Double-narrow-band red light emission fluorescent material and application thereof in ink-jet printing ink

Abstract

The invention provides a double-narrow-band red light emission fluorescent material and application thereof in ink-jet printing ink. A chemical general formula of Sr3Hf (2-x) MnxNb (2-x) Mn1.25xO12 (wherein x is greater than or equal to 0.02 and less than or equal to 0.09) can be used for representing the double-narrow-band red light emission fluorescent material. The fluorescent material can absorb blue light to generate red light emission; under the excitation of light of 450 nm, the emission spectrum is two narrow-band emission peaks, and the two narrow-band emission peaks are located at the wavelength of 627 nm and the wavelength of 639 nm respectively; the full width at half maximum of each of the two narrow-band emission peaks is less than 3nm; under the excitation of 450nm blue light, the quantum efficiency of the dual-narrow-band red light-emitting fluorescent material is greater than 60%; under the excitation of 450 nm blue light, the ratio of the luminous intensity of the double-narrow-band red light emitting fluorescent material at 150 DEG C to the luminous intensity of the fluorescent material at 25 DEG C is greater than 70% and less than 80%.

Description

Technical Field

[0001] The invention relates to the field of fluorescent materials, and in particular to a fluorescent material emitting double narrow-band red light and an application of the same in inkjet printing ink. Background Art

[0002] The current development trend of display and lighting technology is to achieve ultra-thin, large-area and flexible display. Inkjet printing is a non-contact technology with the advantages of high material utilization, suitability for flexible processing, and pattern processing without masks. It is currently the most promising production solution for processing and preparing ultra-thin and large-area flexible displays.

[0003] The premise of inkjet printing is ink that can be used for inkjet printing. At present, (solution phase) cadmium-based and lead-based quantum dot inkjet printing inks are the most common. For example, patent document 1 (Nigel Pickett, Imad Nasani, James Harris, Nathalie Gresty, Quantum dot LEDs for enhancing growth in photosynthetic organisms, CN108605562A) discloses an ink scheme including components such as CdSe, CdTe, CdSeS, CdSeTe, CdSTeCdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, CdZnSeS, CdZnSeTe, CdHgSeS, CdHgSeTe and CdHgSTe; and patent document 2 (Sun Yajuan, Liu Zhijun, Wang Yunjun, Perovskite quantum dot ink for inkjet printing and preparation method thereof, CN109321036A) discloses a lead-based quantum dot inkjet printing ink developed based on lead-containing raw materials such as PbCl2, PbI2 and PbBr2. However, it should be pointed out that cadmium and lead are highly environmentally toxic, so the development of non-cadmium-based and non-lead-based inkjet printing inks has always been a research hotspot in related fields.

[0004] Considering that the three primary colors that make up white light are red, green and blue, the three most important colors of inkjet printing ink are red, green and blue inkjet printing inks. With the advancement of inkjet printing technology, many (solid) inorganic materials can also be directly printed by inkjet technology. For example, patent document 3 (Liu Hong, Ma Baojin, Zhang Shan, Wang Shicai, Qiu Jichuan, Duan Jiazhi, Sang Yuanhua, a kind of amino acid-rare earth complex high-efficiency fluorescent powder and its preparation method, CN106854169B) discloses a technical solution for inkjet printing by replacing the ink in an ordinary inkjet printer with an amino acid-rare earth complex high-efficiency fluorescent powder. That is, inorganic fluorescent materials can also be used in inkjet printing.

[0005] As for inorganic fluorescent materials, there is a relative lack of red light. Currently, the most widely used one is as shown in patent document 4 (Shao Qiyue, Wang Yiwei, Yao Leqi, Xing Junjie, Dong Yan, Jiang Jianqing, a K2SiF6:Mn4+ Preparation method of nano fluorescent powder, CN113355088B) discloses K2SiF6:Mn red fluorescent material. As a Mn-doped fluorescent material, the luminescence of K2SiF6:Mn shows a main peak of ~630nm and multiple sharp emission peaks nearby. Non-patent document 1 (Sadao Adachi, Review—Mn 4+ -Activated Red and Deep Red-Emitting Phosphors, ECSJournal of Solid State Science and Technology, 2020, 9, 1:016001) believes that Mn 4+ The doped fluorescent materials are mostly fluorescent materials that emit single narrow-band red light, which results in the lack of longer wavelength red light in its spectral components.

[0006] In summary, it can be seen from the currently disclosed literature that there is no report on dual narrow-band red light emission for Mn-doped fluorescent materials. The dual narrow-band red light emitting fluorescent material applied for in the present invention is disclosed for the first time by the applicant. Summary of the invention

[0007] One of the purposes of the present invention is to provide a fluorescent material with dual narrow-band red light emission. The fluorescent material can absorb blue light and generate red light emission. Under the excitation of 450nm light, the emission spectrum is two narrow-band emission peaks located at 627nm and 639nm respectively, with a half-width of less than 3nm; under the excitation of 450nm light, the quantum efficiency of the fluorescent material with dual narrow-band red light emission is greater than 60%; under the excitation of 450nm light, the ratio of the luminous intensity of the fluorescent material with dual narrow-band red light emission at 150℃ to the luminous intensity of the fluorescent material at 25℃ is greater than 70% and less than 80%, so that the luminescent material can be applied to white light LED lighting devices.

