WO2021092723A1 - 锰卤荧光粉材料及制备方法和利用锰卤荧光粉材料的发光装置 - Google Patents
锰卤荧光粉材料及制备方法和利用锰卤荧光粉材料的发光装置 Download PDFInfo
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- WO2021092723A1 WO2021092723A1 PCT/CN2019/117121 CN2019117121W WO2021092723A1 WO 2021092723 A1 WO2021092723 A1 WO 2021092723A1 CN 2019117121 W CN2019117121 W CN 2019117121W WO 2021092723 A1 WO2021092723 A1 WO 2021092723A1
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- manganese
- light
- phosphor
- halogen
- emitting device
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 title abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 17
- -1 halogen ions Chemical class 0.000 claims abstract description 9
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001767 cationic compounds Chemical class 0.000 claims abstract description 7
- 229910001411 inorganic cation Inorganic materials 0.000 claims abstract description 7
- 150000002892 organic cations Chemical class 0.000 claims abstract description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 3
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- 238000000034 method Methods 0.000 claims description 5
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- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 3
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- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
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- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
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- 238000000746 purification Methods 0.000 claims description 3
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Definitions
- the invention relates to the field of luminescence technology, in particular to a phosphor material and a preparation method and application thereof.
- White light-emitting diode LED is a solid-state semiconductor device that converts electrical energy into white light, also known as semiconductor lighting. It has many advantages such as high efficiency, small size, long life, safety, low voltage, energy saving, and environmental protection.
- the fourth generation of lighting sources after incandescent lamps, fluorescent lamps, and high-pressure gas discharge lamps are mainstream products in the future lighting market.
- scientists from various countries have additionally developed blue LED chips combined with red and green fluorescent materials and purple LED chips combined with red, green, and blue fluorescent materials, two methods to realize white light LEDs.
- the emission wavelength of InGaN chips has been moved to the near ultraviolet region, which can provide higher excitation energy for phosphors and further increase the light intensity of white light LEDs.
- UV light is invisible, the color of ultraviolet-excited white light LED is only determined by phosphor, so the color is stable and the color rendering index is high.
- Phosphor powder is an indispensable component in this scheme.
- Traditional rare-earth phosphors mostly have a wide half-value width (60-80nm), or multiple emission peaks coexist, resulting in low monochromaticity of green and red, thereby reducing the color gamut.
- the all-inorganic APbX 3 perovskite material has become one of the research hotspots in the field of semiconductor luminescence in recent years because of its high fluorescence quantum efficiency and narrow line width luminescence characteristics.
- Lead halide perovskite quantum dots are used in photoelectric detection, solar cells, lighting, display and other fields due to their high carrier mobility, high quantum efficiency, high color purity, and easily adjustable band gap. Wide range of applications.
- the stability of the all-inorganic APbX 3 perovskite is poor, and the emission peak of the all-inorganic CsPbBr 3 perovskite nanocrystal is mostly located near 510nm, while the emission peak of the current general display green phosphor is 515-545nm, so Luminescence at 510nm is not conducive to display applications.
- the all-inorganic APbX 3 perovskite contains heavy metal lead, which is a threat to the environment and human health.
- Scintillators are a kind of materials that can emit light after absorbing high-energy x-rays and gamma rays, and they play a very important role in the field of radiation detection.
- scintillator is the core component of nuclear medicine imaging equipment, through which doctors can quickly diagnose the lesions of various organs of the human body and the size and location of tumor tissues. So as to help patients find diseases early and prevent and treat them in time.
- the most commonly used inorganic crystals are sodium iodide crystals activated with thallium, namely NaI (Tl); others include CsI (Tl), ZnS (Ag), etc., bismuth germanate, ceramic scintillators, such as: Lu (2-x) ) Gd x O 3 : Ac, organic scintillators anthracene, stilbene, naphthalene, etc.
- the luminous efficiency of traditional scintillators is not high, and the luminous peak is relatively broad.
- the sensitivity of X-ray/ ⁇ -ray detectors needs to be improved.
- the scintillator crystals often contain highly toxic elements, such as thallium (Tl) and gadolinium (Gd), which have an adverse effect on the environment, and the production cost of the crystal is high.
