WO2022252400A1 - Near-infrared light-emitting substance and light-emitting device comprising same - Google Patents

Near-infrared light-emitting substance and light-emitting device comprising same Download PDF

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WO2022252400A1
WO2022252400A1 PCT/CN2021/112373 CN2021112373W WO2022252400A1 WO 2022252400 A1 WO2022252400 A1 WO 2022252400A1 CN 2021112373 W CN2021112373 W CN 2021112373W WO 2022252400 A1 WO2022252400 A1 WO 2022252400A1
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light
elements
infrared
emission
emitting
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PCT/CN2021/112373
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French (fr)
Chinese (zh)
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刘荣辉
孙志聪
刘元红
陈晓霞
高彤宇
马小乐
薛原
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有研稀土新材料股份有限公司
有研稀土高技术有限公司
河北雄安稀土功能材料创新中心有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof

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  • the present application relates to the technical field of luminescent materials, in particular to a near-infrared luminescent substance and a luminescent device containing the substance.
  • near-infrared LEDs In recent years, with the continuous improvement of social needs such as security monitoring, ambient light detection, light touch switches, biometrics, food medical testing, and plant lighting, the demand for near-infrared light sources, especially near-infrared LEDs, has grown sharply in the above fields.
  • the main way to realize near-infrared LEDs is to use near-infrared semiconductor chips.
  • the typical width at half maximum width obtained by LED chips is 40nm, dozens of chips must be assembled to obtain the target width.
  • driving voltage and current are different, and it is technically difficult to realize wide-spectrum infrared emission.
  • the above-mentioned problems can be effectively solved by combining the visible light chip with the mature technology and the near-infrared material.
  • This method has tunable performance and is more excellent and reliable.
  • the luminescent properties of near-infrared luminescent materials directly determine the quality of devices. Therefore, it is imminent to develop high-performance near-infrared luminescent materials for near-infrared LEDs in various bands to meet their diverse application requirements.
  • Chinese patent CN103194232A discloses a near-infrared fluorescent emission material excited by broadband ultraviolet-visible light and its preparation method and application.
  • the chemical formula is Y 1-xz M z Al 3-y (BO 3 ) 4 : Cr x 3+ , Yb y 3+ , where M is one or both of Bi 3+ and La 3+ , 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.2, 0 ⁇ z ⁇ 0.2, the fluorescent material
  • the excitation wavelength is between 350nm-650nm
  • the emission spectrum range is between 900nm-1100nm
  • the emission spectrum range is narrow.
  • European patent EP2480626A2 discloses that the composition is LiGaO 2 : 0.001Cr 3+ , 0.001Ni 2+ , which can produce near-infrared emission between 1000nm and 1500nm under the excitation of ultraviolet light.
  • the phosphor has a long afterglow effect, and the luminous time lasts for several minutes , not suitable for light-emitting devices.
  • the non-patent document "Trivalent Chromium Ions Doped Fluorides with Both Broad Emission Bandwidth and Excellent Luminescence Thermal Stability" discloses a phosphor.
  • phosphor ScF 3 can produce near-infrared emission with a peak position at 853nm and a luminous position between 800nm and 1100nm, but the luminous efficiency is low, and it is synthesized in water phase, which is not conducive to industrial mass production, and its morphology is The cubic shape brings certain difficulties to subsequent packaging.
  • the quantum efficiency of CaHfO 3 : Cr 3+ reported in the non-patent literature "Pushing the Limit of Boltzmann Distribution in Cr(3+)-Doped CaHfO 3 for Cryogenic Thermometry” is about 20%, and the perovskite structure material emits infrared light less efficient.
  • the emission spectra of existing perovskite materials are relatively narrow, and the luminous efficiency is low.
  • the development of perovskite-structured near-infrared emitting materials with higher luminous efficiency and thermal stability can be used in food testing, security monitoring, and standard light sources. And health lighting and other fields have great application prospects.
  • the purpose of this application is to provide a near-infrared luminescent material and a light-emitting device containing the material.
  • the near-infrared luminescent material has the ability to be excited by visible light with a rich wavelength range to produce a high-efficiency broadband with a peak wavelength of 780-1000nm or a high-efficiency narrow-band near-infrared light with a peak wavelength of 780-1000nm.
  • Infrared light emission uses an excitation light source and the near-infrared light-emitting substance described in the present invention, which can produce broadband near-infrared light in the range of 780nm-1000m or high-efficiency narrow-band near-infrared light emission greater than 1000nm.
  • the application provides a near-infrared luminescent substance, which includes an inorganic compound with the chemical formula A x D y E z M a , wherein,
  • a element includes one or two of La, Gd, Y, Tb, which must contain La element;
  • D elements include one or two of Lu, Sc, Ga, Al, which must contain Lu elements;
  • E elements include O elements, or O and F elements
  • M elements include one or more of Cr, Ce, and Eu elements, and must contain Cr elements;
  • the parameters x, y, z, a meet the following conditions: 0.8 ⁇ x ⁇ 1.2; 0.8 ⁇ y ⁇ 1.2; 2.8 ⁇ z ⁇ 3.2; 0.001 ⁇ a ⁇ 0.3; the luminescent substance has the same positive Alternate crystal structure. Compared with other structures, this structure has a more diverse structure and composition, which can provide a flexible local coordination environment for luminescent ions. At the same time, the system is highly inclusive, and the luminescence of the material can be regulated by crystal field engineering design, so as to obtain excellent Luminous properties.
  • the lower limit of x is selected from 0.8, 0.98, 0.99 or 1.0
  • the upper limit of x is selected from 0.98, 0.99, 1.0 or 1.2
  • the lower limit of y is selected from 0.8, 0.99 or 1
  • the upper limit of y is selected from 0.99, 1 or 1.2
  • the lower limit of z is selected from 2.8, 2.97, 3.005 or 3.01
  • the upper limit of z is selected from 2.97, 3.005, 3.01 or 3.2
  • the lower limit of a is selected from 0.001 or 0.0005, and the upper limit of a is selected from 0.01, 0.02 or 0.3.
  • the D element must contain one or two of Lu, Ga, and Al elements, and the mole percentage of the Lu element in the D element is ⁇ 70%.
  • the radius and valence of Lu 3+ , Ga 3+ , and Al 3+ are relatively close to those of Cr 3+ , occupying the position of the hexacoordinated octahedron in the crystallography of the material, and can provide suitable luminescent sites for Cr 3+ .
  • the ionic radius of Lu 3+ is about And the six-coordinated Cr 3+ ionic radius is on the one hand, larger Lu 3+ can provide a weak crystal field for Cr 3+ , and Cr 3+ entering Lu 3+ will cause larger lattice distortion and distortion, which will lead to the broadening of Cr 3+ emission spectrum.
  • the D element must contain Lu element, and also contains one of In, Mg or Zn, and the mole percentage of Lu element in D element is m, and 90% ⁇ m ⁇ 100%.
  • the formula for calculating the tolerance factor in a material with a chemical formula of ABX 3 perovskite structure is:
  • the tolerance factor of LaLuO3 material is roughly 0.76, and its tolerance factor value is not within the stable perovskite range of 0.77-1.10, but close to the lower limit of the stable perovskite structure tolerance factor range.
  • the replacement of D element with small-radius ions In 3+ , Mg 2+ and Zn 2+ can effectively improve the tolerance factor to a stable range and form a relatively stable perovskite structure. Therefore, the small ion radius In 3+ , Mg 2+ and Zn 2+ ions can improve the stability of the material and improve the light efficiency.