[0008] To achieve the above object, the present invention adopts the following technical solution:

[0009] A double narrow-band red light emitting fluorescent material, the chemical formula of the material is:

[0010] S3F 2-x Mn x Nb 2-x Mn 1.25x O 12

[0011] Among them, 0.02≤x≤0.09.

[0012] Preferably, x may be 0.05.

[0013] The second object of the present invention is to provide a method for preparing a fluorescent material with dual narrow-band red light emission. The preparation method comprises the following steps:

[0014] The Sr precursor, Hf precursor, Mn precursor and Nb precursor are subjected to a high temperature solid phase reaction in an air atmosphere to obtain a chemical formula which can be expressed as Sr3Hf 2-x Mn x Nb 2-x Mn 1.25x O 12 A dual narrow-band red light emitting fluorescent material, wherein 0.02≤x≤0.09.

[0015] Preferably, x=0.05.

[0016] Preferably, in this step, the molar ratio of Sr, Hf, Mn and Nb in the Sr precursor, Hf precursor, Mn precursor and Nb precursor is 3:(2-x):2.25x:(2-x), wherein 0.02≤x≤0.09;

[0017] Preferably, in this step, the Sr precursor is selected from one or more of Sr carbonate, Sr oxide, Sr oxalate and Sr nitrate; the Hf precursor is selected from hafnium dioxide; the Mn precursor is selected from one or more of Mn carbonate, Mn oxide, Mn oxalate and Mn nitrate; and the Nb precursor is selected from niobium pentoxide.

[0018] Preferably, the purity of the Sr precursor, the Hf precursor, the Mn precursor and the Nb precursor is not less than 99.5%.

[0019] Preferably, in the above step, the temperature of the high temperature solid phase reaction is 1450-1650° C. under air atmosphere, and the time of the high temperature solid phase reaction is between 4 and 10 hours.

[0020] The third object of the present invention is to provide a dual narrow-band red light emitting fluorescent material for use in preparing inkjet printing ink, wherein the inkjet printing ink comprises toluene, terpineol and a wavelength conversion material, wherein the mass ratio of toluene, terpineol and the wavelength conversion material is 1:0.05:0.95, and the wavelength conversion material at least comprises a chemical formula which can be expressed as Sr3Hf 2-x Mn x Nb 2- x Mn 1.25x O 12 (wherein 0.02≤x≤0.09) dual narrow-band red light emitting fluorescent material.

[0021] The specific plan is as follows:

[0022] The Sr precursor, Hf precursor, Mn precursor and Nb precursor are subjected to a high temperature solid phase reaction in an air atmosphere to obtain a chemical formula which can be expressed as Sr3Hf 2-x Mn x Nb 2-x Mn 1.25x O 12 A dual narrow-band red light emitting fluorescent material, wherein 0.02≤x≤0.09;

[0023] Preferably, x=0.05.

[0024] Furthermore, the Sr precursor is selected from one or more of Sr carbonate, Sr oxide, Sr oxalate and Sr nitrate; the Hf precursor is selected from hafnium dioxide; the Mn precursor is selected from one or more of Mn carbonate, Mn oxide, Mn oxalate and Mn nitrate; and the Nb precursor is selected from niobium pentoxide.

[0025] Furthermore, in the step, the temperature of the high temperature solid phase reaction is 1450-1650° C., and the time of the high temperature solid phase reaction is between 4 and 10 hours.

[0026] Optionally, the purity of the Sr precursor, the Hf precursor, the Mn precursor and the Nb precursor is not less than 99.5%.

[0027] The present invention also provides an inkjet printing ink made of a fluorescent material based on dual narrow-band red light emission, wherein the light-emitting device comprises toluene, terpineol and a wavelength conversion material, wherein the mass ratio of toluene, terpineol and the wavelength conversion material is 1:0.05:0.95, and the wavelength conversion material at least comprises a chemical formula which can be expressed as Sr3Hf 2-x Mn x Nb 2-x Mn 1.25x O 12 (wherein 0.02≤x≤0.09) dual narrow-band red light emitting fluorescent material.