- the technical problem to be solved by the present invention is to avoid the shortcomings of the prior art and propose a high quantum efficiency, narrow green and red emission peaks, higher green and red color purity, and can improve color
- the manganese halide phosphor material and the preparation method thereof and the light emitting device containing the manganese halide phosphor material are to avoid the shortcomings of the prior art and propose a high quantum efficiency, narrow green and red emission peaks, higher green and red color purity, and can improve color
- the manganese halide phosphor material and the preparation method thereof and the light emitting device containing the manganese halide phosphor material are provided.
- a manganese halide phosphor material is provided.
- the inorganic cation is ammonium ion NH 4 + , cesium ion Cs + , rubidium ion Rb + , potassium ion K + , sodium ion Na + or lithium ion Li +
- a preparation method of the above-mentioned manganese halide phosphor material includes the steps:
- Preparation of precursor mixed solution add salt A, manganese salt and halogen source into organic solvent and mix thoroughly; wherein salt A is cesium acetate, cesium carbonate or cesium oleate; manganese salt is manganese acetate, manganese carbonate, nitric acid Manganese, manganese sulfate or manganese bromide; halogen source is halosilane or hydrohalic acid; organic solvent is n-hexane, ethanol, isopropanol, acetone, ethyl acetate, dimethyl sulfoxide or a mixed solvent of the above solvents;
- the molar ratio of A salt to manganese salt is 0.5:1 to 1.5:1, and the molar ratio of manganese salt to halogen source is preferably 1:2 to 1:4.
- the molar ratio of the A salt to the manganese salt is 2:1 to 4:1, and the molar ratio of the manganese salt to the halogen source is 1:4 to 1:6.
- the organic solvent is acetone or isopropanol.
- a light emitting device using the above manganese halide phosphor material the light emitting device further comprising a light source, the phosphor is radiatively coupled with the light source to convert the radiation energy of the light source into visible light, and the light source includes blue LED, ultraviolet light, x-ray or gamma
- the radiation energy ranges from about 2.5eV to about 2.5MeV.
- the light-emitting device is a white LED lighting device
- the phosphor material includes at least one of AMnX 3 red phosphor and A 3 MnX 5 green phosphor
- the light source is a blue LED.
- the light-emitting device is a display backlight device
- the phosphor material includes at least one of AMnX 3 red phosphor and A 3 MnX 5 green phosphor
- the light source is a blue LED.
- the light-emitting device is a medical detector, and the light source is an x-ray or a gamma-ray.
- the luminescence peak of the green phosphor of this patent is 525nm, the half-value width is 42nm, the luminescence peak of the red-emitting phosphor material is 655nm, the luminescence color is pure, and the half-value width is 50nm. Compared with traditional phosphors, it has higher monochromaticity and higher fluorescence quantum efficiency. And A 3 MnX 5 green and AMnX 3 red phosphor materials have good thermal stability.
- the luminescence peak of the green fluorescent material is more conducive to display at 525nm, and the phosphor material of this patent does not contain lead, which is an environmentally friendly material.
- the preparation method of the manganese halogen phosphor material of the invention is simple and easy to prepare.
- Fig. 1 is a schematic cross-sectional view of a light-emitting device according to an embodiment of the present invention, in which reference numeral 1 represents manganese halide phosphor material, 2 represents encapsulant, 3 represents light emitting layer, and 4 represents light source.
- FIG 2 is A 3 MnX 5 green phosphor emission spectra, A 3 MnX 5 upper right is a green phosphor UV light irradiation at 365nm physical FIG.
- a 3 MnX 5 is a green phosphor emission spectra
- a 3 MnX 5 upper right is a green phosphor in x-ray irradiation physical FIG.
- Figure 4 is the chromaticity coordinate diagram "2" of the A 3 MnX 5 green phosphor of the present invention, and the coordinates of the green CsPbBr 3 (CPB) perovskite quantum dot "1" and the traditional rare earth YAG phosphor "3" are also marked Point for comparison.
- CsPbBr 3 (CPB) perovskite quantum dot 1
- the traditional rare earth YAG phosphor "3” are also marked Point for comparison.
