阅读说明：本技术 一种近红外发光材料以及含该发光材料的发光装置 (Near-infrared luminescent material and luminescent device containing same ) 是由 刘元红 刘荣辉 陈晓霞 马小乐 李彦峰 陈明月 于 2018-11-30 设计创作，主要内容包括：本发明属于近红外发光材料技术领域,具体涉及一种近红外发光材料,并进一步公开其制备方法,以及含有该发光材料的发光装置。本发明所述近红外发光材料包括组成式为M<Sub>a</Sub>A<Sub>b</Sub>(QO<Sub>3</Sub>)<Sub>c</Sub>:zZ的无机化合物,该化合物的激发波长在350-750nm,近红外光区的发射主峰为700-1700nm的宽带或者多谱发射,激发波长比较宽泛,能很好的吸收紫外光、蓝光和红光,在近红外区域具有宽带或者多谱发射(700-1700nm),且光谱范围可调可控,相对于峰值波长700-1700nm的红光以及近红外芯片具有更宽或者更多谱线的发射,具有更广泛的用途。(The invention belongs to the technical field of near-infrared luminescent materials, and particularly relates to a near-infrared luminescent material, and further discloses a preparation method thereof, and a luminescent device containing the luminescent material. The near-infrared luminescent material comprises a composition formula M a A b (QO 3 ) c zZ, the excitation wavelength of the compound is 350-750nm, the emission main peak of the near infrared region is 700-1700nm, the excitation wavelength is wider, the compound can well absorb ultraviolet light, blue light and red light, the near infrared region has broadband or multi-spectrum emission (700-1700nm), the spectral range is adjustable and controllable, and the compound has wider or more spectral line emission relative to the peak wavelength of 700-1700nm and the near infrared chip, and has wider application.)

1. A near-infrared luminescent material, characterized in that the near-infrared luminescent material comprises a compound of formula M_aA_b(QO₃)_czZ an inorganic compound, whichIn (1),

the M element is one or two of Sc, Y, La, Lu, Gd, Ca, Sr, Ba or Mg elements;

the element A is one or two of Sc, Y, La, Lu or Gd elements;

the Q element is selected from one or two of Ga, Al, B or In elements;

the Z element includes a Cr element;

the M element and the A element are different;

and the parameters a, b, c and z satisfy the following conditions: a is more than or equal to 0.8 and less than or equal to 3.2, b is more than or equal to 1.8 and less than or equal to 3.2, c is more than or equal to 3.5 and less than or equal to 4.5, and z is more than or equal to 0.0001 and less than or equal to 0.5.

2. The near-infrared phosphor of claim 1, wherein the Z element further comprises one of Ce, Eu, Tb, Bi, Dy, Cr, Yb, Pr, Nd, or Er elements.

3. The near-infrared light-emitting material according to claim 1 or 2, wherein the Q element is a Ga element; or the Q element is Ga element, and one of Al, B or In element is added; or the Q element is a B element.

4. The near-infrared luminescent material according to any one of claims 1 to 3, characterized in that: the M element is selected from one of Ca, Sr, Ba or Mg element, and the A element is selected from one of Sc, Y, La, Lu or Gd element; a is more than or equal to 2.8 and less than or equal to 3.2, and b is more than or equal to 1.8 and less than or equal to 2.2.

5. The near-infrared luminescent material according to any one of claims 1 to 3, characterized in that: the M element and the A element are different from each other and are selected from one of Sc, Y, La, Lu or Gd elements, a is more than or equal to 0.8 and less than or equal to 1.2, and b is more than or equal to 2.8 and less than or equal to 3.2.

6. A near-infrared luminescent material according to any one of claims 1 to 5, wherein the M element is a La element, the A element is a Sc element, the Q element is a Ga element, and the Z element is a Cr element.

7. The near-infrared luminescent material according to any one of claims 1 to 5, wherein the element Q is an element B, and the luminescent material is in an inorganic powder form.

8. A method for preparing the near-infrared luminescent material according to any one of claims 1 to 7, comprising the steps of:

(1) evenly mixing oxides, fluorides, carbonates, chlorides and/or acids corresponding to selected M, A, Q and Z elements according to a selected stoichiometric ratio to obtain a mixture;

(2) and roasting the mixture at the temperature of 1200-1400 ℃ in the atmosphere of air, nitrogen and/or hydrogen for 2-20h to obtain a roasted product, and performing conventional treatment to obtain the required luminescent material.