[0028] Beneficial Effects

[0029] The present invention provides a double narrow-band red light emitting fluorescent material and its inkjet printing ink application. 2-x Mn x Nb 2-x Mn 1.25x O 12(wherein, 0.02≤x≤0.09) represents the dual narrow-band red light emitting fluorescent material. The fluorescent material can absorb blue light to generate red light emission; under the excitation of 450nm light, the emission spectrum is two narrow-band emission peaks, and the two narrow-band emission peaks are respectively located at ~627nm and ~639nm; the half-height width of each of the two narrow-band emission peaks is <3nm; the quantum efficiency of the dual narrow-band red light emitting fluorescent material under the excitation of 450nm light is >60%; under the excitation of 450nm light, the ratio of the luminous intensity of the dual narrow-band red light emitting fluorescent material at 150℃ to the luminous light intensity of the fluorescent material at 25℃ is greater than 70% and less than 80%. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a spectrum of the material obtained in Comparative Example 1 of the present invention;

[0031] Figure 2 This is a spectrum of the material obtained in Comparative Example 2 of the present invention;

[0032] Figure 3 is the X-ray diffraction pattern of the material corresponding to Example 1 of the present invention;

[0033] Figure 4 is a crystal structure diagram of the material matrix corresponding to Example 1 of the present invention;

[0034] Figure 5 The excitation and emission spectra of the corresponding material in Example 1 of the present invention;

[0035] Figure 6 This is the emission spectrum of the material corresponding to Example 4 of the present invention.

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.

[0037] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only used to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0038] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0039] The present application proposes a fluorescent material with dual narrow-band red light emission, which can be represented by a general chemical formula:

[0040] S3F 2-x Mn x Nb 2-x Mn 1.25x O 12

[0041] Among them, 0.02≤x≤0.09.

[0042] In some embodiments of the present application, x is preferably 0.02; in some embodiments of the present application, x is preferably 0.03; in some embodiments of the present application, x is preferably 0.04; in some embodiments of the present application, x is preferably 0.05; in some embodiments of the present application, x is preferably 0.06; in some embodiments of the present application, x is preferably 0.07; in some embodiments of the present application, x is preferably 0.08; in other embodiments of the present application, x is preferably 0.09.

[0043] The present application also proposes a preparation technology of a fluorescent material with dual narrow-band red light emission, the steps of which are as follows:

[0044] The Sr precursor, Hf precursor, Mn precursor and Nb precursor are subjected to a high temperature solid phase reaction in an air atmosphere to obtain a chemical formula which can be expressed as Sr3Hf 2-x Mn x Nb 2-x Mn 1.25x O 12 A dual narrow-band red light emitting fluorescent material, wherein 0.02≤x≤0.09.

[0045] In the above steps, the molar ratio of Sr, Hf, Mn and Nb in the Sr precursor, Hf precursor, Mn precursor and Nb precursor is 3:(2-x):2.25x:(2-x), wherein 0.02≤x≤0.09.

[0046] In the above steps, the Sr precursor can be a compound containing Sr well known in the art, and there is no special limitation. In the present invention, the Sr precursor is preferably selected from one or more of Sr carbonates, Sr oxides, Sr oxalates and Sr nitrates, and more preferably Sr carbonates, i.e. SrCO3; the Hf precursor is selected from HfO2; the Mn precursor is selected from one or more of Mn carbonates, Mn oxides, Mn oxalates and Mn nitrates, and more preferably Mn oxides, i.e. MnO2; the Nb precursor is selected from Nb2O5.

[0047] The purity of the above-mentioned Sr precursor, Hf precursor, Mn precursor and Nb precursor is not less than 99.5%. The higher the purity, the less impurities in the obtained luminescent material.

[0048] In the above steps, the temperature of the high temperature solid phase reaction is between 1450° C. and 1650° C., and the time of the high temperature solid phase reaction is between 4 and 10 hours in an air atmosphere.

[0049] The temperature of the high-temperature solid phase in the above steps is preferably 1450-1650°C in an air atmosphere; in some embodiments provided by the present invention, the temperature of the high-temperature solid phase is preferably 1550°C.

[0050] The high temperature solid phase time in the above steps is preferably 4 to 10 hours, more preferably 5 to 8 hours; in some embodiments provided by the present invention, the high temperature solid phase time is preferably 6 hours.

[0051] The high-temperature solid phase reaction is preferably carried out in a high-temperature furnace; after the reaction described in the step, the furnace is cooled to room temperature to obtain a fluorescent material with dual narrow-band red light emission.

[0052] The embodiment of the present application uses a high-temperature solid-phase reaction to successfully prepare a fluorescent material that emits dual narrow-band red light.

[0053] The inkjet printing ink made of the fluorescent material based on dual narrow-band red light emission, the light-emitting device comprises toluene, terpineol and a wavelength conversion material, wherein the mass ratio of toluene, terpineol and the wavelength conversion material is 1:0.05:0.95, and the wavelength conversion material at least comprises a chemical formula which can be expressed as Sr3Hf 2-x Mn x Nb 2-x Mn 1.25x O 12 (wherein 0.02≤x≤0.09) dual narrow-band red light emitting fluorescent material.

[0054] The raw materials used in the following comparative examples and embodiments are all commercially available.

[0055] Comparative Example 1

[0056] The raw materials are SrCO3, HfO2, MnO2 and Nb2O5. According to the target chemical formula Sr3Hf 1.99 Mn 0.01 Nb 1.99 Mn 0.0125 O 12 The above raw materials were weighed, ground and mixed, and then put into a crucible. After sintering at 1550℃ for 6h in a high-temperature furnace under air atmosphere, the furnace was cooled to room temperature to obtain a nominal composition of Sr3Hf 1.99 Mn 0.01 Nb 1.99 Mn 0.0125 O 12 materials.