- Figure 5 is the emission spectrum diagram of the AMnX 3 type phosphor. The upper left is the actual picture of the AMnX 3 type red phosphor irradiated by a 365nm ultraviolet lamp.
- Fig. 6 is a chromaticity coordinate diagram of a white light LED based on blue gallium nitride light-emitting diodes made with green A 3 MnX 5 phosphors and red AMnX 3 phosphors.
- the phosphor material includes at least one of AMnX 3 and A 3 MnX 5.
- the inorganic cation can be ammonium ion NH 4 + , cesium ion Cs + , rubidium ion Rb + , potassium ion K + , sodium ion Na + or lithium ion Li +
- the basic principle of the manganese halide phosphor material is that the phosphor converts radiant energy into visible light.
- the color of visible light produced depends on the specific chemical composition of the phosphor material.
- the crystal field theory if a Mn 2+ ion is surrounded by four ligands to form an independent [MnX 4 ] 2- tetrahedral unit, the unit is arranged in a certain way and the surrounding space is filled by other organic molecules, then Tetrahedral coordinated Mn 2+ ions with weak magnetic field strength usually show green luminescence.
- the distance between Mn 2+ ions is large enough to eliminate direct spin coupling, so its optical transition is controlled by independent manganese ions.
- [MnX 6 ] 4- octahedron (surrounded by six ligands) is shared face to face, forming a linear chain structure along the crystal direction, in which the distance between Mn-Mn decreases significantly in one direction, In the orthogonal direction, it becomes larger due to the blocking of organic or inorganic A-site molecules.
- This anisotropic structure has a limiting effect on the Mn 2+ ionic chain, and has an important influence on the dd transition law and transition energy of different sizes. Therefore, octahedral coordinated Mn 2+ ions in a strong field environment usually show red light emission.
- a 3 MnX 5 is formed by Mn-X tetrahedrons. Due to the MnX 4 coordination unit in the crystal, the whole crystal emits green fluorescence. Under the irradiation of ultraviolet light and x-rays, the luminescence peak of A 3 MnX 5 crystal phosphor is at 525 nm and the half-peak width is 42 nm, as shown in Fig. 2 and Fig. 3. In addition, A 3 MnX 5 is more suitable for display in green light than rare earth YAG phosphors and APbX 3 perovskites. The color coordinate comparison diagram of the three materials is shown in Fig. 4. As shown in Figure 5, the emission peak of AMX 3 is located at 655 nm, showing red light emission.
- Thermogravimetric analysis showed that the A 3 MnX 5 crystal began to lose weight after being heated to above 400°C, indicating that the A 3 MnX 5 crystal had relatively good thermal stability.
- the A 3 MX 5 green phosphor powder and the red commercial fluoride KSF powder are mixed and packaged in a blue GaN LED chip to obtain a white light-emitting LED. As shown in Figure 6, the coordinate point of the white light is (0.29, 0.33), and the color temperature is 7575K. Suitable for lighting and display products.
- a preparation method of the above-mentioned manganese halide phosphor material includes the steps:
- Preparation of precursor mixed solution add salt A, manganese salt and halogen source into organic solvent and mix thoroughly; wherein salt A is cesium acetate, cesium carbonate or cesium oleate; manganese salt is manganese acetate, manganese carbonate, nitric acid Manganese, manganese sulfate or manganese bromide; halogen source is halosilane or hydrohalic acid; organic solvent is n-hexane, ethanol, isopropanol, acetone, ethyl acetate, dimethyl sulfoxide or a mixed solvent of the above solvents;
- the molar ratio of A salt to manganese salt is 0.5:1 to 1.5:1, and the molar ratio of manganese salt to halogen source is preferably 1:2 to 1:4.
- the molar ratio of A salt to manganese salt is 2:1 to 4:1, and the molar ratio of manganese salt to halogen source is 1:4 to 1:6.
- the organic solvent is preferably acetone or isopropanol.
- Example 1 Weigh 268 mg of cesium acetate pentahydrate and 343 mg of manganese acetate tetrahydrate, add 580 ⁇ L of bromosilane to 20 mL of acetone, and mix by shaking. The mixed solution was put into ultrasound to react for 30 minutes, the solution was taken out, centrifuged at 8000 rpm for 10 minutes, and the supernatant was removed. The remaining product was put into an oven at 70°C for drying, and the product was taken out for storage.
