A nickel-doped double perovskite-type luminescent material and its preparation method and application

Abstract

The present invention belongs to the technical field of luminescent materials and discloses a nickel-doped double perovskite luminescent material and its preparation method and application. The molecular formula of the luminescent material is M 1 3M 2 2‑x Ni x SbO6; among which M 1 Selected from Li and / or Na, M 2 Selected from Mg and / or Zn; 0.001≤x≤0.03. Due to the different constituent elements, the double perovskite-type luminescent material of the present invention can have an excitation peak wavelength in the ultraviolet light band of 325nm or 395nm, and emits near-infrared light with a peak wavelength of approximately 1380-1480nm. This material is well matched to ultraviolet LEDs and has great application potential in the field of near-infrared spectroscopy technology.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and in particular relates to a nickel-doped double perovskite-type luminescent material and a preparation method and application thereof. Background Art

[0002] In recent years, near-infrared spectroscopy technology has played an important role in food safety testing, security systems, environmental protection, modern agriculture, and biological imaging due to its non-destructive, convenient, and rapid characteristics. Due to the shortcomings of traditional light sources (halogen lamps and incandescent lamps) such as high power consumption, narrow bandwidth, and low efficiency, they cannot meet the needs of near-infrared spectroscopy technology. In contrast, conversion light-emitting diodes (NIR pc-LEDs) based on near-infrared luminescent materials have significant advantages such as low power consumption, high safety assurance, and adjustable emission spectra, and are considered to be highly promising near-infrared light sources. Among them, Ni 2 +-doped luminescent materials have attracted much attention due to their broadband emission, high stability, and potential in biomedical imaging. 2+ It is extremely sensitive to the octahedral crystal field, so tunable broadband emission in the near infrared can be achieved by adjusting the crystal field strength. 2+ Doped luminescent materials have many advantages, but most of the Ni 2+ The fluorescence quantum yield (QY) of single-doped luminescent materials is still less than 30%. The best performance is Mg4Ta2O9:Ni developed by Mou Zhongfei's team at Guangdong University of Technology. 2+ The fluorescence quantum yield (QY) of the phosphor (see Ceram. Int. 50 (11), 18647-18654 (2024).) is only 64.2%. The low fluorescence quantum yield is always the limiting factor for Ni 2+ Therefore, research and development of a Ni-doped luminescent material 2+ High fluorescence quantum yield phosphors and near-infrared conversion LED devices using activator ions are the main research targets at present and are of great significance. Summary of the Invention

[0003] The present invention addresses the problems existing in the prior art. Its primary purpose is to provide a nickel-doped double perovskite-type luminescent material. This luminescent material can be efficiently excited by 325nm or 395nm ultraviolet light, with a peak emission wavelength between 1380nm and 1480nm and high relative luminescence intensity.

[0004] Another object of the present invention is to provide a method for preparing the above-mentioned nickel-doped double perovskite-type light-emitting material.

[0005] Another object of the present invention is to provide an application of the above nickel-doped double perovskite-type light-emitting material.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] A nickel-doped double perovskite-type luminescent material, the molecular formula of the luminescent material is M 1 3M 2 2-x Ni x SbO6; among which M 1 Selected from Li and / or Na, M 2 Selected from Mg and / or Zn; 0.001≤x≤0.03.

[0008] The method for preparing the nickel-doped double perovskite-type luminescent material comprises the following specific steps:

[0009] S1.M 1 Compound, M 2 The compound, the Sb compound and the Ni compound are ground and mixed uniformly to obtain a mixture;

[0010] S2. Sinter the mixture in air at 1200-1500° C. for 4-48 hours, and grind it to obtain a double perovskite-type light-emitting material.

[0011] Preferably, the M in step S1 1 The compound is a Li compound or / and a Na compound, M 2 The compound is a Mg compound and / or a Zn compound.

[0012] More preferably, the Li compound is one or more of lithium carbonate, lithium nitrate, lithium chloride or lithium hydroxide, the Na compound is one or more of sodium carbonate, sodium bicarbonate, sodium chloride or sodium hydroxide, the Mg compound is one or more of magnesium carbonate, basic magnesium carbonate, magnesium oxide, magnesium hydroxide or magnesium nitrate, and the Zn compound is one or more of zinc oxide, zinc sulfate, zinc chloride or zinc carbonate.

[0013] Preferably, in step S1, the Sb compound is antimony pentoxide and / or antimony trioxide; and the Ni compound is nickel oxide and / or nickel nitrate.

[0014] Application of the nickel-doped double perovskite-type luminescent material in light conversion devices.

