Blue light excited narrow-band red light emitting material, preparation method and application thereof
Patent Information
- Application Number
- CN202611051403.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-15
- Publication Date
- 2026-09-29
AI Technical Summary
但其合成需要大量氢氟酸（HF），存在环境污染与健康风险
[0015]本申请提供了一种蓝光激发的窄带红光发光材料，具有式（Ⅰ）的化学式：CamLanAlO3:xEu2+（Ⅰ）；其中，1≤m+n≤1.2，0.008≤x≤0.11。本申请以CamLanAlO3为基质，Eu2+为激活离子，通过精确设计基质组分以增强晶体场分裂强度，配合掺杂浓度的优化调控，实现了窄带发射特性，有效扩展显示的色域，满足高端显示技术对广色域红色发光材料的迫切需求。实验结果表明，所述材料的激发光谱覆盖250nm~600nm波段，兼容紫外和蓝光激发源；发射光谱在550nm~750nm波段具有窄带特征，半高峰宽仅58nm，明显窄于现有主流氮化物红粉。同时，所述制备方法具有步骤简单、成本低廉的特点，且无需在无氧或高压条件下进行，适于工业化推广。
Smart Images
Figure CN122832718A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of luminescent materials, and more particularly to a narrowband red luminescent material excited by blue light, its preparation method, and its application. Background Technology
[0002] One of the core bottlenecks in achieving wide color gamut white light output in LCD backlight systems lies in the spectral characteristics of red phosphor materials. Currently, the mainstream commercial red phosphor is CaAlSiN3:Eu. 2+ (CASN:Eu) 2+ However, its emission spectrum half-peak width (FWHM) is about 70nm. The wide spectral band results in insufficient red purity of the backlight source, which in turn compresses the color gamut that the display device can cover.
[0003] To obtain a narrower red light emission, researchers turned their attention to Mn 4+ Fluoride-doped systems. Although Mn 4+ Doped fluorides have attracted researchers' attention because they can be effectively excited by blue light and exhibit narrow-band red light emission (FWHM of approximately 10 nm). However, their synthesis requires large amounts of hydrofluoric acid (HF), posing environmental pollution and health risks. Another candidate material, Ce... 3+ / Eu 2+ Doped nitrides, such as Sr2Si5N8, CaAlSiN3 and SrLiAl3N4, have advantages such as high quantum efficiency and good thermal stability, but the harsh synthesis conditions (such as high pressure and high temperature) lead to high cost, and the wide emission bandwidth (FWHM>70nm) limits their widespread application. Summary of the Invention
[0004] In view of this, this application provides a blue light-excited narrowband red light-emitting material, its preparation method and application. The blue light-excited narrowband red light-emitting material provided by this application can effectively expand the color gamut of the display, and the preparation method is simple and low cost.
[0005] This application provides a narrowband red-emitting material excited by blue light, having the chemical formula (I): Ca m La n AlO3:xEu 2+ (I); Where 1≤m+n≤1.2, 0.008≤x≤0.11.
[0006] In some specific implementations, 0.01 ≤ x ≤ 0.09.
[0007] In some specific implementations, m+n=1.
[0008] In some specific implementations, the chemical formula of formula (II) is: Ca 0.4 La 0.6 AlO3:xEu 2+ (II); Where 0.01≤x≤0.09.
[0009] In some specific implementations, it has the following chemical formula: Ca 0.4 La 0.6 AlO3: 0.01Eu 2+ Ca 0.4 La 0.6 AlO3:0.03Eu 2+ Ca 0.4 La 0.6 AlO3:0.05Eu 2+ Ca 0.4 La 0.6 AlO3:0.07Eu 2+ or Ca 0.4 La 0.6 AlO3: 0.09Eu 2+ .
[0010] This application also provides a method for preparing the blue-light-excited narrowband red-light-emitting material described in the above technical solution, comprising the following steps: By grinding and sintering Ca, La, Al, Eu sources and reducing agents, a narrowband red light-emitting material excited by blue light is obtained.
[0011] In some specific implementations, the reducing agent is selected from (NH4)2SO4; The molar ratio of the reducing agent to the Eu source is 0.2:(0.008~0.11).
[0012] In some specific implementations, the Ca source is selected from CaCO3; the La source is selected from La2O3; the Al source is selected from Al2O3; and the Eu source is selected from Eu2O3.