- Example 2 Weigh 268 mg of cesium acetate pentahydrate and 343 mg of manganese acetate tetrahydrate, add 580 ⁇ L of bromosilane to 20 mL of isopropanol, and mix by shaking. The mixed solution was put into ultrasound to react for 30 minutes, the solution was taken out, centrifuged at 8000 rpm for 10 minutes, and the supernatant was removed. The remaining product was put into an oven at 70°C for drying, and the product was taken out for storage. .
- Example 3 Weigh 376 mg of cesium acetate pentahydrate, 343 mg of manganese acetate tetrahydrate, add 320 ⁇ L of bromosilane to 15 mL of acetone and 5 mL of isopropanol, shake and mix, put the mixed solution in ultrasound for 30 minutes, take the solution out, and centrifuge at 8000 rpm 10min, remove the supernatant. The remaining product was put into an oven at 70°C for drying, and the product was taken out for storage.
- Example 4 268 mg of cesium bromide was dissolved in 20 mL of methanol; 146 mg of manganese bromide was dissolved in 20 mL of tetrahydrofuran. 5mL of cesium bromide solution was added to the manganese bromide solution. The mixed solution was put into ultrasound to react for 30 minutes, the solution was taken out, centrifuged at 8000 rpm for 10 minutes, and the supernatant was removed. The remaining product was put into an oven at 70°C for drying, and the product was taken out for storage.
- Example 5 268 mg of cesium bromide was dissolved in 20 mL of water; 146 mg of manganese bromide was dissolved in 20 mL of ethyl acetate. The mixed solution was put into ultrasound to react for 30 minutes, the solution was taken out, centrifuged at 8000 rpm for 10 minutes, and the supernatant was removed. The remaining product was put into an oven at 70°C for drying, and the product was taken out for storage. .
- Example 6 268 mg of cesium bromide was dissolved in 20 mL of dimethyl sulfoxide; 146 mg of manganese bromide was dissolved in 20 mL of isopropanol. The mixed solution was put into ultrasound to react for 30 minutes, the solution was taken out, centrifuged at 8000 rpm for 10 minutes, and the supernatant was removed. The remaining product was put into an oven at 70°C for drying, and the product was taken out for storage.
- a light emitting device using the above manganese halide phosphor material includes manganese halide phosphor material 1, encapsulant 2, light emitting layer 3 and light source 4, said manganese halide phosphor material 1 and light source 4
- the radiation coupling converts the radiation energy of the light source into visible light
- the light source includes blue LED, ultraviolet light, x-ray or gamma-ray, and its radiation energy range is between about 2.5 eV to about 2.5 MeV.
- the manganese halogen phosphor material 1 is dispersed in the encapsulant 2.
- the light emitting device is a white light LED lighting device or a display backlight device
- the phosphor material includes at least one of AMnX 3 red phosphor and A 3 MnX 5 green phosphor
- the light source is a blue LED.
- the manganese halide phosphor material reduces the radiant energy of the light source ranging from about 2.5eV to about 2.5MeV, such as blue light (400-500nm), ultraviolet light (10-400nm), x-ray (0.001-10nm) and gamma rays ( ⁇ 0.001nm), converted to visible light.
- the manganese halogen phosphor material can provide different colors of light emission. Phosphor powder compositions and blends, and their applications in light sources such as light emitting diodes (LED), ultraviolet light (UV), x-rays and gamma rays.
- a single-color manganese halide phosphor, two or more basic color manganese halide phosphors, or a combination of manganese halide phosphors and ordinary phosphors can emit light of different colors.
- the blue LED and the green manganese halide phosphor and the red manganese halide phosphor are mixed to emit white light.
- the X-ray in the medical detector irradiates the green manganese halide phosphor to produce green light.
- the color of the visible light produced depends on the specific composition of the phosphor material.