[0015] Preferably, the light conversion device is a near-infrared LED device.

[0016] The present invention uses the optically active element Ni 2+ Dissolved in M 1 3M 2 2-x Ni xA new structure and new composition of perovskite-type luminescent material system was obtained in the crystalline phase of SbO6 double perovskite compound. Its excitation peak wavelength is located at 325 / 395nm, and its emission peak is located at 1380-1480nm. It has potential applications in the field of near-infrared spectroscopy technology.

[0017] This invention relates to Ni 2+ Doping M alone 1 3M 2 2-x Ni x SbO6, or on this basis, a luminescent material with a new component is formed, as well as a mixture mainly containing the above components. The double perovskite luminescent material can be obtained by changing M 1 or M 2 The proportion of components is adjusted to achieve fine control of the luminescence peak position and luminescence efficiency.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] 1. The double perovskite-type luminescent material of the present invention has an excitation peak wavelength in the 325nm or 395nm band, and can emit near-infrared light with a peak wavelength of approximately 1380 to 1480nm. It can be well matched with ultraviolet LEDs and has great application potential in the field of near-infrared spectroscopy technology.

[0020] 2. The raw materials of the double perovskite-type light-emitting material of the present invention are cheap and easily available, and the synthesis temperature is relatively low. The preparation process is simple and does not require special reaction equipment, making industrial production very convenient. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Li3Mg of Example 1 1.985 Ni 0.015 X-ray powder diffraction pattern of SbO6;

[0022] Figure 2 Li3Mg of Example 1 1.985 Ni 0.015 Excitation spectrum of SbO6;

[0023] Figure 3 Li3Mg in Example 1 1.985 Ni 0.015 Emission spectrum of SbO6;

[0024] Figure 4 Li3Zn in Example 7 1.985 Ni 0.005 X-ray powder diffraction pattern of SbO6;

[0025] Figure 5 Li3Zn in Example 71.985 Ni 0.005 Excitation spectrum of SbO6;

[0026] Figure 6 Li3Zn in Example 7 1.985 Ni 0.005 Emission spectrum of SbO6.

[0027] Figure 7 Li3Mg in Example 1 1.985 Ni 0.015 Graph of SbO6 near-infrared device output power and photoelectric conversion efficiency. DETAILED DESCRIPTION

[0028] The present invention will be further described below in conjunction with specific examples, but should not be construed as limiting the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0029] Example 1

[0030] 0.015 mol Li2CO3, 0.01985 mol MgO, 0.005 mol Sb2O3, and 0.00015 mol NiO, all of analytically pure, were thoroughly ground for 30 minutes, mixed, and then placed in an alumina crucible and calcined at 1350°C for 4 hours. After cooling to room temperature, the product was crushed, ground, washed, and processed to obtain a nickel-doped double perovskite luminescent material with the chemical formula Li3Mg 1.985 Ni 0.015 SbO6.

[0031] Figure 1 Li3Mg of Example 1 1.985 Ni 0.015 X-ray powder diffraction pattern of SbO6. Figure 1 It can be seen that the X-ray powder diffraction pattern (Cu target, λ = 0.15406nm) is similar to that of Li3Mg 1.985 Ni 0.015 SbO6 standard card comparison Figure 1 As shown, Figure 2 Li3Mg of Example 1 1.985 Ni 0.015 Excitation spectrum of SbO6. Figure 2 It can be seen that the luminescent powder can be effectively excited by ultraviolet light and red light in the range of 350 to 850 nm, and the main excitation peak is located at 395 nm. Figure 3 In this embodiment, Li3Mg 1.985 Ni 0.015 The emission spectrum of SbO6 is given by Figure 3 It can be seen that the emission spectrum covers 1000-1700 nm, with the main emission peak located at 1380 nm. Under 395 nm ultraviolet light excitation, the relative luminescence intensity is 100% (see Table 1).

[0032] Example 2

[0033] 0.015 mol Li2CO3, 0.01995 mol MgO, 0.005 mol Sb2O3 and 0.00005 mol NiO, all of which were analytically pure, were fully ground for 30 minutes, mixed evenly, and then placed in an alumina crucible and calcined at 1350°C for 4 hours. After cooling to room temperature, the product was crushed, ground, washed, and other post-processing to obtain a nickel-doped double perovskite luminescent material with the molecular formula Li3Mg 1.995 Ni 0.005 SbO6.

[0034] Under 395nm ultraviolet light excitation, the double perovskite luminescent material has an emission spectrum covering 1000-1700nm, a main emission peak at 1380nm, and a relative luminous intensity of 55.5% (see Table 1).