[0057] Comparative Example 1 was obtained under the condition of low Mn doping concentration. The luminescence performance of the obtained material was measured by fluorescence spectrometer, and its spectrum is as follows: Figure 1As shown. The results show that under the excitation of 450nm light, the main peak of the emission spectrum of the material is located at 627.5nm, which is a single narrow-band red light emission, surrounded by some emission peaks of extremely low intensity, and the half-width of the emission spectrum (main peak) is 2.4nm. The quantum efficiency of the material was measured using a quantum efficiency tester, and the quantum efficiency of the material was determined to be 54.1%. The thermal quenching performance of the material was measured using a luminescent material thermal quenching performance tester. The ratio of the luminescence intensity of the material when heated to 150°C to the luminescence intensity of the fluorescent material at 25°C was 0.69. Specific data are shown in Table 1.

[0058] That is, since the concentration of doped Mn is too low, the luminescence performance of the material obtained in Comparative Example 1 is similar to that of common Mn-doped fluorescent materials such as K2SiF6:Mn. It is a fluorescent material with a single narrow-band emission spectrum under blue light excitation and a main peak located near ~630nm.

[0059] Comparative Example 2

[0060] The raw materials are SrCO3, HfO2, MnO2 and Nb2O5. According to the target chemical formula Sr3Hf 1.9 Mn 0.1 Nb 1.9 Mn 0.125 O 12 The above raw materials were weighed, ground and mixed, and then put into a crucible. After sintering at 1550℃ for 6h in a high-temperature furnace under air atmosphere, the furnace was cooled to room temperature to obtain a nominal composition of Sr3Hf 1.9 Mn 0.1 Nb 1.9 Mn 0.125 O 12 materials.

[0061] Comparative Example 2 was obtained under the condition of high Mn doping concentration. The luminescence performance of the obtained material was measured using a fluorescence spectrometer, and its spectrum is as follows: Figure 2 As shown. The results show that under the excitation of 450nm light, the main peak of the emission spectrum of the material is located at 627.8nm, which is a single narrow-band red light emission, surrounded by some emission peaks of extremely low intensity, and the half-width of the emission spectrum (main peak) is 2.9nm. The quantum efficiency of the material was measured using a quantum efficiency tester, and the quantum efficiency of the material was determined to be 55.5%. The thermal quenching performance of the material was measured using a luminescent material thermal quenching performance tester. The ratio of the luminescence intensity of the material when heated to 150°C to the luminescence intensity of the fluorescent material at 25°C was 0.66. Specific data are shown in Table 1.

[0062] That is, since the concentration of doped Mn is too high, the material obtained in Comparative Example 2 is similar to common Mn-doped fluorescent materials such as K2SiF6:Mn, and is a fluorescent material with a single narrow-band emission spectrum under blue light excitation and a main peak located near ~630nm.

[0063] Example 1

[0064] The raw materials are SrCO3, HfO2, MnO2 and Nb2O5. According to the target chemical formula Sr3Hf 1.98 Mn 0.02 Nb 1.98 Mn 0.025 O 12 The above raw materials were weighed, ground and mixed, and then put into a crucible. After sintering at 1550℃ for 6h in a high-temperature furnace under air atmosphere, the furnace was cooled to room temperature to obtain a nominal composition of Sr3Hf 1.98 Mn 0.02 Nb 1.98 Mn 0.025 O 12 materials.

[0065] The material obtained in Example 1 was analyzed by X-ray diffraction using an X-ray diffractometer. The results are as follows: Figure 3 By searching the crystallographic database, it was found that the X-ray diffraction pattern of the material was completely different from the X-ray diffraction pattern of the previously reported material, which indicated that the material in Example 1 was a completely new result and had not been disclosed before. Figure 4 The corresponding matrix (Sr3Hf2Nb2O 12 ) is a schematic diagram of the crystal structure. The luminescence properties of the obtained material were measured using a fluorescence spectrometer, and its spectrum is shown in FIG. Figure 5 As shown. Under the excitation of 450nm light, the material has two main peaks in the emission spectrum, located at 627.5nm and 638.7nm respectively, which is a dual narrow-band red light emission, surrounded by some emission peaks of extremely low intensity, and the half-width of the emission spectrum (main peak) is 2.3nm and 2.5nm respectively. The quantum efficiency of the material was measured using a quantum efficiency tester, and the quantum efficiency of the material was determined to be 60.3%, which is greater than 60%. The thermal quenching performance of the material was measured using a luminescent material thermal quenching performance tester. The ratio of the luminescence intensity of the material when heated to 150°C to the luminescence intensity of the fluorescent material at 25°C was 0.72, which is greater than 0.7 (70%) and less than 0.8 (80%). Specific data are shown in Table 1.