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Abstract
一种锰卤荧光粉材料及制备方法和利用锰卤荧光粉材料的发光装置，所述荧光粉为含有锰离子(Mn 2+)和卤素离子的A nMnX n+2荧光粉，其中：n＝1时，AMnX 3为红色荧光粉，其Mn 2+为八面体配位；n＝3时，A 3MnX 5为绿色荧光粉，其Mn 2+为四面体配位；A为正一价无机阳离子、正一价有机阳离子或者其中几种阳离子的混合；X为F -、Cl -、Br -和I -其中的一种或者几种的阴离子混合；所述荧光粉材料包括AMnX 3和A 3MnX 5中的至少一种。所述锰卤荧光粉材料适宜于在LED照明、显示器件背光源和医用探测器等方面应用。
Description
本发明涉及发光技术领域，特别是涉及荧光粉材料及其制备方法和用途。
白光发光二极管LED是一种将电能转换为白光的固态半导体器件，又称半导体照明，具有效率高、体积小、寿命长、安全、低电压、节能和环保等诸多优点，被人们看成是继白炽灯、荧光灯、高压气体放电灯之后第四代照明光源，是未来照明市场上的主流产品。为了提高白光LED的显色性，各国科学家另外研发了蓝光LED芯片与红、绿色荧光材料组合和紫光LED芯片与红、绿、蓝三基色荧光材料组合这两种实现白光LED的方法。目前InGaN芯片的发射波长已经移至近紫外区域,能为荧光粉提供更高的激发能量，进一步提高白光LED的光强。由于紫外光不可见,紫外线激发白光LED的颜色只由荧光粉决定，因此颜色稳定，显色指数高，使用近紫外InGaN芯片和蓝、黄荧光粉或者与三基色荧光粉组合来实现白光的方案成为目前白光LED行业发展的重点。荧光粉是该方案中不可缺少的成分。传统稀土荧光粉，大多具有较宽的半峰宽(60-80nm)，或者有多个发射峰并存，造成绿光和红色单色性低从而降低显色色域。
全无机APbX
3钙钛矿材料因为高的荧光量子效率且线宽窄的发光特性，近年来成为半导体发光领域的研究热点之一。铅卤钙钛矿量子点因其较高的载流子迁移率、高的量子效率、高的色纯度，以及易调节的带隙等特点，在光电探测、太阳能电池、照明、显示等领域有着广泛的应用。但是，全无机APbX
3钙钛矿稳定性较差，且全无机CsPbBr
3钙钛矿纳米晶体的发射峰位大多位于510nm附近，而目前通用显示用绿色荧光粉的发光峰在515-545nm，因此510nm的发光不利于显示应用。同时全无机APbX
3钙钛矿含有重金属铅，对环境以及人类身体健康均有威胁。
闪烁体是一类吸收高能x射线和γ射线后能够发光的材料，在辐射探测领域发挥着十分重要的作用。在医学上，闪烁体是核医学影像设备的核心部件，通过它医生可以快速诊断出人体各器官的病变、肿瘤组织的大小和位置。从而 帮助病人及早发现疾病并及时预防和治疗。最常用的无机晶体是用铊激活的碘化钠晶体，即NaI(Tl)；其他还有CsI(Tl)、ZnS(Ag)等,锗酸铋，陶瓷闪烁体，如：Lu
(2-x)Gd
xO
3:Ac，有机闪烁体蒽、茋、萘等。传统的闪烁体的发光效率不高，发光峰较宽。用于x射线/γ射线探测器检测时的灵敏度有待提高。此外，闪烁体晶体的往往含有剧毒元素，如铊(Tl)和钆(Gd)，对坏境有不利影响，晶体的制作成本高。
发明内容
本发明要解决的技术问题在于避免现有技术的不足之处而提出一种有着高量子效率，窄的绿光和红光发射峰，具有更高的绿光和红光色纯度，能提高色域的锰卤荧光粉材料及其制备方法和含有锰卤荧光粉材料的发光装置。
本发明解决所述技术问题所采用的技术方案为：
提供一种锰卤荧光粉材料，所述荧光粉为含有锰离子(Mn