9. The method according to claim 8, wherein the selected M element oxide, a element oxide, a Q element oxide or an acid, Cr element oxide are used as raw materials, mixed uniformly according to a selected stoichiometric ratio, added with a flux, grown as a seed crystal by a molten salt method, and grown as a transparent crystal by the seed crystal by a czochralski method.

10. A light-emitting device comprising a light source and a luminescent material, wherein the luminescent material comprises the near-infrared luminescent material of any one of claims 1 to 7.

11. The light-emitting device according to claim 10, wherein the light source is a semiconductor chip having an emission peak wavelength range of 350-750 nm.

Technical Field

The invention belongs to the technical field of near-infrared luminescent materials, and particularly relates to a near-infrared luminescent material, and further discloses a preparation method thereof, and a luminescent device containing the luminescent material.

Background

With the rise and rapid development of the fields of modern internet of things, biological identification, wearable devices, food/medical detection and the like, various sensors and image identification technologies become more important. Among these technologies, the red and near infrared spectroscopy has advantages of convenience, rapidness, low cost, no damage, no pollution, etc., and is widely applied to the fields of petrochemical industry, polymer, pharmacy, clinical medicine, environmental science, textile industry, biological identification, security monitoring, food/medical detection, etc., and the near infrared LED becomes an important auxiliary light source in view of its wide application characteristics.

The near-infrared LED is a near-infrared light emitting diode, which is a near-infrared light emitting device for converting electric energy into light energy, has a series of advantages of small volume, low power consumption, good directivity and the like, and is widely used for systems such as remote control, remote measurement, optical isolation, optical switching, photoelectric control, target tracking and the like. The near-infrared LED can be applied to special required applications such as iris identification, face identification and the like by combining a sensing device and an identification technology; or the near-infrared LED technology is applied to the biosensor of the wearable device, so that the physiological state of the human body can be quantified, and the method becomes a new tool for health management. Meanwhile, in view of the rapid increase of the permeability of smart phones, automobiles, monitoring systems and other near-infrared LEDs, the near-infrared LED technology is widely concerned.

At present, near infrared LEDs are mainly used in the fields of communications, security monitoring and sensors, and mainly infrared LEDs with wavelengths of 850nm and 940 nm. In addition, the red light and near infrared region in the range of 700nm-1700nm covers the frequency doubling and frequency combination characteristic information of the vibration of the hydrogen-containing group (O-H, N-H, C-H). By scanning the near infrared spectrum of the sample, the characteristic information of the hydrogen-containing groups of the organic molecules in the sample can be obtained. Therefore, the application of near infrared LEDs in the field of food detection is also increasing.

The near-infrared LED commonly used in the current market mainly adopts a semiconductor chip directly, and has the defects of small power of a single chip, poor thermal stability, narrow emission spectrum, incapability of realizing multi-spectrum, high cost and the like. Particularly, the maximum half-height width of the near-infrared LED is 40nm (typically 20nm), which cannot be realized by using a single chip for many applications requiring a wide spectrum or multiple spectra (for example, the food detection field requires a 650-1700nm ultra-wide spectrum); to obtain such a broad spectrum in the range of 650nm-1700nm (red and near infrared), tens of chips are required to obtain the spectrum. For example, in a multichannel parallel near infrared spectroscopy imaging system disclosed in chinese patent CN103156620A, because the packaging form, driving voltage, and driving current of each chip are different, it results in using multiple chips to implement ultra-wide range or multi-spectral red light and near infrared spectroscopy (650nm-1700nm), which not only has great technical difficulty, but also has high cost and poor device stability. Therefore, it is of positive significance to develop a near-infrared light-emitting material with wide or multi-spectral and adjustable spectrum, and further develop a low-cost and high-thermal stability near-infrared light-emitting device.

Disclosure of Invention

Therefore, the present invention is to provide a near-infrared luminescent material, which can be effectively excited by blue light, ultraviolet light, and red light, and has the characteristic of emitting a broad spectrum or multiple spectra.

The second technical problem to be solved by the present invention is to provide a light emitting device containing the near-infrared light emitting material, which can realize the emission of wide-spectrum or multi-spectrum near-infrared light under the excitation of blue light, ultraviolet light and red light, and solve the problems of poor stability, high technical difficulty, incapability of realizing wide-spectrum or multi-spectrum and adjustability of the existing near-infrared light emitting device.