  • the A element contains elements Y, Gd, and Tb with smaller radii than La, the same rule applies.
  • the D element is Lu and Zn elements.
  • the efficiency of Zn 2+ in increasing luminous intensity is better than that of Mg 2+ and In 3+ .
  • the D element is Lu and Sc elements
  • the mole percentage of Lu element in D element is m, and 30% ⁇ m ⁇ 70%.
  • the coexistence of Lu and Sc elements can not only obtain broad-spectrum near-infrared emission, but also obtain stronger luminous intensity.
  • the radius of Sc is smaller than that of Lu, which can increase the tolerance factor to a stable range. Therefore, the presence of Sc can weaken the distortion of the crystal structure, thereby improving the emission intensity and material stability.
  • the incorporation of Sc can increase the crystal field strength.
  • the emission peak of Cr 3+ can be shifted to the short-wave direction, which can reduce the Stokes shift and improve the luminous efficiency.
  • Sc can also affect the grain growth orientation, resulting in a larger grain size morphology.
  • the ionic radius of Lu 3+ is larger than that of Sc 3+ , which can weaken the crystal field and shift the emission peak position to the long-wave direction.
  • m is less than 30%, there is too little Lu 3+ to form a pure phase; when m is greater than 70%, there is too much Lu 3+ , and Sc 3+ cannot effectively weaken the degree of lattice distortion, and at the same time, it has an effect on the grain
  • the role of growth is also limited. Therefore, only when the mole percentage of Lu element in D element satisfies 30% ⁇ m ⁇ 70%, can high-intensity broad-spectrum near-infrared emission be obtained.
  • the A element is La element, and the tolerance factor is closer to the stable range, as the skeleton atoms stably support the material system.
  • the E element is O and F elements, wherein the mole percentage of F element to E element is n, 0.001% ⁇ n ⁇ 0.05%.
  • Fluoride has relatively low phonon energy and weak electron phonon coupling (EPC). The introduction of F - can help reduce non-radiative transitions and improve light efficiency, but too much F - will lead to phase impurity, It will also reduce the light efficiency, so the upper limit of F - doping is 0.05%.
  • the M element is Cr and Ce elements or Cr and Eu elements or Cr and Yb elements, or Cr and Er, or Cr and Nd.
  • the introduced strong absorbing ions Ce 3+ and Eu 2+ can transfer energy to Cr 3+ through energy transfer to achieve the purpose of improving light efficiency.
  • Yb 3+ , Nd 3+ and Er 3+ can further broaden and enhance the luminescence of the material system in the infrared.
  • the preparation method of luminescent material in the present invention comprises:
  • the raw materials are mixed and sintered to obtain a luminescent material.
  • the raw materials are preferably oxides, carbonates, nitrates or fluorides of elements A, D, E, and M; the particle size of the raw materials is preferably 2-15 ⁇ m.
  • the sintering conditions include:
  • the sintering temperature is 1300-1500° C., and the sintering time is 2-10 hours.
  • the invention provides a light-emitting device, which includes a light source and a near-infrared luminescent substance, the near-infrared luminescent substance is any one of the above-mentioned near-infrared luminescent substances, and the light-emitting light source includes a light-emitting diode, a laser diode or an organic EL light-emitting substance device.
  • the present invention provides a new perovskite material that must contain Lu and La, which can be used by visible light sources, especially Blue light excitation produces a luminescent substance with a peak wavelength in the high-intensity broadband of 780-1000nm or a narrow-band near-infrared emission greater than 1000nm, which can significantly broaden the emission spectrum, make the spectrum shift to long-wavelength, obtain a variety of broad-spectrum emission bands, and increase the luminous intensity; another On the one hand, it provides a light-emitting device containing it, which has great application scenarios in the fields of security monitoring, food detection, calibration light source and healthy lighting.
  • Fig. 1 is that the X-ray diffraction spectrum of the fluorescent powder obtained in the embodiment of the present invention 1 is compared with the standard card;
  • Fig. 2 is the emission spectrogram of the fluorescent powder obtained in Example 1 of the present invention under 460nm excitation;
  • Fig. 3 is the excitation spectrogram of the fluorescent powder obtained in Example 1 of the present invention at a monitoring wavelength of 884nm;
  • Fig. 5 is the emission spectrogram of the fluorescent powder obtained in Example 4 of the present invention under 460nm excitation;
  • Fig. 6 is the emission spectrogram of the fluorescent powder obtained in Example 6 of the present invention under 460nm excitation;
  • Fig. 7 is the emission spectrogram of the fluorescent powder obtained in Example 7 of the present invention under 460nm excitation;
  • Fig. 8 is the emission spectrogram of the fluorescent powder obtained in Example 8 of the present invention under 460nm excitation;
  • Fig. 9 is an emission spectrum diagram of the fluorescent powder obtained in Example 9 of the present invention under excitation at 460 nm.
  • the near-infrared luminescent substance described in this comparative example contains a compound with the formula LaSc 0.99 O 3 Cr 0.01 .
  • the near-infrared luminescent substance described in this embodiment contains a compound with a composition formula of LaLu 0.99 O 3 Cr 0.01 .
  • the stoichiometric ratio of the chemical formula LaLu 0.99 O 3 Cr 0.01 accurately weigh the raw materials La 2 O 3 , Lu 2 O 3 and Cr 2 O 3 , grind and mix the above raw materials into a crucible, and sinter in a nitrogen/hydrogen mixed atmosphere , in a high-temperature furnace, sintered at 1300 ° C for 10 hours; cooled to room temperature with the furnace, and then the sample was ball milled, washed and sieved to obtain the required near-infrared luminescent material.
  • Example 1 The fluorescent material obtained in Example 1 was analyzed by X-ray diffraction, and its X-ray diffraction pattern was obtained, as shown in FIG. 1 .
  • Example 1 The fluorescent material obtained in Example 1 was analyzed by a fluorescence spectrometer, excited by blue light at 460 nm, and its emission spectrum was obtained, as shown in FIG. 2 .
  • the excitation spectrum of the phosphor powder at a monitoring wavelength of 884nm is shown in Figure 3 . It can be seen that the red and near-infrared spectra of the material under blue light excitation are very broad, reaching 700nm-1200nm, the peak wavelength is 884nm, and the intensity is also high.
  • the broad-band emitting near-infrared luminescent substance described in this embodiment contains a compound with a composition formula of La 0.999 Lu 0.99 O 2.999 F 0.001 Cr 0.01 .
  • Example 2 The fluorescent material obtained in Example 2 was analyzed by a fluorescence spectrometer, excited by blue light at 460 nm, and its emission spectrum was obtained, as shown in FIG. 4 . It can be seen that the red and near-infrared spectra of the material under the excitation of blue light are very broad, reaching 700nm-1200nm, and the peak wavelength is 880nm.
  • Fig. 5 is the emission spectrogram of the fluorescent powder obtained in embodiment 4 under 460nm excitation
  • Fig. 6 is the emission spectrogram of the phosphor obtained in embodiment 6 under 460nm excitation
  • Fig. 7 is the fluorescence obtained in embodiment 7
  • Fig. 8 is the emission spectrum of the phosphor obtained in Example 8 under the excitation of 460nm
  • Fig. 9 is the emission spectrum of the phosphor obtained in Example 9 under the excitation of 460nm.