[0066] That is, when the doping concentration of Mn is within a specific range, the material obtained in Example 1 is completely different from common Mn-doped fluorescent materials such as K2SiF6:Mn. It is not a fluorescent material with a single narrow-band emission spectrum under blue light excitation and a main peak located near 630nm, but a fluorescent material that can absorb blue light and produce two narrow-band emission peaks located at 627nm and 639nm respectively. The half-width of the two narrow-band emission peaks of the material is less than 3nm; its quantum efficiency is greater than 60% under 450nm light excitation, and the ratio of the luminous intensity at 150℃ to the luminous light intensity of the fluorescent material at 25℃ is greater than 70% and less than 80%.

[0067] Example 2

[0068] The raw materials are SrCO3, HfO2, MnO2 and Nb2O5. According to the target chemical formula Sr3Hf 1.97 Mn 0.03 Nb 1.97 Mn 0.0375 O 12 The above raw materials were weighed, ground and mixed, and then put into a crucible. After sintering at 1550℃ for 6h in a high-temperature furnace under air atmosphere, the furnace was cooled to room temperature to obtain a nominal composition of Sr3Hf 1.97 Mn 0.03 Nb 1.97 Mn 0.0375 O 12 materials.

[0069] The luminescence properties of the obtained material were measured using a fluorescence spectrometer. The results showed that under the excitation of 450nm light, the material had two main peaks in the emission spectrum, located at 627.1nm and 638.5nm, respectively, which was a dual narrow-band red light emission, surrounded by some emission peaks of extremely low intensity, and the half-widths of the emission spectrum (main peak) were 2.7nm and 2.2nm, respectively. The quantum efficiency of the material was measured using a quantum efficiency tester, and the quantum efficiency of the material was determined to be 65.7%, which is greater than 60%. The thermal quenching performance of the material was measured using a luminescent material thermal quenching performance tester. The ratio of the luminescence intensity of the material when heated to 150°C to the luminescence intensity of the fluorescent material at 25°C was 0.75, which is greater than 0.7 (70%) and less than 0.8 (80%). Specific data are shown in Table 1.

[0070] That is, when the doping concentration of Mn is within a specific range, the material obtained in Example 2 is completely different from common Mn-doped fluorescent materials such as K2SiF6:Mn. It is not a fluorescent material with a single narrow-band emission spectrum under blue light excitation and a main peak located near 630nm, but a fluorescent material that can absorb blue light and produce two narrow-band emission peaks located at 627nm and 639nm respectively. The half-width of the two narrow-band emission peaks of the material is less than 3nm; its quantum efficiency is greater than 60% under 450nm light excitation, and the ratio of the luminous intensity at 150℃ to the luminous light intensity of the fluorescent material at 25℃ is greater than 70% and less than 80%.

[0071] Example 3

[0072] The raw materials are SrCO3, HfO2, MnO2 and Nb2O5. According to the target chemical formula Sr3Hf 1.96 Mn 0.04 Nb 1.96 Mn 0.05 O 12 The above raw materials were weighed, ground and mixed, and then put into a crucible. After sintering at 1550℃ for 6h in a high-temperature furnace under air atmosphere, the furnace was cooled to room temperature to obtain a nominal composition of Sr3Hf 1.96 Mn 0.04 Nb 1.96 Mn 0.05 O 12 materials.

[0073] The luminescence properties of the obtained material were measured using a fluorescence spectrometer. The results showed that under the excitation of 450nm light, the material had two main peaks in the emission spectrum, located at 627.3nm and 638.2nm respectively, which was a dual narrow-band red light emission, surrounded by some emission peaks of extremely low intensity, and the half-widths of the emission spectrum (main peak) were 2.6nm and 2.3nm respectively. The quantum efficiency of the material was measured using a quantum efficiency tester, and the quantum efficiency of the material was determined to be 82.5%, which was greater than 60%. The thermal quenching performance of the material was measured using a luminescent material thermal quenching performance tester. The ratio of the luminescence intensity of the material when heated to 150°C to the luminescence intensity of the fluorescent material at 25°C was 0.73, which was greater than 0.7 (70%) and less than 0.8 (80%). Specific data are shown in Table 1.

[0074] That is, when the doping concentration of Mn is within a specific range, the material obtained in Example 3 is completely different from common Mn-doped fluorescent materials such as K2SiF6:Mn. It is not a fluorescent material with a single narrow-band emission spectrum under blue light excitation and a main peak located near 630nm, but a fluorescent material that can absorb blue light and produce two narrow-band emission peaks located at 627nm and 639nm respectively. The half-width of the two narrow-band emission peaks of the material is less than 3nm; its quantum efficiency is greater than 60% under 450nm blue light excitation, and the ratio of the luminous intensity at 150℃ to the luminous light intensity of the fluorescent material at 25℃ is greater than 70% and less than 80%.

[0075] Example 4

[0076] The raw materials are SrCO3, HfO2, MnO2 and Nb2O5. According to the target chemical formula Sr3Hf 1.95 Mn 0.05 Nb 1.95 Mn 0.0625 O 12 The above raw materials were weighed, ground and mixed, and then put into a crucible. After sintering at 1550℃ for 6h in a high-temperature furnace under air atmosphere, the furnace was cooled to room temperature to obtain a nominal composition of Sr3Hf 1.95 Mn 0.05 Nb 1.95 Mn 0.0625 O 12 materials.

