A near-infrared fluorescent powder and a light emitting device

Abstract

The application relates to the technical field of light-emitting materials, in particular to a near-infrared fluorescent powder and a light-emitting device. a (D d M m R r Q q )E e G g The inorganic compound has a composition formula A2.9-aMmRrQqDdEeGgO12.9+d+m+r+q, 2.9<=a<=3.1, 1.9<=d+m+r+q<=2.1, 2.9<=e<=3.1, 11.8<=g<=12.2, 0 12 The near-infrared fluorescent powder has the same cubic phase garnet structure as Ca3Ga2Ge3O12; the emission peak wavelength position of the near-infrared fluorescent powder is located in the range of 1470-1602 nm, the near-infrared fluorescent powder can be excited by blue light and red light, can be matched with a blue light chip, can enrich the emission wave band of the near-infrared fluorescent powder, and solves the problem of material shortage; further, the near-infrared fluorescent powder has a large half-peak width, high quantum efficiency and good thermal stability, and can be effectively applied to application scenes such as water detection, beauty lamps and medical analgesia.

Description

Technical Field

[0001] This invention relates to the field of luminescent materials technology, and in particular to a near-infrared phosphor and a luminescent device. Background Technology

[0002] In recent years, the application of near-infrared light sources in information detection fields such as medical / food testing, water quality testing, component analysis, and semiconductor material detection has become a focus of the industry.

[0003] Near-infrared phosphors are a special type of fluorescent material composed of near-infrared materials and fluorescent groups. When excited, such as by ultraviolet or blue light, near-infrared phosphors emit fluorescence signals characteristic of the near-infrared band. Near-infrared phosphors have the advantage of having excitation and fluorescence wavelengths similar, which can greatly reduce absorption and scattering by biological tissues, thereby improving the quality and depth of imaging. This makes them particularly suitable for applications in the biomedical field, such as fluorescence imaging technology.

[0004] Near-infrared phosphors, as a core component of near-infrared light sources, offer numerous advantages. Their high quantum efficiency means they can more effectively convert absorbed energy into near-infrared light, while their excellent stability ensures the durability and reliability of the light source. Furthermore, the tunable emission wavelength of near-infrared phosphors provides greater flexibility for their applications, meeting diverse detection needs. Combined with their relatively low manufacturing cost and high compatibility with commercial blue LED chips, fluorescence-converting near-infrared light sources (NIR pc-LEDs) are increasingly becoming the ideal choice for portable near-infrared spectroscopy applications.

[0005] However, despite the numerous advantages of near-infrared phosphors, the variety of materials currently available on the market remains limited, and their spectral coverage is relatively narrow, which restricts their widespread application to some extent. The luminous efficiency of existing near-infrared phosphors still needs improvement. Low luminous efficiency not only affects the sensitivity and accuracy of spectrometers but may also increase energy consumption, thus limiting the usage time of portable devices. Summary of the Invention

[0006] (I) Purpose of the Invention

[0007] The purpose of this invention is to provide a near-infrared phosphor and a light-emitting device that can be excited by blue light and deep red light, enrich the emission band of the near-infrared phosphor, and have high luminous efficiency.

[0008] (II) Technical Solution

[0009] To address the above problems, the present invention provides a near-infrared phosphor, wherein the phosphor comprises a component with the formula A a (D d M m R r Qq E e G g Inorganic compounds, wherein the inorganic compounds have a similarity to Ca3Ga2Ge3O 12 The same cubic garnet structure; among which,

[0010] Element A includes one or two of Ca, Sr, Ba, Bi, La, and Gd;

[0011] The D element includes one or two of Al, Ga, In, and Sc;

[0012] The M element includes one or two of Li, Mg, and Zn;

[0013] The R element includes one or two of Zr, Hf, Sn, Ti, Ta, and Nb;

[0014] The element E is selected from one or both of Si and Ge;

[0015] The element G is selected from one or two of O, N, and F;

[0016] The element Q is selected from one or two of Mn, Eu, Cr and Ni;

[0017] 2.9≤a≤3.1, 1.9≤d+m+r+q≤2.1, 2.9≤e≤3.1, 11.8≤g≤12.2, 0<m≤1.1, 0<r≤1.1, 0<q≤0.25.

[0018] In another aspect of the present invention, preferably, element A must contain Ca, and Ca accounts for more than or equal to 96% of element A; element D must contain Ga, and Ga accounts for more than or equal to 0.1% of element D; element E must contain Ge, and Ge accounts for more than or equal to 83.33% of element E; element G must contain O, and O accounts for more than or equal to 92% of element D; and element Q must contain Ni.