  • the constituent elements of the examples and comparative examples, the peak wavelength and relative luminous intensity under the excitation of a 460nm blue light source are shown in Table 1 at the end of the article.
  • the luminous intensity of LaSc 0.99 O 3 Cr 0.01 in the comparative example is taken as 100%.
  • Examples 1-32 all have the luminescent material with the composition of the present application.
  • the emission peak wavelength is adjusted in the infrared region through the method of composition adjustment to achieve spectral adjustment.
  • the luminous intensity of all the examples of the present invention is greater than that of the comparative example.
  • Nd, Er, Yb and other elements also have obvious infrared luminescence phenomenon in this system.
  • the doping of Ce and Eu can effectively enhance the luminescence intensity of Cr.
  • Doping part of Sc, Zn, and Mg can modify the crystal structure and improve the tolerance factor of the material to a stable range, so it can also increase the luminous intensity of Cr.
  • the doping of small-radius ions can provide a stronger crystal field intensity lattice.
  • the emission peak of Cr can be shifted to the short-wave direction, which can reduce the Stokes shift and improve the luminous efficiency.
  • the present invention relates to a near-infrared luminescent substance and a luminescent device containing it.
  • Near-infrared luminescent substances including inorganic compounds with the chemical formula A x D y E z M a
  • a elements include one or two of La, Gd, Y, Tb, which must contain La elements
  • D elements include Lu, Sc One or two of , Ga, Al, which must contain Lu elements
  • E elements include O elements, or O and F elements
  • M elements include Cr, Ce, Eu, Yb, Nd, Er elements or one or More than one kind, which must contain Cr element
  • the parameters x, y, z, a meet the following conditions: 0.8 ⁇ x ⁇ 1.2; 0.8 ⁇ y ⁇ 1.2; 2.8 ⁇ z ⁇ 3.2; 0.001 ⁇ a ⁇ 0.3
  • the luminescent material has the same perovskite orthorhombic crystal structure as LaLuO3 .
  • the luminescent material Under the excitation of ultraviolet light, purple light, blue light and red light, the luminescent material can produce high-efficiency broad-spectrum emission with a peak wavelength of 780-1000 nm or high-efficiency narrow-band near-infrared light emission with a peak wavelength greater than 1000 nm. It has great application prospects in food testing, security monitoring, standard light source and health lighting and other fields.

Abstract

The present application discloses a near-infrared light-emitting substance and a light-emitting device comprising same. The near-infrared light-emitting substance comprises an inorganic compound having a chemical formula of AxDyEzMa; an element A comprises one or two of La, Gd, Y, and Tb, and necessarily comprises the element La; an element D comprises one or two of Lu, Sc, Ga, and Al, and necessarily comprises the element Lu; an element E comprises an element O or elements O and F; an element M comprises one or more of Cr, Ce, Eu, Yb, Nd, and Er, and necessarily comprises the element Cr; and the parameters x, y, z, and a meet the following conditions: 0.8≤x≤1.2; 0.8≤y≤1.2; 2.8≤z≤3.2; and 0.001≤a≤0.3. The light-emitting substance has a perovskite orthorhombic system structure which is the same as that of LaLuO3. Under excitation of ultraviolet light, purple light, blue light, and red light, the light-emitting material can generate efficient wide-spectrum emission having a peak wavelength of 780-1,000 nm or efficient narrow-band near-infrared light emission having a peak wavelength greater than 1,000 nm. The present invention has a great application prospect in the fields of food testing, security monitoring, standard light sources, healthy illumination, etc.

Description

一种近红外发光物质及包含该物质的发光器件A near-infrared luminescent substance and a light-emitting device containing the substance
交叉引用cross reference
本申请基于申请号为202110623906.9、申请日为2021年6月4日的中国专利申请提出，并要求该中国专利申请的优先权，该中国专利申请的全部内容在此引入本申请作为参考。This application is based on a Chinese patent application with application number 202110623906.9 and a filing date of June 4, 2021, and claims the priority of this Chinese patent application. The entire content of this Chinese patent application is hereby incorporated by reference into this application.
技术领域technical field
本申请涉及发光材料技术领域，尤其涉及一种近红外发光物质及包含该物质的发光器件。The present application relates to the technical field of luminescent materials, in particular to a near-infrared luminescent substance and a luminescent device containing the substance.
背景技术Background technique
近年来，随着安防监控、环境光检测、光触开关、生物识别、食品医疗检测、植物照明等社会需求持续提升，近红外光源，尤其近红外LED在上述领域的需求急剧增长。目前近红外LED的主要实现方式是采用近红外半导体芯片的方法，但是由于LED芯片获得的半高宽典型宽度为40nm，为获得目标宽度需要数十个芯片组装而成才能获得，但由于不同芯片组装形式，驱动电压、电流各异，实现宽谱红外发射，存在技术难度。利用技术成熟的可见光芯片与近红外材料复合的方式可有效解决上述问题。该方式具有可调谐性能，并且更加优异可靠。作为近红外LED光源关键材料，近红外发光材料的发光性能直接决定了器件的品质，因此，开发各波段近红外LED用高性能近红外发光材料，实现其多样化的应用需求迫在眉睫。In recent years, with the continuous improvement of social needs such as security monitoring, ambient light detection, light touch switches, biometrics, food medical testing, and plant lighting, the demand for near-infrared light sources, especially near-infrared LEDs, has grown sharply in the above fields. At present, the main way to realize near-infrared LEDs is to use near-infrared semiconductor chips. However, since the typical width at half maximum width obtained by LED chips is 40nm, dozens of chips must be assembled to obtain the target width. However, due to different chips The assembly form, driving voltage and current are different, and it is technically difficult to realize wide-spectrum infrared emission. The above-mentioned problems can be effectively solved by combining the visible light chip with the mature technology and the near-infrared material. This method has tunable performance and is more excellent and reliable. As a key material for near-infrared LED light sources, the luminescent properties of near-infrared luminescent materials directly determine the quality of devices. Therefore, it is imminent to develop high-performance near-infrared luminescent materials for near-infrared LEDs in various bands to meet their diverse application requirements.