[0035] Example 3

[0036] 0.015 mol Li2CO3, 0.0199 mol MgO, 0.005 mol Sb2O3 and 0.0001 mol NiO of analytically pure materials were thoroughly ground for 30 minutes, mixed evenly, and then placed in an alumina crucible and calcined at 1350°C for 4 hours. After cooling to room temperature, the product was crushed, ground, washed, and processed to obtain a nickel-doped double perovskite luminescent material with the molecular formula of Li3Mg 1.990 Ni 0.010 SbO6.

[0037] Under 395nm ultraviolet light excitation, the double perovskite luminescent material has an emission spectrum covering 1000-1700nm, a main emission peak at 1380nm, and a relative luminous intensity of 67.7% (see Table 1).

[0038] Example 4

[0039] 0.015 mol Li2CO3, 0.0198 mol MgO, 0.005 mol Sb2O3 and 0.0002 mol NiO of analytically pure materials were thoroughly ground for 30 minutes, mixed evenly, and then placed in an alumina crucible and calcined at 1350°C for 4 hours. After cooling to room temperature, the product was crushed, ground, washed, and processed to obtain a nickel-doped double perovskite luminescent material with the molecular formula of Li3Mg 1.98 Ni 0.02 SbO6.

[0040] Under 395nm ultraviolet light excitation, the double perovskite luminescent material has an emission spectrum covering 1000-1700nm, a main emission peak at 1380nm, and a relative luminous intensity of 95.8% (see Table 1).

[0041] Example 5

[0042] 0.015 mol Li2CO3, 0.01975 mol MgO, 0.005 mol Sb2O3 and 0.00025 mol NiO of analytical grade were fully ground for 30 minutes, mixed evenly and then placed in an alumina crucible and calcined at 1350°C for 4 hours. After cooling to room temperature, the product was crushed, ground, washed and other post-processing to obtain a nickel-doped double perovskite luminescent material with the molecular formula of Li3Mg 1.975 Ni 0.025 SbO6.

[0043] Under 395nm ultraviolet light excitation, the double perovskite luminescent material has an emission spectrum covering 1000-1700nm, a main emission peak at 1380nm, and a relative luminous intensity of 87.6% (see Table 1).

[0044] Example 6

[0045] 0.015 mol Li2CO3, 0.01970 mol MgO, 0.005 mol Sb2O3 and 0.0003 mol NiO of analytical grade were fully ground for 30 minutes, mixed evenly, and then placed in an alumina crucible and calcined at 1350°C for 4 hours. After cooling to room temperature, the product was crushed, ground, washed and other post-processing to obtain a nickel-doped double perovskite luminescent material with the molecular formula of Li3Mg 1.97 Ni 0.03 SbO6.

[0046] Under 395nm ultraviolet light excitation, the double perovskite luminescent material has an emission spectrum covering 1000-1700nm, a main emission peak at 1380nm, and a relative luminous intensity of 60.1% (see Table 1).

[0047] Example 7

[0048] 0.015 mol Li2CO3, 0.01995 mol ZnO, 0.005 mol Sb2O3, and 0.00005 mol NiO of analytically pure material were weighed and thoroughly ground for 30 minutes. After mixing, the mixture was placed in an alumina crucible and calcined at 1350°C for 4 hours. After cooling to room temperature, the product was crushed, ground, washed, and processed to obtain a nickel-doped double perovskite luminescent material with the molecular formula of Li3Mg 1.995 Ni 0.005 SbO6.

[0049] Figure 4 Li3Zn in Example 7 1.995 Ni 0.005 X-ray powder diffraction pattern of SbO6. Figure 4 It can be seen that the X-ray powder diffraction pattern (Cu target, λ = 0.15406nm) is similar to that of Li3Zn 1.995 Ni 0.005 Compared with the standard card of SbO6, it was concluded that the sample XRD had no impurity peaks and was highly pure. Figure 5 Li3Zn in Example 7 1.995 Ni 0.005 Excitation spectrum of SbO6. Figure 5 It can be seen that the luminescent powder can be effectively excited by ultraviolet light and red light in the range of 250 to 850 nm, and the main excitation peak is located at 325 nm. Figure 6 Li3Mg of Example 7 1.985 Ni 0.015 The emission spectrum of SbO6 is given by Figure 6 It can be seen that the emission spectrum covers 1000-1700 nm, with the main emission peak located at 1480 nm. Under 325 nm ultraviolet light excitation, the relative luminescence intensity is 45.1% (see Table 1).