[0019] In another aspect of the present invention, preferably, the phosphor emission peak wavelength range is 1470-1602 nm.

[0020] In another aspect of the present invention, preferably, when the element M is Zn and the element R is Zr, and 0.8 ≤ m / r ≤ 1.

[0021] In another aspect of the present invention, preferably, when the M element is Zn and the R element is Hf, and 0.9≤m / r≤1.1.

[0022] In another aspect of the present invention, preferably, when the M element is Zn and the R element is Sn, and 0.85≤m / r≤1.

[0023] In another aspect of the invention, preferably, when the Q element is Ni and Cr, and the molar ratio of Cr in Q is α, 0.1% ≤ α ≤ 80%.

[0024] In another aspect of the present invention, preferably, element A is Ca, D is Ga, M is Zn, E is Ge, G is O, and Q is Ni and Cr.

[0025] In another aspect of the present invention, preferably, a light-emitting device includes an excitation light source and a light-emitting material, said light-emitting material comprising near-infrared phosphor as described above.

[0026] In another aspect of the present invention, preferably, the excitation light source is a semiconductor chip with an emission peak wavelength range of 400-470 nm.

[0027] (III) Beneficial Effects

[0028] The above-described technical solution of the present invention has the following beneficial technical effects:

[0029] The near-infrared phosphor of the present invention has properties similar to Ca3Ga2Ge3O 12The same cubic garnet structure is used. In this invention, Sr, Ba, Bi, La, and Gd are used to replace part of Ca at position A. Since Sr, Ba, Bi, La, and Gd have similar properties or radii to Ca, this facilitates adjustment of the matrix band gap of the near-infrared phosphor and improves concentration quenching. Si is used to replace part of Ge, as Si has similar properties to Ge and does not cause significant structural distortion. N and F are used to replace part of O, utilizing the electronegativity difference between N and F to influence the crystal field environment of the luminescence center. Together with O, they achieve controllable spectral tuning. The substitution of Ga with Al, Sc, and In elements, which have similar properties, is beneficial for regulating the crystal field environment, improving lattice distortion, and maintaining structural stability. The introduction of low-valence elements Li, Mg, and Zn, and high-valence elements Zr, Hf, Sn, Ti, Ta, and Nb at the B site creates suitable active optical sites for Ni stability and provides charge compensation, effectively regulating the crystal field and thus enriching the emission band of the near-infrared phosphor. Doping with Mn, Eu, and Cr elements leverages Ni's strong absorption in the deep red region, using energy transfer to expand the excitation spectrum range of Ni and improve absorption efficiency, thereby enhancing emission intensity. The near-infrared phosphor of this invention… The emission peak wavelength of the phosphor is located in the 1470-1602nm range. This near-infrared phosphor can be excited by blue and red light, and can be matched with blue light chips, which can enrich the emission band of near-infrared phosphors and solve the problem of material scarcity. Furthermore, the near-infrared phosphor of the present invention has a large half-width, high quantum efficiency and good thermal stability, and can be effectively applied to applications such as moisture detection, beauty lamps, and medical analgesia. Moreover, the near-infrared phosphor of the present invention can be absorbed in the 680-850nm deep red-near-infrared domain, which is suitable for making doped fiber materials or ink materials for anti-counterfeiting or commemorative coin marking. Attached Figure Description

[0030] Figure 1 This is the excitation spectrum of the near-infrared phosphor sample prepared in Example 1;

[0031] Figure 2 The emission spectrum of the near-infrared phosphor sample prepared in Example 1;

[0032] Figure 3 The XRD pattern of the near-infrared phosphor sample prepared in Example 1;

[0033] Figure 4 This is a schematic diagram of the light-emitting device. Detailed Implementation

[0034] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments and the accompanying drawings. It should be understood that these descriptions are merely exemplary and not intended to limit the scope of the invention. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concept of the invention.