目前如中国专利CN103194232A公开了一种宽带紫外-可见光激发的近红外荧光发射材料及其制备方法和应用，该发光材料中，化学式为Y 1-x-zM zAl 3-y(BO 3) 4:Cr x 3+,Yb y 3+，其中M为Bi 3+和La 3+中的一种或两种，0<x≤0.2，0<y≤0.2，0≤z≤0.2，该荧光材料的激发波长为350nm-650nm间，发射光谱范围在900nm-1100nm之间，发射光谱范 围偏窄。欧洲专利EP2480626A2公开了成分为LiGaO 2:0.001Cr 3+,0.001Ni 2+，在紫外光激发下可产生1000nm-1500nm之间的近红外发射，该荧光粉有长余辉效果，发光时间持续数分钟，不适合做发光器件。非专利文献《Photoluminescence Intensity and Spectral Properties in Yb 3+Codoped LiScP 2O 7:Cr 3+》报道了一种化学成分为LiScP 2O 7的荧光粉，在470nm的蓝光的激发下，共掺离子Cr 3+与Yb 3+可产生750nm-1100nm的近红外发射，但发射光谱并不是平滑的宽带发射，为后续红外化学检测分析带来干扰因素。非专利文献《Trivalent Chromium Ions Doped Fluorides with Both Broad Emission Bandwidth and Excellent Luminescence Thermal Stability》公开了一种荧光粉。在蓝光激发下，荧光粉ScF 3可产生峰值位置在853nm，发光位置位于800nm-1100nm之间的近红外发射，但发光效率较低，为水相合成，不利于工业批量生产，且形貌为立方状，给后续封装带来一定困难。非专利文献《Cr 3+/Er 3+co-doped LaAlO 3perovskite phosphor:a near-infrared persistent luminescence probe covering the first and third biological windows》公开了一种在405nm光激发下发射红外光的钙钛矿结构荧光粉，Cr 3+产生了峰值位置位于737nm的尖锐峰。非专利文献《Pushing the Limit of Boltzmann Distribution in Cr(3+)-Doped CaHfO 3 for Cryogenic Thermometry》报道的CaHfO 3:Cr 3+经过实验得到的量子效率约为20％，钙钛矿结构材料红外发光效率较低。 At present, Chinese patent CN103194232A discloses a near-infrared fluorescent emission material excited by broadband ultraviolet-visible light and its preparation method and application. In this luminescent material, the chemical formula is Y 1-xz M z Al 3-y (BO 3 ) 4 : Cr x 3+ , Yb y 3+ , where M is one or both of Bi 3+ and La 3+ , 0<x≤0.2, 0<y≤0.2, 0≤z≤0.2, the fluorescent material The excitation wavelength is between 350nm-650nm, the emission spectrum range is between 900nm-1100nm, and the emission spectrum range is narrow. European patent EP2480626A2 discloses that the composition is LiGaO 2 : 0.001Cr 3+ , 0.001Ni 2+ , which can produce near-infrared emission between 1000nm and 1500nm under the excitation of ultraviolet light. The phosphor has a long afterglow effect, and the luminous time lasts for several minutes , not suitable for light-emitting devices. The non-patent literature “Photoluminescence Intensity and Spectral Properties in Yb 3+ Codoped LiScP 2 O 7 : Cr 3+ ” reports a phosphor with the chemical composition LiScP 2 O 7 , which is co-doped with ionic Cr under the excitation of 470nm blue light 3+ and Yb 3+ can produce near-infrared emission at 750nm-1100nm, but the emission spectrum is not a smooth broadband emission, which brings interference factors to the subsequent infrared chemical detection and analysis. The non-patent document "Trivalent Chromium Ions Doped Fluorides with Both Broad Emission Bandwidth and Excellent Luminescence Thermal Stability" discloses a phosphor. Under the excitation of blue light, phosphor ScF 3 can produce near-infrared emission with a peak position at 853nm and a luminous position between 800nm and 1100nm, but the luminous efficiency is low, and it is synthesized in water phase, which is not conducive to industrial mass production, and its morphology is The cubic shape brings certain difficulties to subsequent packaging. The non-patent literature "Cr 3+ /Er 3+ co-doped LaAlO 3 perovskite phosphor: a near-infrared persistent luminescence probe covering the first and third biological windows" discloses a perovskite that emits infrared light under 405nm light excitation Structured phosphor, Cr 3+ produces a sharp peak at 737nm. The quantum efficiency of CaHfO 3 : Cr 3+ reported in the non-patent literature "Pushing the Limit of Boltzmann Distribution in Cr(3+)-Doped CaHfO 3 for Cryogenic Thermometry" is about 20%, and the perovskite structure material emits infrared light less efficient.
综上，已有的钙钛矿材料的发射光谱都比较窄，且发光效率低，开发具有更高发光效率和热稳定性的钙钛矿结构近红外发射材料在食品检测、安防监控、标准光源以及健康照明等领域都有极大的应用前景。In summary, the emission spectra of existing perovskite materials are relatively narrow, and the luminous efficiency is low. The development of perovskite-structured near-infrared emitting materials with higher luminous efficiency and thermal stability can be used in food testing, security monitoring, and standard light sources. And health lighting and other fields have great application prospects.
发明内容Contents of the invention
本申请的目的是提供一种近红外发光物质及包含该物质的发光器件，近红外发光物质具有被波长范围丰富的可见光激发而产生峰值波长位于780-1000nm的高效宽带或者大于1000nm的高效窄带近红外光发射；发光器件使用激发光源及本发明所述的近红外发光物质，能产生780nm-1000m范围的宽带近红外光或者大于1000nm的高效窄带近红外光发射。The purpose of this application is to provide a near-infrared luminescent material and a light-emitting device containing the material. The near-infrared luminescent material has the ability to be excited by visible light with a rich wavelength range to produce a high-efficiency broadband with a peak wavelength of 780-1000nm or a high-efficiency narrow-band near-infrared light with a peak wavelength of 780-1000nm. Infrared light emission: The light-emitting device uses an excitation light source and the near-infrared light-emitting substance described in the present invention, which can produce broadband near-infrared light in the range of 780nm-1000m or high-efficiency narrow-band near-infrared light emission greater than 1000nm.
为了解决上述问题，本申请提供了一种近红外发光物质，该发光物质包括化学式为A xD yE zM a的无机化合物，其中， In order to solve the above problems, the application provides a near-infrared luminescent substance, which includes an inorganic compound with the chemical formula A x D y E z M a , wherein,
A元素包括La、Gd、Y、Tb中的一种或者两种，其中必含La元素；A element includes one or two of La, Gd, Y, Tb, which must contain La element;
D元素包括Lu、Sc、Ga、Al中的一种或者两种，其中必含Lu元素；D elements include one or two of Lu, Sc, Ga, Al, which must contain Lu elements;
E元素包括O元素，或者O和F元素；E elements include O elements, or O and F elements;
M元素包括Cr、Ce、Eu元素中的一种或一种以上，其中必含Cr元素；M elements include one or more of Cr, Ce, and Eu elements, and must contain Cr elements;
且所述参数x、y、z、a满足如下条件：0.8≤x≤1.2；0.8≤y≤1.2；2.8≤z≤3.2；0.001≤a≤0.3；所述发光物质具有与LaLuO 3相同的正交晶系结构。相对于其它结构该结构具有更加多样化的结构和组成，可为发光离子提供灵活的局部配位环境，同时该体系包容性强，可以通过晶体场工程设计调控该材料的发光，从而获得优异的发光特性。 And the parameters x, y, z, a meet the following conditions: 0.8≤x≤1.2; 0.8≤y≤1.2; 2.8≤z≤3.2; 0.001≤a≤0.3; the luminescent substance has the same positive Alternate crystal structure. Compared with other structures, this structure has a more diverse structure and composition, which can provide a flexible local coordination environment for luminescent ions. At the same time, the system is highly inclusive, and the luminescence of the material can be regulated by crystal field engineering design, so as to obtain excellent Luminous properties.
可选地，x的下限选自0.8、0.98、0.99或1.0，x的上限选自0.98、0.99、1.0或1.2；y的下限选自0.8、0.99或1，y的上限选自0.99、1或1.2；z的下限选自2.8、2.97、3.005或3.01，z的上限选自2.97、3.005、3.01或3.2；a的下限选自0.001或0.0005，a的上限选自0.01、0.02或0.3。Alternatively, the lower limit of x is selected from 0.8, 0.98, 0.99 or 1.0, the upper limit of x is selected from 0.98, 0.99, 1.0 or 1.2; the lower limit of y is selected from 0.8, 0.99 or 1, and the upper limit of y is selected from 0.99, 1 or 1.2; the lower limit of z is selected from 2.8, 2.97, 3.005 or 3.01, the upper limit of z is selected from 2.97, 3.005, 3.01 or 3.2; the lower limit of a is selected from 0.001 or 0.0005, and the upper limit of a is selected from 0.01, 0.02 or 0.3.