[0050] Example 8

[0051] 0.015 mol Li2CO3, 0.0199 mol ZnO, 0.005 mol Sb2O3 and 0.0001 mol NiO of analytically pure material were fully ground for 30 minutes, mixed evenly, and then placed in an alumina crucible and calcined at 1350℃ for 4 hours. After cooling to room temperature, the product was crushed, ground, washed and other post-processing to obtain a nickel-doped double perovskite luminescent material with the molecular formula of Li3Zn 1.9 Ni 0.01 SbO6.

[0052] Under 325nm ultraviolet light excitation, the double perovskite luminescent material has an emission spectrum covering 1000-1700nm, a main emission peak at 1480nm, and a relative luminous intensity of 29.4% (see Table 1).

[0053] Example 9

[0054] 0.015 mol Li2CO3, 0.01985 mol ZnO, 0.005 mol Sb2O3, and 0.00015 mol NiO of analytically pure material were weighed and thoroughly ground for 30 minutes. After mixing, they were placed in an alumina crucible and calcined at 1350°C for 4 hours. After cooling to room temperature, the product was crushed, ground, washed, and processed to obtain a nickel-doped double perovskite luminescent material with a chemical composition of Li3Mg1.985 Ni 0.015 SbO6.

[0055] Under 325nm ultraviolet light excitation, the double perovskite luminescent material has an emission spectrum covering 1000-1700nm, a main emission peak at 1480nm, and a relative luminous intensity of 19.5% (see Table 1).

[0056] Example 10

[0057] 0.015 mol Li2CO3, 0.0198 mol ZnO, 0.005 mol Sb2O3, and 0.0002 mol NiO of analytically pure material were weighed and thoroughly ground for 30 minutes. After mixing, they were placed in an alumina crucible and calcined at 1350°C for 4 hours. After cooling to room temperature, the product was crushed, ground, washed, and processed to obtain a nickel-doped double perovskite luminescent material with a chemical composition of Li3Zn 1.98 Ni 0.020 SbO6.

[0058] Under 395nm ultraviolet excitation, the double perovskite luminescent material has an emission spectrum covering 1000-1700nm, a main emission peak at 1480nm, and a relative luminous intensity of 12.9% (see Table 1).

[0059] Example 11

[0060] 0.0125mol Li2CO3, 0.00025mol Na2CO3, 0.01985mol MgO, 0.005mol Sb2O3 and 0.00015mol NiO, all of which were analytically pure, were fully ground for 30 minutes, mixed evenly, and then placed in an alumina crucible and calcined at 1300℃ for 6 hours. After cooling to room temperature, the product was crushed, ground, washed and other post-processing to obtain a nickel-doped double perovskite luminescent material with the molecular formula Li 2.5 Na 0.5 Mg 1.985 Ni 0.015 SbO6.

[0061] Under 395nm ultraviolet light excitation, the double perovskite luminescent material has an emission spectrum covering 1000-1700nm, a main emission peak at 1391nm, and a relative luminous intensity of 86.5% (see Table 1).

[0062] Example 12

[0063] 0.010 mol Li2CO3, 0.005 mol Na2CO3, 0.01985 mol MgO, 0.005 mol Sb2O3, and 0.00015 mol NiO, all of analytically pure, were thoroughly ground for 30 minutes, mixed evenly, and then placed in an alumina crucible and calcined at 1300°C for 6 hours. After cooling to room temperature, the product was crushed, ground, washed, and processed to obtain a nickel-doped double perovskite luminescent material with the molecular formula Li2NaMg 1.985 Ni 0.015 SbO6.

[0064] Under 395nm ultraviolet excitation, the double perovskite luminescent material has an emission spectrum covering 1000-1700nm, a main emission peak at 1420nm, and a relative luminous intensity of 72.9% (see Table 1).

[0065] Application Example 1

[0066] The Li3Mg of Example 1 1.985 Ni 0.015 The pc-LED device was manufactured by packaging SbO6 luminescent material with 395nm LED chip. The near-infrared output power and photoelectric conversion efficiency of the device were measured under the excitation of 25-250mA driving current. Figure 7 The output power and photoelectric conversion efficiency of the near-infrared device made of the double perovskite type luminescent material of Example 1 are shown in FIG. Figure 7 It can be seen that at a current of 100mA, a near-infrared output of 307.9mW@0.72% was obtained, indicating that the luminescent material Li3Mg 1.985 Ni 0.015 SbO6 is compatible with 395nm LED chips and emits near-infrared light when excited by them. PC-LED devices made by packaging the luminescent materials of other embodiments with 395nm LED chips can also emit near-infrared light when excited by a current of 25-250mA, the difference being the brightness.