[0035] Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0036] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0037] A near-infrared phosphor, the phosphor comprising the formula A a (D d M m R r Q q E e G g Inorganic compounds, wherein the inorganic compounds have a similarity to Ca3Ga2Ge3O 12 The same cubic garnet structure; among which,

[0038] Element A includes one or two of Ca, Sr, Ba, Bi, La, and Gd;

[0039] The D element includes one or two of Al, Ga, In, and Sc;

[0040] The M element includes one or two of Li, Mg, and Zn;

[0041] The R element includes one or two of Zr, Hf, Sn, Ti, Ta, and Nb;

[0042] The element E is selected from one or both of Si and Ge;

[0043] The element G is selected from one or two of O, N, and F;

[0044] The element Q is selected from one or two of Mn, Eu, Cr and Ni;

[0045] 2.9≤a≤3.1, 1.9≤d+m+r+q≤2.1, 2.9≤e≤3.1, 11.8≤g≤12.2, 0<m≤1.1, 0<r≤1.1, 0<q≤0.25.

[0046] Furthermore, in this embodiment, 2.95≤a≤3.05, 1.97≤d+m+r+q≤2.03, 2.98≤e≤3.03, 11.9≤g≤12.05, 0<m≤0.95, 0<r≤1.03, and 0<q≤0.25.

[0047] Furthermore, in this embodiment, element A must contain Ca, and Ca accounts for more than or equal to 96% of element A; element D must contain Ga, and Ga accounts for more than or equal to 0.1% of element D; element E must contain Ge, and Ge accounts for more than or equal to 83.33% of element E; element G must contain O, and O accounts for more than or equal to 92% of element D; and element Q must contain Ni.

[0048] The phosphor emits peak wavelengths in the range of 1470-1602 nm.

[0049] The near-infrared phosphor in this embodiment has properties similar to Ca3Ga2Ge3O 12 The same cubic garnet structure is used. In this invention, Sr, Ba, Bi, La, and Gd are used to replace part of Ca at position A. Since Sr, Ba, Bi, La, and Gd have similar properties or radii to Ca, this facilitates adjustment of the matrix band gap of the near-infrared phosphor and improves concentration quenching. Si is used to replace part of Ge, as Si has similar properties to Ge and does not cause significant structural distortion. N and F are used to replace part of O, utilizing the electronegativity difference between N and F to influence the crystal field environment of the luminescence center. Together with O, they achieve controllable spectral tuning. The substitution of Ga with Al, Sc, and In elements, which have similar properties, is beneficial for regulating the crystal field environment, improving lattice distortion, and maintaining structural stability. The introduction of low-valence elements Li, Mg, and Zn and high-valence elements Zr, Hf, Sn, Ti, Ta, and Nb at the B site creates suitable active optical sites for Ni stability and provides charge compensation, effectively regulating the crystal field and thus enriching the emission band of the near-infrared phosphor. The doping of Mn, Eu, and Cr elements takes advantage of Ni's strong absorption in the deep red light region, using energy transfer to expand the excitation spectrum range of Ni and improve absorption efficiency, thereby promoting the enhancement of emission intensity.

[0050] Furthermore, in this embodiment, when the M element is Zn and the R element is Zr, and 0.8≤m / r≤1.

[0051] When element M is Zn and element R is Hf, and 0.9≤m / r≤1.1.

[0052] When element M is Zn and element R is Sn, and 0.85≤m / r≤1.

[0053] In this embodiment, considering that Mg is an alkali metal element and has similar properties to Ca, it often more easily substitutes for A. Therefore, M was chosen as Zn. Co-doping with Zn-R elements in this system can effectively improve the luminescence performance of Ni: on the one hand, Zn provides Ni with a suitable divalent environment and appropriate ion sites, improving the structural distortion caused by Ni and promoting the generation of optically active sites; on the other hand, the introduction of tetravalent R elements can act as a charge compensator, suppressing the valence change behavior of Ni during synthesis, thereby effectively improving its luminescence intensity and stability. Controlling the appropriate Zn / R ratio yields better luminescence without producing impurities that cause interference. Furthermore, the non-equivalent substitution of Ga by Zn / R ions with different radii and valence states easily modulates its crystal field intensity to obtain rich emission wavelengths, thus broadening its application areas. However, when Zn is used in combination with different R ions, different ratios have different effects on the matrix; therefore, the Zn / R ratio must vary within a certain range.