[0013] In some specific implementations, the grinding time is 15 min to 45 min; The sintering temperature is 1200℃~1800℃, the time is 4h~8h, and the heating rate is 3℃ / min~10℃ / min.
[0014] This application also provides a light-emitting device, including the blue-light-excited narrowband red-light-emitting material described in the above technical solution or the blue-light-excited narrowband red-light-emitting material prepared by the preparation method described in the above technical solution.
[0015] This application provides a blue-light-excited narrowband red-light-emitting material having the chemical formula of formula (I): Ca m La n AlO3:xEu 2+ (I); where 1≤m+n≤1.2, 0.008≤x≤0.11. This application uses Ca m La n AlO3 is the matrix, Eu 2 + To activate the ions, a narrow-band emission characteristic was achieved by precisely designing the matrix composition to enhance the crystal field splitting intensity, coupled with optimized control of the doping concentration. This effectively expands the color gamut of the display, meeting the urgent need of high-end display technologies for wide-gamut red luminescent materials. Experimental results show that the excitation spectrum of the material covers the 250nm~600nm band, compatible with ultraviolet and blue light excitation sources; the emission spectrum exhibits a narrow band characteristic in the 550nm~750nm band, with a half-peak width of only 58nm, significantly narrower than existing mainstream nitride red powders. Furthermore, the preparation method is simple, low-cost, and does not require oxygen-free or high-pressure conditions, making it suitable for industrial application. Attached Figure Description
[0016] Figure 1 The Ca described in Embodiment 1 of this application 0.4 La 0.6 AlO3: 0.01Eu 2+ XRD patterns; Figure 2 The Ca described in embodiments 2-5 of this application 0.4 La 0.6 AlO3:xEu 2+ XRD patterns; Figure 3 The Ca described in Examples 1-5 of this application 0.4 La 0.6 AlO3:xEu 2+ The excitation emission spectrum, Figure 3 a is Ca as described in embodiments 1-5 of this application. 0.4 La 0.6 AlO3:xEu 2+ The excitation spectrum, Figure 3 The Ca described in embodiments 1-5 of this application 0.4 La 0.6 AlO3:xEu 2+ The emission spectrum. Detailed Implementation
[0017] It should be understood that the expression “one or more of…” individually includes each of the objects described after the expression, as well as various different combinations of two or more of the described objects, unless otherwise understood from the context and usage. The expression “and / or” combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.
[0018] The terms “including,” “having,” or “containing,” including the use of their grammatical synonyms, should generally be understood as open-ended and non-restrictive, for example, not excluding other unstated elements or steps, unless otherwise specifically stated or understood from the context.
[0019] It should be understood that the order of steps or the sequence of actions is not important as long as this application remains operational. Furthermore, two or more steps or actions can be performed simultaneously.
[0020] The use of any and all instances or exemplary language such as “e.g.” or “including” herein is merely intended to better illustrate the application and does not constitute a limitation on the scope of the application unless the claims are made. No language in this specification should be construed as indicating that any unclaimed element is essential to the practice of this application.
[0021] Furthermore, the numerical ranges and parameters used to define this application are approximate values, and the relevant values in the specific embodiments have been presented as precisely as possible. However, any numerical value inevitably contains standard deviations due to individual test methods. Therefore, unless otherwise explicitly stated, it should be understood that all ranges, quantities, values, and percentages used in this disclosure are modified with the word "approximately." Here, "approximately" generally means that the actual value is within plus or minus 10%, 5%, 1%, or 0.5% of a specific value or range.
[0022] This application provides a blue-light-excited narrowband red-light-emitting material having the chemical formula of formula (I): Ca m La n AlO3:xEu 2+ (I); where 1≤m+n≤1.2, 0.008≤x≤0.11; Preferably, the chemical formula having formula (Ⅰ) is: Ca m La n AlO3:xEu 2+ (I); where 1≤m+n≤1.2, 0.01≤x≤0.09; More preferably, it has the chemical formula of formula (I): Ca m La n AlO3:xEu 2+(I); where m+n=1, 0.01≤x≤0.09.
[0023] In some specific implementations, the chemical formula of equation (II) is: Ca 0.4 La 0.6 AlO3:xEu 2+ (II); where 0.01≤x≤0.09.
