yb 2O 3、Cr 2O 3为原料，按照其成分为Ca 0.899AlSiN 3：0.05Yb，0.06Cr的化学计量比，在手套箱内准确称取所述原料，并将原料放入混料罐在混料器上混合30min，取出后过筛，混合后的原料在1750℃、氮气气氛焙烧10h获得焙烧产物，焙烧产物经破碎、过筛、水洗、包膜、烘干得到所需要的荧光物质。
经测定，该荧光物质在455nm半导体芯片激发下，发射光谱呈宽带发射，发射峰位于994nm和1278nm，分别对应Cr 3+和Yb 3+的发射峰，发射最高峰值波长为1278nm，相对强度109％。
实施例5-22
下述实施例5-22的氮化物荧光物质，根据下表1中所示的实施例5-22通式中的化学计量比，将Ca 3N 2、Sr 2N、AlN、Si 3N 4、EuN、CeO 2、Nd 2O 3和Fe 2O 3在手套箱内准确称量，并将上述原料放入混料罐在混料器上混合5h，取出后过筛，混合后的原料在1800℃、氮气气氛焙烧13h获得焙烧产物，焙烧产物经破碎、过筛、水洗、包膜、烘干，即得到具有实施例5-22化学式的样品。
分别取实施例1-22的氮化物荧光物质进行光学性能测试，在460nm激发下，实施例5-22氮化物荧光物质红外区域相对强度如表1所示，以现有 技术中Y 2.92Al 5O 12：0.04Ce，0.04Nd的发光强度为100计算。
表1 实施例1-22中合成的氮化物荧光物质的化学式与相对强度
Figure PCTCN2018105574-appb-000001
Figure PCTCN2018105574-appb-000002
可见，本发明所述氮化物荧光物质具有更高的发光强度和发光性能。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

  1. 一种氮化物荧光物质，其特征在于，所述荧光物质含有化学式为M mAl xSi yN 3：aR，bEu，cCe的化合物，其中，
    所述M元素选自Ca元素和/或Sr元素；
    所述R元素选自Er元素、Nd元素、Yb元素、Cr元素、Fe元素中的至少一种；
    所述参数m、x、y、a、b、c满足如下关系：0.8≤m≤1.0，0.9≤x≤1.1，0.9≤y≤1.1，0.001≤a≤0.20，0≤b≤0.20，0≤c≤0.1。
  2. 根据权利要求1所述的氮化物荧光物质，其特征在于，所述荧光物质具有与CaAlSiN 3相同的晶体结构。
  3. 根据权利要求1或2所述的氮化物荧光物质，其特征在于，所述M元素为Ca元素和Sr元素，且所述Ca元素占所述M元素的摩尔比不低于0.8。
  4. 根据权利要求1-3任一项所述的氮化物荧光物质，其特征在于，所述参数b、c满足如下关系：0.001≤b≤0.10，0.001≤c≤0.05；
    优选地，3≤b/c≤6。
  5. 根据权利要求1-4任一项所述的氮化物荧光物质，其特征在于，所述参数x、y满足如下关系：1≤y/x≤1.3。
  6. 根据权利要求1-5任一项所述的氮化物荧光物质，其特征在于，所述M元素为Ca元素，所述R元素为Er元素。
  7. 一种发光装置，所述发光装置至少包括权利要求1-6任一项所述的氮化物荧光物质以及激发光源。
  8. 根据权利要求7所述的发光装置，其特征在于，所述激发光源的发射波长为360-480nm。
  9. 根据权利要求8所述的发光装置，其特征在于，所述激发光源为紫光/近紫外光半导体芯片，或蓝光半导体芯片。
  10. 根据权利要求7-9任一项所述的发光装置，其特征在于，所述激发光源为发射波长范围介于390-430nm的紫光/近紫外光半导体芯片，或者，所述激发光源为发射波长范围介于430-470nm的蓝光半导体芯片。
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