[0054] Furthermore, in this embodiment, when Q is composed of Ni and Cr, and the molar ratio of Cr in Q is α, 0.1% ≤ α ≤ 80%. Considering the strong absorption of activator Ni in the blue and deep red light ranges, Mn, Eu, and Cr ions, which emit deep red light when excited by blue light, are selected as sensitizers. This broadens the absorption range of the phosphor, redshifting the excitation spectrum to a position more compatible with the blue light chip; and improves the luminescence intensity and thermal stability of the phosphor through a more efficient energy transfer method. Experimental studies have shown that when the Cr content is too low, the energy transfer effect is not significant due to insufficient sensitizer, resulting in low luminescence intensity. When the Cr content is too high, concentration quenching occurs, increasing the probability of non-radiative transitions. Therefore, the preferred molar percentage of Cr in Q is α, and further, 0.4 < α ≤ 0.8, yields the best energy transfer effect.

[0055] The element A is Ca, D is Ga, M is Zn, E is Ge, G is O, and Q is Ni and Cr. Ni has good luminescent properties in this system.

[0056] The aforementioned near-infrared phosphor can be prepared using the following methods:

[0057] According to the molecular formula A of the inorganic substances contained in the near-infrared phosphor... a (D d M m R r Q q E e G g Raw materials are weighed according to stoichiometric ratios; the raw materials include corresponding oxides, carbonates, nitrates, and fluorides, etc.

[0058] The symmetrically selected raw materials are ground and mixed to obtain a raw material mixture;

[0059] The raw material mixture was placed in an alumina crucible and calcined in air to obtain the calcined product.

[0060] The sintering temperature for roasting is 1250-1350℃, and the heating rate is 5-8℃ / min, while the roasting holding time is 2-6h.

[0061] The calcined product was successively crushed, washed, sieved, and dried to obtain near-infrared phosphor.

[0062] A light-emitting device, Figure 4 A schematic diagram of the structure of a light-emitting device according to an embodiment of the present invention is shown, as follows: Figure 4 As shown, it includes an excitation light source and a light-emitting material 1. The light-emitting material includes near-infrared phosphor. The excitation light source is a semiconductor chip 2 with an emission peak wavelength range of 400-470nm. By adding glue 3 between the infrared phosphor and the semiconductor chip 2, the infrared phosphor is kept away from the high-temperature area. Preferably, the glue 3 is white glue, which helps to reduce the performance reduction of the lamp bead caused by the attenuation of the infrared phosphor.

[0063] Example 1

[0064] Compound formula Ca3Ga 0.93 Zn 0.45 Zr 0.5 Cr 0.07 Ni 0.05 Ge3O 12 According to the stoichiometric ratio, the corresponding oxide raw materials were weighed. CaCO3, Ga2O3, ZnO, ZrO2, Cr2O3, NiO, and GeO2 with an average particle size of 5.0 μm were used as the original powders. The above raw materials were ground and mixed evenly and then placed into a crucible. The crucible was calcined at 1300℃ for 6 hours. After cooling, the calcined product was obtained. The obtained calcined product was subjected to post-treatment such as crushing, grinding, grading, and sieving to obtain the near-infrared phosphor of Example 1. Figure 1 The absorption spectrum of the near-infrared phosphor sample prepared in Example 1 is shown; as follows: Figure 1 As shown, the near-infrared phosphor obtained in Example 1 was detected using X-ray spectroscopy. Its XRD diffraction pattern was consistent with PDF#11-0023 and was consistent with Ca3Ga2Ge3O. 12 They have the same cubic garnet structure; Figure 2 The emission spectrum of the near-infrared phosphor sample prepared in Example 1 is shown. Figure 3 The XRD pattern of the near-infrared phosphor sample prepared in Example 1 is shown; as follows: Figure 2 and Figure 3As shown, the absorption and emission spectra of the near-infrared phosphor of Example 1 were tested using a fluorescence spectrometer. The near-infrared phosphor prepared in Example 1 showed effective absorption in the 400-550 nm and 600-800 nm wavelength ranges, and its emission wavelength covered 1470-1602 nm, with the emission peak position λ. em =1549nm.

[0065] The near-infrared phosphors of Examples 2-68 were prepared according to the molecular formulas shown in Table 1, using the same preparation method as in Example 1. Table 1 shows the molecular formulas, corresponding emission peak wavelengths, and relative intensities of Examples 1-68 and the comparative examples. The relative intensities in the examples are based on the luminescence intensity of the comparative examples as a baseline value of 100. The relative luminescence intensity of the examples is the actual luminescence intensity divided by the actual luminescence intensity of the comparative examples, and then multiplied by 100%.