作为优选，所述D元素必含Lu、Ga、Al元素中的一种或两种，Lu元素占D元素的摩尔百分比≥70％。Lu 3+、Ga 3+、Al 3+元素半径和价态与Cr 3+比较接近，占据该材料晶体学六配位八面体的位置，可以为Cr 3+提供合适的发光格位。Lu 3+的离子半径约为
Figure PCTCN2021112373-appb-000001
而六配位Cr 3+离子半径为
Figure PCTCN2021112373-appb-000002
一方面较大的Lu 3+能够为Cr 3+提供一个弱晶体场，Cr 3+进入Lu 3+引起较大的晶格扭曲与畸变可导致Cr 3+发射光谱宽化现象。 Preferably, the D element must contain one or two of Lu, Ga, and Al elements, and the mole percentage of the Lu element in the D element is ≥ 70%. The radius and valence of Lu 3+ , Ga 3+ , and Al 3+ are relatively close to those of Cr 3+ , occupying the position of the hexacoordinated octahedron in the crystallography of the material, and can provide suitable luminescent sites for Cr 3+ . The ionic radius of Lu 3+ is about
Figure PCTCN2021112373-appb-000001
And the six-coordinated Cr 3+ ionic radius is
Figure PCTCN2021112373-appb-000002
On the one hand, larger Lu 3+ can provide a weak crystal field for Cr 3+ , and Cr 3+ entering Lu 3+ will cause larger lattice distortion and distortion, which will lead to the broadening of Cr 3+ emission spectrum.
作为优选，所述D元素必含Lu元素，还含有In、Mg或Zn中的一种，且Lu元素占D元素的摩尔百分比为m，90％≤m＜100％。在化学式为ABX 3钙钛矿结构的材料中容忍度因子计算公式为： Preferably, the D element must contain Lu element, and also contains one of In, Mg or Zn, and the mole percentage of Lu element in D element is m, and 90%≤m<100%. The formula for calculating the tolerance factor in a material with a chemical formula of ABX 3 perovskite structure is:
Figure PCTCN2021112373-appb-000003
Figure PCTCN2021112373-appb-000003
例如当A元素为La元素时，LaLuO 3材料的容忍度因子大致为0.76，其容忍因子数值不在稳定的钙钛矿范围0.77～1.10内，但接近稳定钙钛矿结构容忍因子范围的下限。根据计算公式可得，D元素替换成小半径离子In 3+、Mg 2+和Zn 2+可以有效提高容忍因子的数值至稳定范围，形成比较稳定钙钛矿结构。因此小离子半径In 3+、Mg 2+和Zn 2+离子可以提高该材料的稳定性，提高光效。当A元素包含比La半径更小的元素Y、Gd、Tb时，也具有相同的规律。 For example, when the A element is La element, the tolerance factor of LaLuO3 material is roughly 0.76, and its tolerance factor value is not within the stable perovskite range of 0.77-1.10, but close to the lower limit of the stable perovskite structure tolerance factor range. According to the calculation formula, the replacement of D element with small-radius ions In 3+ , Mg 2+ and Zn 2+ can effectively improve the tolerance factor to a stable range and form a relatively stable perovskite structure. Therefore, the small ion radius In 3+ , Mg 2+ and Zn 2+ ions can improve the stability of the material and improve the light efficiency. When the A element contains elements Y, Gd, and Tb with smaller radii than La, the same rule applies.
作为优选，所述D元素为Lu和Zn元素。Zn 2+提升发光强度的效率优于Mg 2+与In 3+。 Preferably, the D element is Lu and Zn elements. The efficiency of Zn 2+ in increasing luminous intensity is better than that of Mg 2+ and In 3+ .
作为优选，所述D元素为Lu和Sc元素，且Lu元素占D元素的摩尔百分比为m，30％≤m≤70％。Lu和Sc元素共同存在既可以得到宽谱近红外发射，也可以获得更强的发光强度。当Lu含量较多时，Sc的半径较Lu的半径小，可以提高容忍度因子到稳定范围内，因此Sc元素的存在可以减弱晶体结构扭曲程度，从而提高发射强度和材料稳定性。同时，Sc的掺入可以增加晶体场强度，根据Cr 3+的能级图，可 以使Cr 3+的发射峰向短波方向移动，减小斯托克斯位移，提高发光效率。Sc还可影响晶粒生长取向，获得晶粒尺寸更大的形貌。当Sc含量较多时，Lu 3+的离子半径比Sc 3+的离子半径更大，可以减弱晶体场，发射峰位置向长波方向移动。当m小于30％时，Lu 3+太少，无法形成纯相；当m大于70％时，Lu 3+太多，Sc 3+对晶格扭曲程度起不到有效的减弱，同时对晶粒生长的作用也有限。因此，只有当且Lu元素占D元素的摩尔百分比满足30％≤m≤70％的比例，才能获得高强度的宽谱近红外发射。 Preferably, the D element is Lu and Sc elements, and the mole percentage of Lu element in D element is m, and 30%≤m≤70%. The coexistence of Lu and Sc elements can not only obtain broad-spectrum near-infrared emission, but also obtain stronger luminous intensity. When the content of Lu is high, the radius of Sc is smaller than that of Lu, which can increase the tolerance factor to a stable range. Therefore, the presence of Sc can weaken the distortion of the crystal structure, thereby improving the emission intensity and material stability. At the same time, the incorporation of Sc can increase the crystal field strength. According to the energy level diagram of Cr 3+ , the emission peak of Cr 3+ can be shifted to the short-wave direction, which can reduce the Stokes shift and improve the luminous efficiency. Sc can also affect the grain growth orientation, resulting in a larger grain size morphology. When the Sc content is high, the ionic radius of Lu 3+ is larger than that of Sc 3+ , which can weaken the crystal field and shift the emission peak position to the long-wave direction. When m is less than 30%, there is too little Lu 3+ to form a pure phase; when m is greater than 70%, there is too much Lu 3+ , and Sc 3+ cannot effectively weaken the degree of lattice distortion, and at the same time, it has an effect on the grain The role of growth is also limited. Therefore, only when the mole percentage of Lu element in D element satisfies 30%≤m≤70%, can high-intensity broad-spectrum near-infrared emission be obtained.
作为优选，所述A元素为La元素，容忍因子更接近稳定范围，作为骨架原子稳定地支撑该材料体系。Preferably, the A element is La element, and the tolerance factor is closer to the stable range, as the skeleton atoms stably support the material system.
作为优选，所述E元素为O和F元素，其中，F元素占E元素的摩尔百分比为n，0.001％≤n≤0.05％。氟化物有相对较低的声子能量和弱电子声子耦合(EPC)，F -的引入可以有助于降低非辐射跃迁，提高光效，但是过多的F -会导致物相不纯，也会降低光效，因此F -掺杂上限为0.05％。 Preferably, the E element is O and F elements, wherein the mole percentage of F element to E element is n, 0.001%≤n≤0.05%. Fluoride has relatively low phonon energy and weak electron phonon coupling (EPC). The introduction of F - can help reduce non-radiative transitions and improve light efficiency, but too much F - will lead to phase impurity, It will also reduce the light efficiency, so the upper limit of F - doping is 0.05%.