[0024] In some specific implementations, it has the following chemical formula: Ca 0.4 La 0.6 AlO3: 0.01Eu 2+ Ca 0.4 La 0.6 AlO3:0.03Eu 2+ Ca 0.4 La 0.6 AlO3:0.05Eu 2+ Ca 0.4 La 0.6 AlO3:0.07Eu 2+ or Ca 0.4 La 0.6 AlO3: 0.09Eu 2+ .
[0025] In some specific implementations, the excitation wavelength of the blue-excited narrowband red-emitting material is 250nm~600nm, and the emission wavelength is 550nm~750nm.
[0026] This application uses Ca m La n AlO3 is the matrix, Eu 2+ As an activator, Eu 2+ Because its 4f-5d outer orbitals are located outside the ion orbitals, the crystal field splitting intensity and the doping concentration of activating ions can be changed by precisely controlling the matrix composition. As a result, the half-maximum width of the red light-emitting material provided in this application is only 58nm, which effectively expands the color gamut of the display and meets the urgent need of high-end display technology for wide color gamut red light-emitting materials.
[0027] This application also provides a method for preparing the blue-light-excited narrowband red-light-emitting material described in the above technical solution, comprising the following steps: By grinding and sintering Ca, La, Al, Eu sources and reducing agents, a narrowband red light-emitting material excited by blue light is obtained.
[0028] This application first grinds Ca source, La source, Al source, Eu source and reducing agent as precursors to obtain a mixed powder.
[0029] This application uses Ca, La, Al, and Eu sources as raw materials to prepare the blue light-excited narrowband red light-emitting material described in the above technical solution. This application does not have any special restrictions on the Ca, La, Al, and Eu sources; any raw materials commonly used by those skilled in the art can be used.
[0030] In some specific implementations, the Ca source is selected from CaCO3. In some specific implementations, the La source is selected from La2O3. In some specific implementations, the Al source is selected from Al2O3. In some specific implementations, the Eu source is selected from Eu2O3.
[0031] This application controls the proportion of each element in the final narrowband red light emitting material by controlling the molar ratio of Ca source, La source, Al source and Eu source. Since the La source will be lost to some extent during the sintering process, the La source will be in excess.
[0032] In some specific implementations, the molar ratio of the Ca source, La source, Al source, and Eu source is m:n z :1:(0.008~0.11), where 1≤m+n≤1.2, 1.3≤n z With n ≤ 1.4, the chemical formula of the resulting blue-excited narrowband red-emitting material is Ca. m La n AlO3:(0.008~0.11)Eu 2+ ; Preferably, the molar ratio of the Ca source, La source, Al source, and Eu source is m:n z :1:(0.01~0.09), where 1≤m+n≤1.2, 1.3≤n z With n ≤ 1.4, the chemical formula of the resulting blue-excited narrowband red-emitting material is Ca. m La n AlO3:(0.01~0.09)Eu 2+ ; More preferably, the molar ratio of the Ca source, La source, Al source, and Eu source is m:n z :1:(0.01~0.09), where m+n=1, 1.3≤n z With n ≤ 1.4, the chemical formula of the resulting blue-excited narrowband red-emitting material is Ca. m La n AlO3:(0.01~0.09)Eu 2+ ; More preferably, the molar ratio of the Ca source, La source, Al source, and Eu source is 0.4:0.8:1:(0.01~0.09), and the resulting blue-light-excited narrowband red-light-emitting material has the chemical formula Ca.0.4 La 0.6 AlO3:(0.01~0.09)Eu 2+ .
[0033] In some specific implementations, the reducing agent is selected from (NH4)2SO4. In some specific implementations, the molar ratio of the reducing agent to the Eu source is 0.2:(0.008~0.11), preferably 1:(0.01~0.09). In some specific implementations, the grinding time is 15 min~45 min, preferably 15 min~25 min.
[0034] After obtaining the mixed powder, the mixed powder is sintered and cooled to obtain a narrowband red light emitting material excited by blue light.
[0035] In some specific implementations, the sintering and cooling of the mixed powder are preferably carried out in a reducing gas mixture of H2 and N2, wherein the volume ratio of H2 to N2 is 1:(9~19), preferably 1:(12~16). In some specific implementations, the sintering temperature is 1200℃~1800℃, preferably 1400℃~1600℃, more preferably 1500℃~1600℃. In some specific implementations, the sintering time is 4h~8h, preferably 5h~7h. In some specific implementations, the sintering heating rate is 3℃ / min~10℃ / min, preferably 4℃ / min~8℃ / min, more preferably 4℃ / min~6℃ / min. In some specific implementations, the cooling rate is 3℃ / min~10℃ / min, preferably 4℃ / min~8℃ / min, more preferably 4℃ / min~6℃ / min.