[0077] The luminescence properties of the obtained material were measured using a fluorescence spectrometer. Figure 4 As shown. The results show that under the excitation of 450nm light, the material has two main peaks in the emission spectrum, located at 627.6nm and 638.3nm respectively, which is a dual narrow-band red light emission, surrounded by some emission peaks of extremely low intensity, and the half-width of the emission spectrum (main peak) is 2.9nm and 2.8nm respectively. The quantum efficiency of the material was measured using a quantum efficiency tester, and the quantum efficiency of the material was determined to be 90.2%, which is greater than 60%. The thermal quenching performance of the material was measured using a luminescent material thermal quenching performance tester. The ratio of the luminescence intensity of the material when heated to 150°C to the luminescence intensity of the fluorescent material at 25°C was 0.79, which is greater than 0.7 (70%) and less than 0.8 (80%). Specific data are shown in Table 1.

[0078] That is, when the doping concentration of Mn is within a specific range, the material obtained in Example 4 is completely different from common Mn-doped fluorescent materials such as K2SiF6:Mn. It is not a fluorescent material with a single narrow-band emission spectrum under blue light excitation and a main peak located near 630nm, but a fluorescent material that can absorb blue light and produce two narrow-band emission peaks located at 627nm and 639nm respectively. The half-width of the two narrow-band emission peaks of the material is less than 3nm; its quantum efficiency is greater than 60% under 450nm blue light excitation, and the ratio of the luminous intensity at 150℃ to the luminous light intensity of the fluorescent material at 25℃ is greater than 70% and less than 80%.

[0079] Example 5

[0080] The raw materials are SrCO3, HfO2, MnO2 and Nb2O5. According to the target chemical formula Sr3Hf 1.94 Mn 0.06 Nb 1.94 Mn 0.075 O 12 The above raw materials were weighed, ground and mixed, and then put into a crucible. After sintering at 1550℃ for 6h in a high-temperature furnace under air atmosphere, the furnace was cooled to room temperature to obtain a nominal composition of Sr3Hf 1.94 Mn 0.06 Nb 1.94 Mn 0.075 O 12 materials.

[0081] The luminescence properties of the obtained material were measured using a fluorescence spectrometer. The results showed that under the excitation of 450nm light, the material had two main peaks in the emission spectrum, located at 627.5nm and 638.9nm, respectively, which was a dual narrow-band red light emission, surrounded by some emission peaks of extremely low intensity, and the half-widths of the emission spectrum (main peak) were 2.8nm and 2.4nm, respectively. The quantum efficiency of the material was measured using a quantum efficiency tester, and the quantum efficiency of the material was determined to be 81.1%, which was greater than 60%. The thermal quenching performance of the material was measured using a luminescent material thermal quenching performance tester. The ratio of the luminescence intensity of the material when heated to 150°C to the luminescence intensity of the fluorescent material at 25°C was 0.77, which was greater than 0.7 (70%) and less than 0.8 (80%). Specific data are shown in Table 1.

[0082] That is, when the doping concentration of Mn is within a specific range, the material obtained in Example 5 is completely different from common Mn-doped fluorescent materials such as K2SiF6:Mn. It is not a fluorescent material with a single narrow-band emission spectrum under blue light excitation and a main peak located near 630nm, but a fluorescent material that can absorb blue light and produce two narrow-band emission peaks located at 627nm and 639nm respectively. The half-height width of the two narrow-band emission peaks of the material is less than 3nm; its quantum efficiency is greater than 60% under 450nm blue light excitation, and the ratio of the luminous intensity at 150℃ to the luminous light intensity of the fluorescent material at 25℃ is greater than 70% and less than 80%.

[0083] Example 6

[0084] The raw materials are SrCO3, HfO2, MnO2 and Nb2O5. According to the target chemical formula Sr3Hf 1.93 Mn 0.07 Nb 1.93 Mn 0.0875 O 12 The above raw materials were weighed, ground and mixed, and then put into a crucible. After sintering at 1550℃ for 6h in a high-temperature furnace under air atmosphere, the furnace was cooled to room temperature to obtain a nominal composition of Sr3Hf 1.93 Mn 0.07 Nb 1.93 Mn 0.0875 O 12 materials.

[0085] The luminescence properties of the obtained material were measured using a fluorescence spectrometer. The results showed that under the excitation of 450nm light, the material had two main peaks in the emission spectrum, located at 627.4nm and 638.5nm, respectively, which was a dual narrow-band red light emission, surrounded by some emission peaks of extremely low intensity, and the half-widths of the emission spectrum (main peak) were 2.5nm and 2.6nm, respectively. The quantum efficiency of the material was measured using a quantum efficiency tester, and the quantum efficiency of the material was determined to be 76.4%, which is greater than 60%. The thermal quenching performance of the material was measured using a luminescent material thermal quenching performance tester. The ratio of the luminescence intensity of the material when heated to 150°C to the luminescence intensity of the fluorescent material at 25°C was 0.76, which is greater than 0.7 (70%) and less than 0.8 (80%). Specific data are shown in Table 1.