作为优选，所述M元素为Cr和Ce元素或Cr和Eu元素或Cr和Yb元素，或者Cr和Er，或Cr和Nd。引入的强吸收离子Ce 3+与Eu 2+能够通过能量传递将能量传递给Cr 3+，达到提高光效的目的。Yb 3+、Nd 3+与Er 3+可以进一步拓宽和增强该材料体系在红外的发光。 Preferably, the M element is Cr and Ce elements or Cr and Eu elements or Cr and Yb elements, or Cr and Er, or Cr and Nd. The introduced strong absorbing ions Ce 3+ and Eu 2+ can transfer energy to Cr 3+ through energy transfer to achieve the purpose of improving light efficiency. Yb 3+ , Nd 3+ and Er 3+ can further broaden and enhance the luminescence of the material system in the infrared.
本发明中发光材料的制备方法，包括：The preparation method of luminescent material in the present invention comprises:
根据上述的无机化合物配比称取原料；Take raw materials according to the above-mentioned inorganic compound proportioning;
对所述原料进行混合、烧结，得到发光材料。The raw materials are mixed and sintered to obtain a luminescent material.
其中，原料优选A、D、E、M元素的氧化物、碳酸盐、硝酸盐或者氟化物；原料粒径优选2-15μm。Among them, the raw materials are preferably oxides, carbonates, nitrates or fluorides of elements A, D, E, and M; the particle size of the raw materials is preferably 2-15 μm.
优选地，所述烧结的条件包括：Preferably, the sintering conditions include:
烧结温度为1300-1500℃，烧结时间为2-10小时。The sintering temperature is 1300-1500° C., and the sintering time is 2-10 hours.
本发明提供了一种发光器件，该发光器件包含光源和近红外发光物质，所述近红外发光物质为上述任一项近红外发光物质，所述发光光源包括发光二极管、激光二极管或有机EL发光器件。The invention provides a light-emitting device, which includes a light source and a near-infrared luminescent substance, the near-infrared luminescent substance is any one of the above-mentioned near-infrared luminescent substances, and the light-emitting light source includes a light-emitting diode, a laser diode or an organic EL light-emitting substance device.
本发明具备的优点包括：The advantages that the present invention possesses include:
针对现有技术中近红外钙钛矿材料发射光谱窄，效率低的问题，本发明一方面本发明提供了一种必含Lu和La的新钙钛矿材料，该材料可被可见光光源尤其是蓝光激发产生峰值波长位于780-1000nm高强度宽带或者大于1000nm窄带近红外发光的发光物质，可明显拓宽发射光谱，使光谱发生长波移动，获得多种的宽谱发射波段，提升发光强度；另一方面，提供了包含其的发光器件，在安防监控、食品检测、校准光源以及健康照明领域有极大的应用场景。Aiming at the problems of narrow emission spectrum and low efficiency of near-infrared perovskite materials in the prior art, on the one hand, the present invention provides a new perovskite material that must contain Lu and La, which can be used by visible light sources, especially Blue light excitation produces a luminescent substance with a peak wavelength in the high-intensity broadband of 780-1000nm or a narrow-band near-infrared emission greater than 1000nm, which can significantly broaden the emission spectrum, make the spectrum shift to long-wavelength, obtain a variety of broad-spectrum emission bands, and increase the luminous intensity; another On the one hand, it provides a light-emitting device containing it, which has great application scenarios in the fields of security monitoring, food detection, calibration light source and healthy lighting.
附图说明Description of drawings
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：In order to make the content of the present invention more easily understood, the present invention will be described in further detail below according to specific embodiments of the present invention in conjunction with the accompanying drawings, wherein:
图1为本发明实施例1中得到的荧光粉的X射线衍射图谱与标准卡比较；Fig. 1 is that the X-ray diffraction spectrum of the fluorescent powder obtained in the embodiment of the present invention 1 is compared with the standard card;
图2为本发明实施例1中得到的荧光粉在460nm激发下的发射光谱图；Fig. 2 is the emission spectrogram of the fluorescent powder obtained in Example 1 of the present invention under 460nm excitation;
图3为本发明实施例1中得到的荧光粉在884nm监测波长下的激发光谱图；Fig. 3 is the excitation spectrogram of the fluorescent powder obtained in Example 1 of the present invention at a monitoring wavelength of 884nm;
图4本发明实施例2中得到的荧光粉在460nm激发下的发射光谱图；The emission spectrogram of the fluorescent powder obtained in the embodiment of the present invention 2 under 460nm excitation of Fig. 4;
图5本发明实施例4中得到的荧光粉在460nm激发下的发射光谱图；Fig. 5 is the emission spectrogram of the fluorescent powder obtained in Example 4 of the present invention under 460nm excitation;
图6本发明实施例6中得到的荧光粉在460nm激发下的发射光谱图；Fig. 6 is the emission spectrogram of the fluorescent powder obtained in Example 6 of the present invention under 460nm excitation;
图7本发明实施例7中得到的荧光粉在460nm激发下的发射光谱图；Fig. 7 is the emission spectrogram of the fluorescent powder obtained in Example 7 of the present invention under 460nm excitation;
图8本发明实施例8中得到的荧光粉在460nm激发下的发射光谱图；Fig. 8 is the emission spectrogram of the fluorescent powder obtained in Example 8 of the present invention under 460nm excitation;
图9本发明实施例9中得到的荧光粉在460nm激发下的发射光谱图。Fig. 9 is an emission spectrum diagram of the fluorescent powder obtained in Example 9 of the present invention under excitation at 460 nm.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚明了，下面结合具体实施方式并参照附图，对本发明进一步详细说明。应该理解，这些描述只是示例性的，而并非要限制本发明的范围。此外，在以下说明中，省略了对公知结构和技术的描述，以避免不必要地混淆本发明的概念。In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in combination with specific embodiments and with reference to the accompanying drawings. It should be understood that these descriptions are exemplary only, and are not intended to limit the scope of the present invention. Also, in the following description, descriptions of well-known structures and techniques are omitted to avoid unnecessarily obscuring the concept of the present invention.
以下实施例中所用的器件和试剂均为市售。The devices and reagents used in the following examples are commercially available.
对比例1Comparative example 1
本对比例所述的近红外发光物质，其包含的化合物组成式为LaSc 0.99O 3Cr 0.01。 The near-infrared luminescent substance described in this comparative example contains a compound with the formula LaSc 0.99 O 3 Cr 0.01 .
按化学式LaSc 0.99O 3Cr 0.01的化学计量比，准确称量原料La 2O 3、Sc 2O 3和Cr 2O 3，将上述原料研磨混匀装入坩埚，在氮气/氢气混合气气氛下烧结，在高温炉内，于1300℃烧结10小时；随炉冷却到室温，然后将样品经过球磨、水洗和筛分得到所需的近红外发光材料。 According to the stoichiometric ratio of the chemical formula LaSc 0.99 O 3 Cr 0.01 , accurately weigh the raw materials La 2 O 3 , Sc 2 O 3 and Cr 2 O 3 , grind and mix the above raw materials into a crucible, and put them in a nitrogen/hydrogen mixed gas atmosphere. Sintering, in a high-temperature furnace, sintering at 1300°C for 10 hours; cooling to room temperature with the furnace, and then ball milling, washing and sieving the sample to obtain the required near-infrared luminescent material.