In order to solve the technical problem, the near-infrared luminescent material comprises a compound represented by the chemical formula M_aA_b(QO₃)_czZ, wherein,

the M element is one or two of Sc, Y, La, Lu, Gd, Ca, Sr, Ba or Mg elements;

the element A is one or two of Sc, Y, La, Lu or Gd elements;

the Q element is selected from one or two of Ga, Al, B or In elements;

the Z element includes a Cr element;

the M element and the A element are different;

and the parameters a, b, c and z satisfy the following conditions: a is more than or equal to 0.8 and less than or equal to 3.2, b is more than or equal to 1.8 and less than or equal to 3.2, c is more than or equal to 3.5 and less than or equal to 4.5, and z is more than or equal to 0.0001 and less than or equal to 0.5.

Preferably, the Z element also comprises one of Ce, Eu, Tb, Bi, Dy, Cr, Yb, Pr, Nd or Er elements.

Preferably, the Q element is Ga element or the Q element is Ga element, and one of Al, B or In element is added; or the Q element is a B element.

Preferably, the M element is selected from one of Ca, Sr, Ba or Mg element, and the A element is selected from one of Sc, Y, La, Lu or Gd element; a is more than or equal to 2.8 and less than or equal to 3.2, and b is more than or equal to 1.8 and less than or equal to 2.2.

Preferably, the M element and the A element are different from each other and are one selected from Sc, Y, La, Lu or Gd element, and 0.8. ltoreq. a.ltoreq.1.2, 2.8. ltoreq. b.ltoreq.3.2.

Preferably, the M element is La element, the a element is Sc element, the Q element is Ga element, and the Z element is Cr element.

Preferably, in the near-infrared luminescent material of the present invention, when Q is B, the luminescent material prepared is in the form of inorganic powder.

The invention also discloses a method for preparing the near-infrared luminescent material, which comprises the following steps:

(1) evenly mixing oxides, fluorides, carbonates, chlorides and/or acids corresponding to selected M, A, Q and Z elements according to a selected stoichiometric ratio to obtain a mixture;

(2) and roasting the mixture at the temperature of 1200-1400 ℃ in the atmosphere of air, nitrogen and/or hydrogen for 2-20h to obtain a roasted product, and performing conventional treatment to obtain the required luminescent material.

The compound corresponding to the M element comprises oxide, fluoride, carbonate or chloride of the M element;

the corresponding compound of the element A comprises an oxide, a fluoride, a carbonate or a chloride of the element A;

the compound corresponding to the Q element comprises an oxide or an acid of the Q element;

the compound corresponding to the Z element comprises oxide, fluoride or carbonate of the Z element.

The invention also discloses a preparation method of the luminescent material when the Z element is Cr element, which comprises the steps of uniformly mixing the selected M element oxide, A element oxide, Q element oxide or acid and Cr element oxide as raw materials according to the selected stoichiometric ratio, adding a fluxing agent, growing a seed crystal by a molten salt growth method, and growing a transparent crystal by the seed crystal by a pulling method.

The invention also discloses a light-emitting device which comprises a light source and a luminescent material, wherein the luminescent material comprises the near-infrared luminescent material.

Preferably, the light source is a semiconductor chip with an emission peak wavelength range of 350-750nm, and more preferably a semiconductor chip with an emission peak wavelength range of 440-460 nm.

The near-infrared luminescent material comprises a composition formula M_aA_b(QO₃)_czZ, the excitation wavelength of the compound is 350-750nm, the main emission peak of the near-infrared region is broadband or multispectral emission of 700-1700nm, the excitation wavelength is relatively wide, ultraviolet light, blue light and red light can be well absorbed, broadband or multispectral emission (700-1700nm) is provided in the near-infrared region, the spectral range is adjustable and controllable, and the chip has wider or more spectral emission compared with the red light with the peak wavelength of 700-1700nm and a near-infrared chip, and has wider application.

The near-infrared luminescent material can be used for preparing a luminescent device, the luminescent device can emit the broadband 1700nm and multispectral near-infrared light under the excitation of a blue light chip and an ultraviolet chip, and can realize wider spectrum or more spectrums by compounding various fluorescent powders, and the spectrums are adjustable and controllable. The light-emitting device can meet the requirements of various fields such as light effect communication, face iris recognition, security monitoring, anti-counterfeiting, laser radar, food detection, digital medical treatment, 3D sensing and the like; and the defects of high cost and poor stability of a light-emitting device directly using a near-infrared chip are avoided, and the method becomes a new way for generating near-infrared light.

Drawings

In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,

FIG. 1 shows the excitation and emission spectra of the phosphor prepared in example 1, with the monitoring wavelength of the left curve being 869nm and the excitation wavelength of the right curve being 460 nm.

Detailed Description