[0086] That is, when the doping concentration of Mn is within a specific range, the material obtained in Example 6 is completely different from common Mn-doped fluorescent materials such as K2SiF6:Mn. It is not a fluorescent material with a single narrow-band emission spectrum under blue light excitation and a main peak located near 630nm, but a fluorescent material that can absorb blue light and produce two narrow-band emission peaks located at 627nm and 639nm respectively. The half-width of the two narrow-band emission peaks of the material is less than 3nm; its quantum efficiency is greater than 60% under 450nm blue light excitation, and the ratio of the luminous intensity at 150℃ to the luminous light intensity of the fluorescent material at 25℃ is greater than 70% and less than 80%.

[0087] Example 7

[0088] The raw materials are SrCO3, HfO2, MnO2 and Nb2O5. According to the target chemical formula Sr3Hf 1.92 Mn 0.08 Nb 1.92 Mn 0.1 O 12 The above raw materials were weighed, ground and mixed, and then put into a crucible. After sintering at 1550℃ for 6h in a high-temperature furnace under air atmosphere, the furnace was cooled to room temperature to obtain a nominal composition of Sr3Hf 1.92 Mn 0.08 Nb 1.92 Mn 0.1 O 12 materials.

[0089] The luminescence properties of the obtained material were measured using a fluorescence spectrometer. The results showed that under the excitation of 450nm light, the material had two main peaks in the emission spectrum, located at 627.2nm and 638.2nm, respectively, which was a dual narrow-band red light emission, surrounded by some emission peaks of extremely low intensity, and the half-widths of the emission spectrum (main peak) were 2.3nm and 2.9nm, respectively. The quantum efficiency of the material was measured using a quantum efficiency tester, and the quantum efficiency of the material was determined to be 72.1%, which is greater than 60%. The thermal quenching performance of the material was measured using a luminescent material thermal quenching performance tester. The ratio of the luminescence intensity of the material when heated to 150°C to the luminescence intensity of the fluorescent material at 25°C was 0.77, which is greater than 0.7 (70%) and less than 0.8 (80%). Specific data are shown in Table 1.

[0090] That is, when the doping concentration of Mn is within a specific range, the material obtained in Example 7 is completely different from common Mn-doped fluorescent materials such as K2SiF6:Mn. It is not a fluorescent material with a single narrow-band emission spectrum under blue light excitation and a main peak located near 630nm, but a fluorescent material that can absorb blue light and produce two narrow-band emission peaks located at 627nm and 639nm respectively. The half-width of each of the two narrow-band emission peaks of the material is less than 3nm; its quantum efficiency is greater than 60% under 450nm blue light excitation, and the ratio of the luminous intensity at 150℃ to the luminous light intensity of the fluorescent material at 25℃ is greater than 70% and less than 80%.

[0091] Example 8

[0092] The raw materials are SrCO3, HfO2, MnO2 and Nb2O5. According to the target chemical formula Sr3Hf 1.91 Mn 0.09 Nb 1.91 Mn 0.1125 O 12 The above raw materials were weighed, ground and mixed, and then put into a crucible. After sintering at 1550℃ for 6h in a high-temperature furnace under air atmosphere, the furnace was cooled to room temperature to obtain a nominal composition of Sr3Hf 1.91 Mn 0.09 Nb 1.91 Mn 0.1125 O 12 materials.

[0093] The luminescence properties of the obtained material were measured using a fluorescence spectrometer. The results showed that under the excitation of 450nm light, the material had two main peaks in the emission spectrum, located at 627.6nm and 638.8nm respectively, which was a dual narrow-band red light emission, surrounded by some emission peaks of extremely low intensity, and the half-widths of the emission spectrum (main peak) were 2.6nm and 2.7nm respectively. The quantum efficiency of the material was measured using a quantum efficiency tester, and the quantum efficiency of the material was determined to be 68.8%, which is greater than 60%. The thermal quenching performance of the material was measured using a luminescent material thermal quenching performance tester. The ratio of the luminescence intensity of the material when heated to 150°C to the luminescence intensity of the fluorescent material at 25°C was 0.78, which is greater than 0.7 (70%) and less than 0.8 (80%). Specific data are shown in Table 1.

[0094] That is, when the doping concentration of Mn is within a specific range, the material obtained in Example 8 is completely different from common Mn-doped fluorescent materials such as K2SiF6:Mn. It is not a fluorescent material with a single narrow-band emission spectrum under blue light excitation and a main peak located near 630nm, but a fluorescent material that can absorb blue light and produce two narrow-band emission peaks located at 627nm and 639nm respectively. The half-height width of the two narrow-band emission peaks of the material is less than 3nm; its quantum efficiency is greater than 60% under 450nm blue light excitation, and the ratio of the luminous intensity at 150℃ to the luminous light intensity of the fluorescent material at 25℃ is greater than 70% and less than 80%.