2+)和卤素离子的A
nMnX
n+2荧光粉，其中：n＝1时，AMnX
3为红色荧光粉，其Mn
2+为八面体配位；n＝3时，A
3MnX
5为绿色荧光粉，其Mn
2+为四面体配位；A为正一价无机阳离子、正一价有机阳离子或者其中几种阳离子的混合；X为F
-、Cl
-、Br
-和I
-其中的一种或者几种的阴离子混合；所述荧光粉材料包括AMnX
3和A
3MnX
5中的至少一种。
进一步地：
所述无机阳离子为铵离子NH
4
+、铯离子Cs
+、铷离子Rb
+、钾离子K
+、钠离子Na
+或锂离子Li
+，所述有机阳离子为甲胺CH3NH
3
+、甲脒CH
2(NH
2)
2
+、胍CH(NH
2)
3
+、吡啶(C5H6N+)、乙胺CH
3CH
2CH
2NH
3
+、丙胺CH
3CH
2CH
2NH
3
+、丁胺CH
3CH
2CH
2CH
2NH
3
+、戊胺CH
3CH
2CH
2CH
2CH
2NH
3
+或者有机胺CH
3(CH2)
nNH
3
+(n＝0-20)。
一种如上述锰卤荧光粉材料的制备方法，包括步骤：
1.前驱体混合溶液的制备：将A盐、锰盐以及卤源加入到有机溶剂中充分混合；其中A盐是乙酸铯，碳酸铯或油酸铯；锰盐是乙酸锰、碳酸锰、硝酸锰、硫酸锰或溴化锰；卤源是卤硅烷或氢卤酸；有机溶剂是正己烷、乙醇、异丙醇、丙酮、乙酸乙酯、二甲亚砜或者是以上溶剂的混合溶剂；
2.反应：将前驱体混合溶液超声反应1分钟至1小时；
3.纯化：将反应得到的荧光粉离心分离，并加热烘干保存。
其中，制备AMnX
3红色荧光粉时，其中A盐和锰盐的摩尔比为0.5:1至 1.5:1，锰盐和卤源的摩尔比优选为1:2至1:4。
制备A
3MnX
5的绿色荧光粉时，其中A盐和锰盐的摩尔比为2:1至4:1，锰盐和卤源的摩尔比为1:4至1:6。
有机溶剂为丙酮或异丙醇。
一种利用上述锰卤荧光粉材料的发光装置，该发光装置还包括光源，所述荧光粉与光源辐射耦合将光源辐射能量转化为可见光，所述光源包括蓝光LED、紫外光、x射线或γ射线，其辐射能量范围在约2.5eV至约2.5MeV之间。
所述发光装置为白光LED照明装置，所述荧光粉材料包括AMnX
3红色荧光粉和A
3MnX
5绿色荧光粉中的至少一种，所述光源为蓝光LED。
所述发光装置为显示器背光源装置，所述荧光粉材料包括AMnX
3红色荧光粉和A
3MnX
5绿色荧光粉中的至少一种，所述光源为蓝光LED。
所述发光装置为医用探测器，所述光源为x射线或γ射线。
与现有技术相比，本发明的技术效果在于：
本专利绿色荧光粉发光峰位在525nm，半峰宽42nm，发红光荧光粉材料发光峰位在655nm，发光颜色纯，发光半峰宽为50nm。和传统荧光粉相比具有更高的单色性以及更高的荧光量子效率。并且A
3MnX
5绿色和AMnX
3红色荧光粉材料具有较好的热稳定性。
和经典CsPbBr
3钙钛矿材料相比，本绿色荧光材料发光峰在525nm更利于显示，且本专利荧光粉材料不含铅，是一种环境友好材料。
本发明锰卤荧光粉材料制备方法简单，易于制备。
由于不含重金属，对环境更友好，并且热稳定性良好，因此适宜于在LED照明，液晶显示器件背光源，x射线和γ射线医用探测器上的应用。用于x射线/γ射线医用探测器时的检测灵敏度高，降低了制作成本。
图1是本发明实施例发光装置的横断面示意图，其中，标号①代表锰卤荧光粉材料，②代表封装胶，③代表光发射层，④代表光源。
图2是A
3MnX
5型绿色荧光粉的发射光谱图，右上方为A
3MnX
5型绿色荧光粉在365nm紫外灯辐照下的实物图。
图3是A
3MnX
5型绿色荧光粉的发射光谱图，右上方为A