[0067] Table 1 shows the emission peak positions and relative luminescence intensities of the luminescent materials of Examples 1-12 under 325nm and 395nm ultraviolet light excitation.

[0068] serial number Chemical formula of luminescent material Emission main peak position (nm) Relative luminous intensity (%) Example 1 <![CDATA[Li3Mg 1.985 In 0.015 SbO6]]> 1380 100 Example 2 <![CDATA[Li3Mg 1.995 In 0.005 SbO6]]> 1380 55.5 Example 3 <![CDATA[Li3Mg 1.99 In 0.01 SbO6]]> 1380 67.7 Example 4 <![CDATA[Li3Mg 1.980 In 0.02 SbO6]]> 1380 95.8 Example 5 <![CDATA[Li3Mg 1.975 In 0.025 SbO6]]> 1380 87.6 Example 6 <![CDATA[Li3Mg 1.97 In 0.03 SbO6]]> 1380 60.1 Example 7 <![CDATA[Li3Zn 1.995 In 0.005 SbO6]]> 1480 45.1 Example 8 <![CDATA[Li3Zn 1.99 In 0.010 SbO6]]> 1480 29.4 Example 9 <![CDATA[Li3Zn 1.985 In 0.015 SbO6]]> 1480 19.5 Example 10 <![CDATA[Li3Zn 1.98 In 0.02 SbO6]]> 1480 12.9 Example 11 <![CDATA[Li 2.5 That 0.5 Mg 1.985 By 0.015 SbO6]]> 1391 86.5 Example 12 <![CDATA[Li2NaMg 1.985 In 0.015 SbO6]]> 1420 72.9

[0069] Table 1 shows the emission peak positions and relative luminescence intensities of the luminescent materials of Examples 1-12 under 325nm and 395nm ultraviolet light excitation. 2-x Ni x SbO6 luminescent material emits near-infrared light with a peak wavelength of 1380nm under 395nm ultraviolet light excitation, and can be used as a near-infrared pc-LED phosphor for fluorescence conversion. As shown in Table 1, Ni2+ The doped luminescent material does not show obvious wavelength red shift with the increase of doping concentration. This is because Ni 2+ Ions and Mg 2+ and Zn 2+ The reason is that the ionic radius is similar. At the same time, Zn 2+ Ion substitution Mg 2+ ions, the relative luminescence intensity dropped dramatically with the red shift of the emission main peak position, indicating that the luminescence performance of Mg in this double perovskite structure is significantly better than that of Zn. In the process of Na+ ions replacing Li+ ions, the luminescence intensity slowly decreased with the red shift of the emission main peak position, which has important guiding significance for the further development of long-wavelength luminescent materials.

[0070] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A nickel-doped double perovskite-type luminescent material, characterized in that: The molecular formula of the luminescent material is M 1 3M 2 2- x Ni x SbO6; among which M 1 Selected from Li and / or Na, M 2 Selected from Mg and / or Zn; 0.001≤x≤0.

03.

2. The method for preparing the nickel-doped double perovskite-type luminescent material according to claim 1, wherein: The specific steps include: S1.M 1 Compound, M 2 The compound, the Sb compound and the Ni compound are ground and mixed uniformly to obtain a mixture; S2. Sintering the mixture in air at 1200-1500° C. for 4-48 hours, and grinding the mixture to obtain a double perovskite-type light-emitting material.

3. The method for preparing the nickel-doped double perovskite-type luminescent material according to claim 2, wherein: The M in step S1 1 The compound is a Li compound or / and a Na compound, M 2 The compound is a Mg compound and / or a Zn compound.

4. The method for preparing the nickel-doped double perovskite-type light-emitting material according to claim 3, wherein: The Li compound is one or more of lithium carbonate, lithium nitrate, lithium chloride or lithium hydroxide; the Na compound is one or more of sodium carbonate, sodium bicarbonate, sodium chloride or sodium hydroxide; the Mg compound is one or more of magnesium carbonate, basic magnesium carbonate, magnesium oxide, magnesium hydroxide or magnesium nitrate; and the Zn compound is one or more of zinc oxide, zinc sulfate, zinc chloride or zinc carbonate.

5. The method for preparing the nickel-doped double perovskite-type light-emitting material according to claim 2, wherein: In step S1, the Sb compound is antimony pentoxide and / or antimony trioxide; and the Ni compound is nickel oxide and / or nickel nitrate. 6 . Use of the nickel-doped double perovskite-type luminescent material according to claim 1 in a light conversion device.

7. The use according to claim 6, characterized in that The light conversion device is a near-infrared LED device.

Images