[0066] Table 1. Molecular formulas, corresponding emission peak wavelengths, and relative intensities of Examples 1-68

[0067]

[0068]

[0069]

[0070] By comparing the data from Examples 1-68 and the comparative examples, for A a (D d M m R r Q q E e G g In inorganic compounds, substitution or charge compensation at the A element site and Si substitution for Ge have relatively poor effects on improving overall luminescence performance. Zn-R doping effectively modulates the crystal field intensity of the matrix; as the substitution content increases, the crystal field gradually weakens, resulting in an emission wavelength tunable in the 1470–1602 nm range. Cr sensitization of Ni in this system not only redshifts its excitation wavelength from 415 nm to 467 nm but also exhibits efficient energy transfer, effectively improving the luminescence intensity of Ni and achieving more efficient near-infrared broadband emission.

[0071] Comparing Examples 1-22 with Examples 23-57, it can be found that there is a highly efficient energy transfer between Cr and Ni. In this system, the introduction of Cr ions significantly improves the luminescence performance of Ni ions and makes the phosphor more compatible with the wavelength requirements of blue light chips. When the Cr content is too low, the energy transfer effect is not obvious due to the lack of sensitizer, and the luminescence intensity is low. When the Cr content is too high, concentration quenching will occur, resulting in enhanced non-radiative transition.

[0072] Comparing Examples 23-56 with the comparative examples, it can be seen that Mg, being an alkali metal element, has similar properties to Ca and tends to more easily substitute at the a position. Therefore, the introduction of Mg is not conducive to improving its luminescence performance. Thus, Zn was chosen as the M element. The non-equivalent substitution of Ga-Ga by Zn-R (Zr / Hf / Sn) effectively regulates the crystal field environment, further enriching the types of near-infrared phosphors and expanding their coverage. Furthermore, Zn provides Ni with a suitable divalent environment and appropriate ion sites, improving the structural distortion caused by Ni and promoting the generation of optically active sites. The introduction of tetravalent R can act as a charge compensator, suppressing the valence change behavior of Ni during synthesis and improving the luminescence intensity to some extent. The effect of different Zn-R ratios on luminescence performance varies.

[0073] Examples 55-58 and the comparative examples show that when Zn-Ti substitutes Ga-Ga elements with the same properties, the matrix band gap narrows. The substitution of Li-R (Ta,Nb) results in a large charge imbalance, which leads to a deterioration in luminescence performance.

[0074] Examples 1-22 and 66-68, compared with comparative examples, reveal the presence of emitted Eu in the deep red to near-infrared band. 3+ Mn 4+ Cr 3+ Ions and Ni 2+ There are varying degrees of energy transfer phenomena, with Cr being the most prominent example. 3+ To Ni 2+ ET is relatively efficient. And Cr 3+ Ni achieves efficient energy transfer in a Zn-R co-substituted lattice. 2+ More efficient emission in the 1470-1602nm range.

[0075] Example 69

[0076] The light-emitting device in this embodiment uses a semiconductor chip with a wavelength of 460nm as the light source, and the light-emitting material is a near-infrared phosphor with the chemical formula Ca3Ga. 1.38 Zn 0.25 Hf 0.25 Cr 0.07 Ni 0.05 Ge3O 11.975According to the stoichiometric ratio, the raw materials are accurately weighed and symmetrically ground and mixed to obtain a mixture. The mixture is calcined at 1300℃ for 6 hours, and after cooling, a calcined product is obtained. The calcined product is then crushed, ground, graded, sieved, and washed to obtain near-infrared phosphor. In this embodiment, firstly, a layer of silicone is coated on top of the chip before applying the phosphor adhesive and cured to keep the phosphor away from the high-temperature area of ​​the chip, effectively reducing the attenuation of light source intensity caused by the phosphor being heated. Subsequently, visible light emitting material and silicone are mixed evenly at a mass ratio of 0.28:1 and covered on the silicone. It is then baked to cure into a visible light fluorescent layer. The visible light provided by the visible light emitting material and the visible light absorption of the near-infrared emitting material are used to improve the luminous efficiency of the device, especially the photoelectric conversion efficiency in the near-infrared emission band. Afterward, the near-infrared emitting material and silicone are mixed evenly at a mass ratio of 2.2:1, stirred, and degassed to obtain a visible light fluorescent conversion layer mixture. This mixture is then sprayed onto the surface of the visible light emitting material layer, cured, and encapsulated to obtain the desired LED light-emitting device. Using a high-precision, fast spectroradiometer integrating sphere testing system, the light source of the optical device provided in each embodiment was lit with a constant current (forward voltage 3V, forward current 60.0mA). The test results showed that the light-emitting device described in this embodiment has an optical power of 121.3mW and a photoelectric conversion efficiency of 53.1% in the near-infrared band.