3MnX
5型绿色荧光粉 在x射线辐照下的实物图。
图4是本发明A
3MnX
5绿色荧光粉的色度坐标图“2”，同时标出了绿色CsPbBr
3(CPB)钙钛矿量子点“1”和传统稀土YAG荧光粉“3”的坐标点作为对比。
图5是AMnX
3型荧光粉的发射光谱图，左上方为AMnX
3型红色荧光粉在365nm紫外灯辐照下的实物图。
图6是用绿色A
3MnX
5荧光粉和红色AMnX
3荧光粉制作的基于蓝光氮化镓发光二极管的白光LED的色度坐标图。
以下对本发明的实施例作详细说明。
一种锰卤荧光粉材料，所述荧光粉为含有锰离子(Mn
2+)和卤素离子的A
nMnX
n+2荧光粉，其中：n＝1时，AMnX
3为红色荧光粉，其Mn
2+为八面体配位；n＝3时，A
3MnX
5为绿色荧光粉，其Mn
2+为四面体配位；A为正一价无机阳离子、正一价有机阳离子或者其中几种阳离子的混合；X为F
-、Cl
-、Br
-和I
-其中的一种或者几种的阴离子混合。所述荧光粉材料包括AMnX
3和A
3MnX
5中的至少一种。
所述无机阳离子可以为铵离子NH
4
+、铯离子Cs
+、铷离子Rb
+、钾离子K
+、钠离子Na
+或锂离子Li
+，所述有机阳离子可以为甲胺CH3NH
3
+、甲脒CH
2(NH
2)
2
+、胍CH(NH
2)
3
+、吡啶(C5H6N+)、乙胺CH
3CH
2CH
2NH
3
+、丙胺CH
3CH
2CH
2NH
3
+、丁胺CH
3CH
2CH
2CH
2NH
3
+、戊胺CH
3CH
2CH
2CH
2CH
2NH
3
+或者有机胺CH
3(CH2)
nNH
3
+(n＝0-20)。
所述锰卤荧光粉材料的基本原理是：荧光粉把辐射能量转化为可见光。产生的可见光颜色取决于荧光粉材料的特定化学成份。根据晶体场理论，如果一个Mn
2+离子被四个配体包围形成一个独立的[MnX
4]
2-四面体单元，该单元按照一定的方式排列，周围的空间被其他有机分子填满，则弱磁场强度的四面体配位Mn
2+离子通常表现为绿色发光。在这种情况下，Mn
2+离子之间的距离很大足以消除直接的自旋耦合，因此它的光学跃迁是由独立的锰离子控制的。在八面体配位化合物中，[MnX
6]
4-八面体(被六个配体包围)面对面共享，沿晶体方向形成线性链状结构，其中Mn-Mn间距离在一个方向上显著减小，在其正交方向上由于有机或无机A位分子的阻隔而变大。这种各向异性结构对Mn
2+离子链具有限制作用，对不同尺寸的d-d跃迁规律和跃迁能量具有重要影响。因此，强场环境下的八面体配位Mn
2+离子通常显示红光发射。
A
3MnX
5由Mn-X四面体形成，由于晶体中的MnX
4配位单元，造成整个晶体发绿色荧光。在紫外光和x射线的辐照下，A
3MnX
5晶体荧光粉的发光峰位在525nm，半峰宽42nm，如图2和图3所示。并且A
3MnX
5相比稀土YAG荧光粉以及APbX
3钙钛矿来说，在绿光上更适宜于显示，该三种材料的色坐标对比图具体见图4。如图5所示，AMX
3的发射峰位于655nm，表现出红光发射。热重分析表明A
3MnX
5晶体在加热到400℃以上才开始失重，说明A
3MnX
5晶体有着比较好的热稳定性。将该A
3MX
5绿色荧光粉与红色商用氟化物KSF粉混合，封装在蓝光GaN LED芯片中，得到了发白光LED。如图6所示，白光的坐标点为(0.29,0.33)，色温为7575K。适合于照明和显示产品。
一种如上述的锰卤荧光粉材料的制备方法，包括步骤：