[0095] Example 9

[0096] Toluene and terpineol were mixed with the chemical formula Sr3Hf 1.95 Mn 0.05 Nb 1.95 Mn 0.0625 O 12 The double narrow-band red light emitting fluorescent material (ground to an average particle size of 1 micron) is mixed in a mass ratio of 1:0.05:0.95 to obtain inkjet printing ink. The ink is loaded into an ordinary inkjet printer and it is found that the ink can print normally.

[0097] Table 1 Luminescence performance data of dual narrow-band red luminescent materials

[0098] Serial number Main peak of emission spectrum (nm) Emission spectrum half-width (nm) Quantum efficiency (%) Ratio of luminous intensity at 150℃ to that at 25℃ Comparative Example 1 627.5 2.4 54.1 0.69 Comparative Example 2 627.8 2.9 55.5 0.66 Example 1 627.5 / 638.7 2.3 / 2.5 60.3 0.72 Example 2 627.1 / 638.5 2.7 / 2.2 65.7 0.75 Example 3 627.3 / 638.2 2.6 / 2.3 82.5 0.73 Example 4 627.6 / 638.3 2.9 / 2.8 90.2 0.79 Example 5 627.5 / 638.9 2.8 / 2.4 81.1 0.77 Example 6 627.4 / 638.5 2.5 / 2.6 76.4 0.76 Example 7 627.2 / 638.2 2.3 / 2.9 72.1 0.77 Example 8 627.6 / 638.8 2.6 / 2.7 68.8 0.78

[0099] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0100] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0101] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A fluorescent material with dual narrow-band red light emission, characterized in that: The chemical formula of the dual narrow-band red light emitting fluorescent material can be expressed as: Sr3Hf 2-x Mn x Nb 2-x Mn 1.25x O 12 , wherein 0.02≤x≤0.09; the dual narrow-band red light emitting fluorescent material can absorb blue light to generate red light emission; under the excitation of 450nm light, the emission spectrum of the dual narrow-band red light emitting fluorescent material is two narrow-band emission peaks, and the two narrow-band emission peaks are respectively located at ~627nm and ~639nm; the half-width at half maximum of each of the two narrow-band emission peaks is <3nm; under the excitation of 450nm light, the quantum efficiency of the dual narrow-band red light emitting fluorescent material is >60%; under the excitation of 450nm light, the ratio of the luminous intensity of the dual narrow-band red light emitting fluorescent material at 150℃ to the luminous intensity of the fluorescent material at 25℃ is greater than 70% and less than 80%.

2. The dual narrow-band red light emitting fluorescent material according to claim 1, characterized in that: Said x=0.

05.

3. A dual narrow-band red light emitting fluorescent material according to any one of claims 1 to 2, wherein the preparation method comprises the following steps: subjecting a Sr precursor, a Hf precursor, a Mn precursor and a Nb precursor to a high temperature solid phase reaction in an air atmosphere to obtain a fluorescent material having a chemical formula of Sr3Hf 2-x Mn x Nb 2-x Mn 1.25x O 12 A dual narrow-band red-emitting fluorescent material, wherein 0.02≤x≤0.09。 4. The method for preparing a dual narrow-band red light emitting fluorescent material according to claim 3, characterized in that: In the steps, the molar ratio of Sr, Hf, Mn and Nb in the Sr precursor, the Hf precursor, the Mn precursor and the Nb precursor is 3:(2-x):2.25x:(2-x), wherein 0.02≤x≤0.

09.

5. The method for preparing a fluorescent material with dual narrow-band red light emission as claimed in claim 3, characterized in that: As described above, the purity of the Sr precursor, the Hf precursor, the Mn precursor and the Nb precursor is not less than 99.5%.

6. The method for preparing a dual narrow-band red light emitting fluorescent material according to claim 3, characterized in that: In the steps, the temperature of the high temperature solid phase reaction is 1450-1650° C., and the time of the high temperature solid phase reaction is between 4 and 10 hours.

7. The method for preparing a fluorescent material with dual narrow-band red light emission as claimed in claim 3, characterized in that: In the steps, the Sr precursor is selected from one or more of Sr carbonate, Sr oxide, Sr oxalate and Sr nitrate; the Hf precursor is selected from hafnium dioxide; the Mn precursor is selected from one or more of Mn carbonate, Mn oxide, Mn oxalate and Mn nitrate; and the Nb precursor is selected from niobium pentoxide.

8. An inkjet printing ink, comprising: Toluene, terpineol and a wavelength conversion material, the wavelength conversion material comprising any one of claims 1 and / or 2, the chemical formula of which can be represented by Sr3Hf 2-x Mn x Nb 2-x Mn 1.25x O 12 (in, 0.02≤x≤0.09) dual narrow-band red light emitting fluorescent material.

9. The inkjet printing ink according to claim 8, wherein: The wavelength conversion material also includes a material different from the general chemical formula Sr3Hf 2-x Mn x Nb 2-x Mn 1.25x O 12 (in, 0.02≤x≤0.09) of the dual narrow-band red light emitting inorganic fluorescent material or organic fluorescent material.

10. The inkjet printing ink according to claim 8, characterized in that: The mass ratio of toluene to terpineol and the wavelength conversion material is 1:0.05:0.95.

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