实施例1Example 1
本实施例所述的近红外发光物质，其包含的化合物组成式为LaLu 0.99O 3Cr 0.01。 The near-infrared luminescent substance described in this embodiment contains a compound with a composition formula of LaLu 0.99 O 3 Cr 0.01 .
按化学式LaLu 0.99O 3Cr 0.01的化学计量比，准确称量原料La 2O 3、Lu 2O 3 和Cr 2O 3，将上述原料研磨混匀装入坩埚，在氮气/氢气混合气氛下烧结，在高温炉内，于1300℃烧结10小时；随炉冷却到室温，然后将样品经过球磨、水洗和筛分得到所需的近红外发光材料。 According to the stoichiometric ratio of the chemical formula LaLu 0.99 O 3 Cr 0.01 , accurately weigh the raw materials La 2 O 3 , Lu 2 O 3 and Cr 2 O 3 , grind and mix the above raw materials into a crucible, and sinter in a nitrogen/hydrogen mixed atmosphere , in a high-temperature furnace, sintered at 1300 ° C for 10 hours; cooled to room temperature with the furnace, and then the sample was ball milled, washed and sieved to obtain the required near-infrared luminescent material.
利用X射线衍射对实施例1中得到的荧光材料进行分析，得到其X射线衍射图谱，如图1所示。The fluorescent material obtained in Example 1 was analyzed by X-ray diffraction, and its X-ray diffraction pattern was obtained, as shown in FIG. 1 .
利用荧光光谱仪对实施例1中得到的荧光材料进行分析，在蓝光460nm激发，得到其发射光谱图，如图2所示。荧光粉在884nm监测波长下的激发光谱图如图3所示。可见该材料在蓝光激发下的红光及近红外光谱非常宽，达到700nm-1200nm，峰值波长为884nm，强度也较高。The fluorescent material obtained in Example 1 was analyzed by a fluorescence spectrometer, excited by blue light at 460 nm, and its emission spectrum was obtained, as shown in FIG. 2 . The excitation spectrum of the phosphor powder at a monitoring wavelength of 884nm is shown in Figure 3 . It can be seen that the red and near-infrared spectra of the material under blue light excitation are very broad, reaching 700nm-1200nm, the peak wavelength is 884nm, and the intensity is also high.
实施例2Example 2
本实施例所述的宽谱带发射近红外发光物质，其包含的化合物组成式为La 0.999Lu 0.99O 2.999F 0.001Cr 0.01。 The broad-band emitting near-infrared luminescent substance described in this embodiment contains a compound with a composition formula of La 0.999 Lu 0.99 O 2.999 F 0.001 Cr 0.01 .
按化学式La 0.999Lu 0.99O 2.99997F 0.00003Cr 0.01的化学计量比，准确称量原料La 2O 3、Lu 2O 3、Cr 2O 3和LaF 3，将上述原料研磨混匀装入坩埚，空气下，在高温炉内氮气/氢气混合气下烧结，1400℃烧结10小时，随炉冷却到室温，样品经过球磨、水洗和筛分得到所需的近红外发光材料。 According to the stoichiometric ratio of the chemical formula La 0.999 Lu 0.99 O 2.99997 F 0.00003 Cr 0.01 , accurately weigh the raw materials La 2 O 3 , Lu 2 O 3 , Cr 2 O 3 and LaF 3 , grind and mix the above raw materials into the crucible, air sintering at 1400°C for 10 hours under nitrogen/hydrogen mixture in a high-temperature furnace, and cooling to room temperature with the furnace. The samples were ball milled, washed with water and sieved to obtain the desired near-infrared luminescent material.
利用荧光光谱仪对实施例2中得到的荧光材料进行分析，在蓝光460nm激发，得到其发射光谱图，如图4所示。可见该材料在蓝光激发下的红光及近红外光谱非常宽，达到700nm-1200nm，峰值波长为880nm。The fluorescent material obtained in Example 2 was analyzed by a fluorescence spectrometer, excited by blue light at 460 nm, and its emission spectrum was obtained, as shown in FIG. 4 . It can be seen that the red and near-infrared spectra of the material under the excitation of blue light are very broad, reaching 700nm-1200nm, and the peak wavelength is 880nm.
实施例3-32的发光材料制备方法以及表征方法与实施例1相同，只需根据各实施例中目标化合物组成，选择适当计量的化合物进行混合、研磨、选取适当的焙烧条件和后处理得到发光材料产品。图5为实施例4中得到的荧光粉在460nm激发下的发射光谱图；图6为实施例6中得到的荧光粉在460nm激发下的发射光谱图；图7为实施例7 中得到的荧光粉在460nm激发下的发射光谱图；图8为实施例8中得到的荧光粉在460nm激发下的发射光谱图；图9为实施例9中得到的荧光粉在460nm激发下的发射光谱图。The preparation method and characterization method of the luminescent material in Examples 3-32 are the same as in Example 1, only need to select an appropriate metered compound according to the composition of the target compound in each example for mixing, grinding, selection of appropriate calcination conditions and post-treatment to obtain luminescence material product. Fig. 5 is the emission spectrogram of the fluorescent powder obtained in embodiment 4 under 460nm excitation; Fig. 6 is the emission spectrogram of the phosphor obtained in embodiment 6 under 460nm excitation; Fig. 7 is the fluorescence obtained in embodiment 7 The emission spectrum of the powder under 460nm excitation; Fig. 8 is the emission spectrum of the phosphor obtained in Example 8 under the excitation of 460nm; Fig. 9 is the emission spectrum of the phosphor obtained in Example 9 under the excitation of 460nm.
实施例与对比例的组成元素和在460nm蓝光光源激发下的峰值波长和相对发光强度如文末表1所示。以对比例中LaSc 0.99O 3Cr 0.01的发光强度为100％。 The constituent elements of the examples and comparative examples, the peak wavelength and relative luminous intensity under the excitation of a 460nm blue light source are shown in Table 1 at the end of the article. The luminous intensity of LaSc 0.99 O 3 Cr 0.01 in the comparative example is taken as 100%.
根据表1的数据可以看出，实施例1-32均具有本申请组成的发光材料。发射峰值波长在红外区域内通过成分调节的方法实现光谱调节。以对比例的发光强度定位100％，本发明所有实施例发光强度均大于对比例。Nd、Er、Yb等元素在该体系中也有较为明显的红外发光现象。Ce、Eu的掺入能够有效提升Cr的发光强度。掺入部分Sc、Zn、Mg由于可以修饰晶体结构，提高该材料的容忍度因子到稳定的范围内，所以也可以提升Cr的发光强度。同时小半径离子的掺入可以提供较强晶体场强度格位，根据Cr的能级图，可以使Cr的发射峰向短波方向移动，减小斯托克斯位移，提高发光效率。According to the data in Table 1, it can be seen that Examples 1-32 all have the luminescent material with the composition of the present application. The emission peak wavelength is adjusted in the infrared region through the method of composition adjustment to achieve spectral adjustment. Taking the luminous intensity of the comparative example as 100%, the luminous intensity of all the examples of the present invention is greater than that of the comparative example. Nd, Er, Yb and other elements also have obvious infrared luminescence phenomenon in this system. The doping of Ce and Eu can effectively enhance the luminescence intensity of Cr. Doping part of Sc, Zn, and Mg can modify the crystal structure and improve the tolerance factor of the material to a stable range, so it can also increase the luminous intensity of Cr. At the same time, the doping of small-radius ions can provide a stronger crystal field intensity lattice. According to the energy level diagram of Cr, the emission peak of Cr can be shifted to the short-wave direction, which can reduce the Stokes shift and improve the luminous efficiency.