[0036] This application also provides a light-emitting device, including a narrowband red light-emitting material excited by blue light as described in the above technical solution or a narrowband red light-emitting material excited by blue light prepared by the preparation method described in the above technical solution.
[0037] This application provides a blue-light-excited narrowband red-light-emitting material having the chemical formula of formula (I): Ca m La n AlO3:xEu 2+ (I); where 1≤m+n≤1.2, 0.008≤x≤0.11. This application uses Ca m La n AlO3 is the matrix, Eu 2 +To activate the ions, a narrow-band emission characteristic was achieved by precisely designing the matrix composition to enhance the crystal field splitting intensity, coupled with optimized control of the doping concentration. This effectively expands the color gamut of the display, meeting the urgent need of high-end display technologies for wide-gamut red luminescent materials. Experimental results show that the excitation spectrum of the material covers the 250nm~600nm band, compatible with ultraviolet and blue light excitation sources; the emission spectrum exhibits a narrow band characteristic in the 550nm~750nm band, with a half-peak width of only 58nm, significantly narrower than existing mainstream nitride red powders. Furthermore, the preparation method is simple, low-cost, and does not require oxygen-free or high-pressure conditions, making it suitable for industrial application.
[0038] The present invention is further illustrated below with reference to the embodiments. The scope of protection of the present invention is not limited to the following embodiments.
[0039] Example 1
[0040] This embodiment provides a narrowband red-light-emitting material Ca excited by blue light. 0.4 La 0.6 AlO3: 0.01Eu 2+ The preparation method of [the substance] specifically includes the following steps: (1) Weigh 0.4 mmol (excess) of La2O3, 0.4 mmol of CaCO3, 0.5 mmol of Al2O3, 0.2 mmol of (NH4)2SO4 and 0.005 mmol of Eu2O3 according to the stoichiometric ratio. Place the above raw materials in an agate mortar, mix thoroughly and grind for 20 min to obtain a uniform mixed powder.
[0041] (2) The obtained mixed powder was transferred to a corundum crucible and then placed in a muffle furnace. Under a nitrogen-hydrogen mixed reducing atmosphere (N2 / H2), the furnace temperature was raised to 1550°C at a heating rate of 5°C / min and sintered at this temperature for 6 hours. After sintering, the mixture was cooled to room temperature at a cooling rate of 5°C / min to obtain the red-light luminescent material Ca. 0.4 La 0.6 AlO3: 0.01Eu 2+ .
[0042] Example 2
[0043] The only difference from Example 1 is the amount of Eu2O3 incorporated. Specifically, the amount of Eu2O3 weighed was adjusted from 0.005 mmol to 0.015 mmol. All other raw material types, proportions, and process conditions remained consistent with Example 1, resulting in the red-light-emitting material Ca. 0.4 La 0.6 AlO3:0.03Eu 2+ .
[0044] Example 3
[0045] The only difference from Example 1 is the amount of Eu2O3 incorporated. Specifically, the amount of Eu2O3 weighed was adjusted from 0.005 mmol to 0.025 mmol. All other raw material types, proportions, and process conditions remained consistent with Example 1, resulting in the red-light-emitting material Ca. 0.4 La 0.6 AlO3:0.05Eu 2+ .
[0046] Example 4
[0047] The only difference from Example 1 is the amount of Eu2O3 incorporated. Specifically, the amount of Eu2O3 weighed was adjusted from 0.005 mmol to 0.035 mmol. All other raw material types, proportions, and process conditions remained consistent with Example 1, resulting in the red-light-emitting material Ca. 0.4 La 0.6 AlO3:0.07Eu 2+ .
[0048] Example 5
[0049] The only difference from Example 1 is the amount of Eu2O3 incorporated. Specifically, the amount of Eu2O3 weighed was adjusted from 0.005 mmol to 0.045 mmol. All other raw material types, proportions, and process conditions remained consistent with Example 1, resulting in the red-light-emitting material Ca. 0.4 La 0.6 AlO3: 0.09Eu 2+ .