[0077] Table 2 shows the semiconductor chip, near-infrared luminescent material formula, corresponding optical power, and photoelectric conversion efficiency in the near-infrared band of the light-emitting devices of Examples 70-76. The other settings are the same as in Example 69.

[0078] Table 2 Performance parameters of the optical devices in Examples 69-76

[0079]

[0080]

[0081] In summary, the near-infrared phosphor in the optical device of this invention can be effectively excited by an LED chip, preferably a 460nm blue light chip as the excitation source. The near-infrared phosphor of this invention can be used alone to make optical devices, achieving a continuous emission spectrum in the 1300-1800nm ​​near-infrared band, with a peak emission wavelength range of 1470-1602nm, suitable for specific applications. Alternatively, through optical devices combining visible light emitting materials and near-infrared emitting materials, dual emission in the 500-780nm visible light band and the 780-1300nm near-infrared band can be achieved, with suitable luminous flux and continuous or special waveform emission spectra, effectively applicable to applications such as moisture detection, material detection, medical imaging, and semiconductor material flaw detection.

[0082] It should be understood that the specific embodiments described above are merely illustrative or explanatory of the principles of the invention and do not constitute a limitation thereof. Therefore, any modifications, equivalent substitutions, improvements, etc., made without departing from the spirit and scope of the invention should be included within the protection scope of the invention. Furthermore, the appended claims are intended to cover all variations and modifications falling within the scope and boundaries of the appended claims, or equivalent forms of such scope and boundaries.

[0083] The present invention has been described above with reference to embodiments thereof. However, these embodiments are merely illustrative and not intended to limit the scope of the invention. The scope of the invention is defined by the appended claims and their equivalents. Various substitutions and modifications can be made by those skilled in the art without departing from the scope of the invention, and all such substitutions and modifications should fall within the scope of the invention.

[0084] Although embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and modifications can be made to the embodiments of the present invention without departing from the spirit and scope of the invention.

[0085] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A near-infrared phosphor, characterized in that, The phosphor comprises a compound with the formula A a (D d M m R r Q q E e G g Inorganic compounds, wherein the inorganic compounds have a similarity to Ca3Ga2Ge3O 12 The same cubic garnet structure; among which, Element A is selected from one or two of Ca, Sr, Ba, Bi, La, and Gd; The element D is selected from one or two of Al, Ga, In, and Sc; The element M is selected from one or both of Li and Zn; The element R is selected from one or two of Zr, Hf, and Sn; The element E is selected from one or both of Si and Ge; The element G is selected from one or both of O and F; The element Q is selected from one or two of Mn, Eu, Cr and Ni; 2.9≤a≤3.1, 1.9≤d+m+r+q≤2.1, 2.9≤e≤3.1, 11.8≤g≤12.2, 0<m≤1.1, 0<r≤1.1, 0<q≤0.25; When the elements Q are Ni and Cr, and the molar ratio of Cr in Q is α, 0.1%≤α≤80%; Element A must contain Ca, and Ca accounts for more than or equal to 96% of element A; element D must contain Ga, and Ga accounts for more than or equal to 0.1% of element D; element E must contain Ge, and Ge accounts for more than or equal to 83.33% of element E; element G must contain O, and O accounts for more than or equal to 92% of element G; element Q must contain Ni.

2. The phosphor according to claim 1, characterized in that, The phosphor has an emission peak wavelength range of 1470-1602 nm.

3. The phosphor according to claim 1, characterized in that, When M is Zn and R is Zr, and 0.8≤m / r≤1.

4. The phosphor according to claim 1, characterized in that, When element M is Zn and element R is Hf, and 0.9≤m / r≤1.

1.

5. The phosphor according to claim 1, characterized in that, When element M is Zn and element R is Sn, and 0.85≤m / r≤1.

6. The phosphor according to claim 1, characterized in that, The element A is Ca, D is Ga, M is Zn, E is Ge, G is O, and Q is Ni and Cr.

7. A light-emitting device comprising an excitation light source and a light-emitting material, characterized in that, The luminescent material comprises the near-infrared phosphor as described in any one of claims 1-6.

8. The light-emitting device according to claim 7, characterized in that, The excitation source is a semiconductor chip with an emission peak wavelength range of 400-470 nm.

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