综上所述，本发明涉及一种近红外发光物质及包含其的发光器件。近红外发光物质，包括化学式为A xD yE zM a的无机化合物，A元素包括La、Gd、Y、Tb中的一种或者两种，其中必含La元素；D元素包括Lu、Sc、Ga、Al中的一种或者两种，其中必含Lu元素；E元素包括O元素，或者O和F元素；M元素包括Cr、Ce、Eu、Yb、Nd、Er元素中的一种或一种以上，其中必含Cr元素；且所述参数x、y、z、a满足如下条件：0.8≤x≤1.2；0.8≤y≤1.2；2.8≤z≤3.2；0.001≤a≤0.3；所述发光物质具有与LaLuO 3相同的钙钛矿正交晶系结构。该发光材料在紫外、紫光、蓝光和红光激发下，能够产生峰值波长位于780-1000nm高效宽谱发射或者大于峰值波长1000nm的高效窄带近红外光发射。在食品检测、安防监控、标准光源以及健康照明等领域 都有极大的应用前景。 To sum up, the present invention relates to a near-infrared luminescent substance and a luminescent device containing it. Near-infrared luminescent substances, including inorganic compounds with the chemical formula A x D y E z M a , A elements include one or two of La, Gd, Y, Tb, which must contain La elements; D elements include Lu, Sc One or two of , Ga, Al, which must contain Lu elements; E elements include O elements, or O and F elements; M elements include Cr, Ce, Eu, Yb, Nd, Er elements or one or More than one kind, which must contain Cr element; and the parameters x, y, z, a meet the following conditions: 0.8≤x≤1.2; 0.8≤y≤1.2; 2.8≤z≤3.2; 0.001≤a≤0.3; The luminescent material has the same perovskite orthorhombic crystal structure as LaLuO3 . Under the excitation of ultraviolet light, purple light, blue light and red light, the luminescent material can produce high-efficiency broad-spectrum emission with a peak wavelength of 780-1000 nm or high-efficiency narrow-band near-infrared light emission with a peak wavelength greater than 1000 nm. It has great application prospects in food testing, security monitoring, standard light source and health lighting and other fields.
应当理解的是，本申请的上述具体实施方式仅仅用于示例性说明或解释本申请的原理，而不构成对本申请的限制。因此，在不偏离本申请的精神和范围的情况下所做的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。此外，本申请所附权利要求旨在涵盖落入所附权利要求范围和边界、或者这种范围和边界的等同形式内的全部变化和修改例。It should be understood that the above specific implementation manners of the present application are only used to illustrate or explain the principle of the present application, but not to limit the present application. Therefore, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present application shall fall within the protection scope of the present application. Furthermore, the claims appended to this application are intended to embrace all changes and modifications that come within the scope and metes and bounds of the appended claims, or equivalents of such scope and metes and bounds.
表1 对比例与实施例的组成元素及发光性能Table 1 Constituent elements and luminescent properties of comparative examples and examples
Figure PCTCN2021112373-appb-000004
Figure PCTCN2021112373-appb-000004
Figure PCTCN2021112373-appb-000005
Figure PCTCN2021112373-appb-000005
Figure PCTCN2021112373-appb-000006
Figure PCTCN2021112373-appb-000006

Claims (10)

  1. 一种近红外发光物质，其特征在于，该发光物质包括化学式为A xD yE zM a的无机化合物，其中， A near-infrared luminescent substance, characterized in that the luminescent substance comprises an inorganic compound with a chemical formula of A x D y E z Ma , wherein,
    A元素包括La、Gd、Y、Tb中的一种或者两种，其中必含La元素；A element includes one or two of La, Gd, Y, Tb, which must contain La element;
    D元素包括Lu、Sc、Ga、Al中的一种或者两种，其中必含Lu元素；D elements include one or two of Lu, Sc, Ga, Al, which must contain Lu elements;
    E元素包括O元素，或者O和F元素；E elements include O elements, or O and F elements;
    M元素包括Cr、Ce、Eu元素中的一种或一种以上，其中必含Cr元素；M elements include one or more of Cr, Ce, and Eu elements, and must contain Cr elements;
    且所述参数x、y、z、a满足如下条件：0.8≤x≤1.2；0.8≤y≤1.2；2.8≤z≤3.2；0.001≤a≤0.3；所述发光物质具有与LaLuO 3相同的正交晶系结构。 And the parameters x, y, z, a meet the following conditions: 0.8≤x≤1.2; 0.8≤y≤1.2; 2.8≤z≤3.2; 0.001≤a≤0.3; the luminescent substance has the same positive Alternate crystal structure.
  2. 根据权利要求1所述的近红外发光物质，其特征在于，所述D元素含Lu、Ga、Al元素中的一种或两种，Lu元素占D元素的摩尔百分比≥70％。The near-infrared luminescent material according to claim 1, wherein the D element contains one or two of Lu, Ga, and Al elements, and the mole percentage of Lu element to D element is ≥ 70%.
  3. 根据权利要求2所述的近红外发光物质，其特征在于，所述D元素必含Lu元素，还含有In、Mg或Zn中的一种，且Lu元素占D元素的摩尔百分比为m，90％≤m＜100％。The near-infrared luminescent substance according to claim 2, wherein the D element must contain Lu element, and also contains one of In, Mg or Zn, and the molar percentage of Lu element to D element is m, 90 %≤m<100%.
  4. 根据权利要求3所述的近红外发光物质，其特征在于，所述D元素为Lu和Zn元素。The near-infrared luminescent substance according to claim 3, wherein the D element is Lu and Zn elements.
  5. 根据权利要求1所述的近红外发光物质，其特征在于，所述D元素为Lu和Sc元素，且Lu元素占D元素的摩尔百分比为m，30％≤m≤70％。The near-infrared luminescent material according to claim 1, wherein the D element is Lu and Sc elements, and the molar percentage of Lu element in D element is m, and 30%≤m≤70%.
  6. 根据权利要求2或5所述的近红外发光物质，其特征在于，所述A元素为La元素。The near-infrared luminescent substance according to claim 2 or 5, characterized in that the A element is La element.
  7. 根据权利要求6所述的近红外发光物质，其特征在于，所述E元素为O和F，F占E元素的摩尔百分比为n，0.001％≤n≤0.05％。The near-infrared luminescent substance according to claim 6, characterized in that, the E elements are O and F, and the molar percentage of F in the E element is n, 0.001%≤n≤0.05%.
  8. 根据权利要求7所述的近红外发光物质，其特征在于，所述M元素为Cr和Ce元素、Cr和Eu元素、Cr和Yb元素、Cr和Er元素，或Cr和Nd元素。The near-infrared luminescent substance according to claim 7, wherein the M element is Cr and Ce elements, Cr and Eu elements, Cr and Yb elements, Cr and Er elements, or Cr and Nd elements.
  9. 一种发光器件，包含发光光源和权利要求1-8任一项所述的近红外发光物质。A light-emitting device, comprising a light-emitting light source and the near-infrared light-emitting substance according to any one of claims 1-8.
  10. 根据权利要求9所述的发光器件，其特征在于，所述发光光源包括发光二极管、激光二极管或有机EL发光器件。The light emitting device according to claim 9, wherein the light emitting source comprises a light emitting diode, a laser diode or an organic EL light emitting device.
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