[0050] Experimental Example 1
[0051] The Ca provided in Examples 1-5 of this application 0.4 La 0.6 AlO3:xEu 2+ XRD pattern analysis was performed for x = 0.01, 0.03, 0.05, 0.07, or 0.09. See the results below. Figures 1-2 , Figure 1 The Ca described in Embodiment 1 of this application 0.4 La 0.6 AlO3: 0.01Eu 2+ , Figure 2 The Ca described in embodiments 2-5 of this application 0.4 La 0.6 AlO3:xEu 2+ XRD patterns for (x = 0.03, 0.05, 0.07, or 0.09). (From...) Figures 1-2 It can be seen that the Ca provided in embodiments 1-5 of this application 0.4 La 0.6AlO3:xEu 2+ The XRD results conform to the standard card.
[0052] Experimental Example 2
[0053] The Ca provided in Examples 1-5 of this application 0.4 La 0.6 AlO3:xEu 2+ The excitation and emission spectra of x = 0.01, 0.03, 0.05, 0.07, or 0.09 were measured, and the results are shown in [reference needed]. Figure 3 , Figure 3 The Ca described in Examples 1-5 of this application 0.4 La 0.6 AlO3:xEu 2+ Excitation-emission spectra for (x = 0.01, 0.03, 0.05, 0.07, or 0.09). Figure 3 a is Ca as described in embodiments 1-5 of this application. 0.4 La 0.6 AlO3:xEu 2+ Excitation spectra for (x = 0.01, 0.03, 0.05, 0.07, or 0.09). Figure 3 The Ca described in embodiments 1-5 of this application 0.4 La 0.6 AlO3:xEu 2+ Emission spectra for x = 0.01, 0.03, 0.05, 0.07, or 0.09. (From...) Figure 3 It can be seen that the Ca 0.4 La 0.6 AlO3:xEu 2+ (x=0.01, 0.03, 0.05, 0.07 or 0.09) It exhibits a significant narrowband red light emission in the range of 550nm to 750nm, with a half-peak width of 58nm.
[0054] The above description is merely a preferred embodiment of this application, but the scope of protection of this application is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in this application, based on the technical solution and inventive concept of this application, should be included within the scope of protection of this application.
Claims
1. A narrowband red-light-emitting material excited by blue light, characterized in that, Chemical formulas with formula (Ⅰ): That m to n AlO3:xIu 2+ (Ⅰ); Where 1≤m+n≤1.2, 0.008≤x≤0.
11.
2. The narrowband red-light-emitting material excited by blue light according to claim 1, characterized in that, The condition is 0.01≤x≤0.
09.
3. The narrowband red-light-emitting material excited by blue light according to claim 2, characterized in that, The m+n=1.
4. The narrowband red-light-emitting material excited by blue light according to claim 3, characterized in that, Chemical formula with formula (II): That 0.4 to 0.6 AlO3:xIu 2+ (Ⅱ); Where 0.01≤x≤0.
09.
5. The narrowband red-light-emitting material excited by blue light according to claim 4, characterized in that, It has the following chemical formula: Ca 0.4 La 0.6 AlO3: 0.01Eu 2+ Ca 0.4 La 0.6 AlO3:0.03Eu 2+ Ca 0.4 La 0.6 AlO3:0.05Eu 2+ Ca 0.4 La 0.6 AlO3:0.07Eu 2+ or Ca 0.4 La 0.6 AlO3: 0.09Eu 2+ .
6. A method for preparing a narrowband red-light-emitting material excited by blue light according to any one of claims 1 to 5, characterized in that, Includes the following steps: By grinding and sintering Ca, La, Al, Eu sources and reducing agents, a narrowband red light-emitting material excited by blue light is obtained.
7. The preparation method according to claim 6, characterized in that, The reducing agent is selected from (NH4)2SO4; The molar ratio of the reducing agent to the Eu source is 0.2:(0.008~0.11).
8. The preparation method according to claim 6, characterized in that, The Ca source is selected from CaCO3; the La source is selected from La2O3; the Al source is selected from Al2O3; and the Eu source is selected from Eu2O3.
9. The preparation method according to claim 6, characterized in that, The grinding time is 15 min to 45 min; The sintering temperature is 1200℃~1800℃, the time is 4h~8h, and the heating rate is 3℃ / min~10℃ / min.
10. A light-emitting device, characterized in that, It includes the narrowband red light emitting material excited by blue light as described in any one of claims 1 to 5, or the narrowband red light emitting material excited by blue light prepared by the preparation method described in any one of claims 6 to 9.