1.前驱体混合溶液的制备：将A盐、锰盐以及卤源加入到有机溶剂中充分混合；其中A盐是乙酸铯，碳酸铯或油酸铯；锰盐是乙酸锰、碳酸锰、硝酸锰、硫酸锰或溴化锰；卤源是卤硅烷或氢卤酸；有机溶剂是正己烷、乙醇、异丙醇、丙酮、乙酸乙酯、二甲亚砜或者是以上溶剂的混合溶剂；
2.反应：将前驱体混合溶液超声反应1分钟至1小时；
3.纯化：将反应得到的荧光粉离心分离，并加热烘干保存。
其中，制备AMnX
3红色荧光粉时，其中A盐和锰盐的摩尔比为0.5:1至1.5:1，锰盐和卤源的摩尔比优选为1:2至1:4。制备A
3MnX
5绿色荧光粉时，其中A盐和锰盐的摩尔比为2:1至4:1，锰盐和卤源的摩尔比为1:4至1:6。有机溶剂优选为丙酮或异丙醇。
AMnX
3具体制备实施例如下：
实施例1：称取268mg五水乙酸铯，343mg四水乙酸锰，取580μL溴硅烷加入20mL丙酮中，震荡混合。将混合溶液放入超声中反应30min，将溶液取出，8000rpm离心10min，去除上清液。将剩余产物放入70℃烘箱中烘干，产物取出保存。
实施例2：称取268mg五水乙酸铯，343mg四水乙酸锰，取580μL溴硅烷加入20mL异丙醇中，震荡混合。将混合溶液放入超声中反应30min，将溶液取出，8000rpm离心10min，去除上清液。将剩余产物放入70℃烘箱中烘干，产物取出保存。。
实施例3：称取376mg五水乙酸铯，343mg四水乙酸锰，取320μL溴硅烷加入15mL丙酮与5mL异丙醇中，震荡混合将混合溶液放入超声中反应30min， 将溶液取出，8000rpm离心10min，去除上清液。将剩余产物放入70℃烘箱中烘干，产物取出保存。
A
3MnX
5具体制备实施例如下：
实施例4：268mg溴化铯溶于20mL甲醇；146mg溴化锰溶于20mL四氢呋喃中。5mL溴化铯溶液加入溴化锰溶液中。将混合溶液放入超声中反应30min，将溶液取出，8000rpm离心10min，去除上清液。将剩余产物放入70℃烘箱中烘干，产物取出保存。
实施例5：268mg溴化铯溶于20mL水；146mg溴化锰溶于20mL乙酸乙酯中。将混合溶液放入超声中反应30min，将溶液取出，8000rpm离心10min，去除上清液。将剩余产物放入70℃烘箱中烘干，产物取出保存。。
实施例6：268mg溴化铯溶于20mL二甲亚砜；146mg溴化锰溶于20mL异丙醇中。将混合溶液放入超声中反应30min，将溶液取出，8000rpm离心10min，去除上清液。将剩余产物放入70℃烘箱中烘干，产物取出保存。
一种利用上述锰卤荧光粉材料的发光装置，如图1所示，包括锰卤荧光粉材料①、封装胶②、光发射层③和光源④，所述锰卤荧光粉材料①与光源④辐射耦合将光源辐射能量转化为可见光，所述光源包括蓝光LED、紫外光、x射线或γ射线，其辐射能量范围在约2.5eV至约2.5MeV之间。锰卤荧光粉材料①分散在封装胶②中。
所述发光装置为白光LED照明装置或显示器背光源装置，所述荧光粉材料包括AMnX
3红色荧光粉和A
3MnX
5绿色荧光粉中的至少一种，所述光源为蓝光LED。
锰卤荧光粉材料把范围在约2.5eV至约2.5MeV之间的光源辐射能量，如：蓝光(400-500nm)，紫外光(10-400nm)，x射线(0.001-10nm)和γ射线(<0.001nm)，转化为可见光。锰卤荧光粉材料可以提供不同颜色的光发射。荧光粉组合物和共混物，以及它们在发光二极管(LED)，紫外光(UV)，x射线和γ射线等光源中的应用。单一颜色的锰卤荧光粉、两个或多个基本颜色锰卤荧光粉，或者锰卤荧光粉与普通荧光粉组合可以发不同颜色的光。例如：LED灯中，蓝光LED和绿色锰卤荧光粉和红色锰卤荧光粉混合发出白光。医用探测器中X射线照射绿色锰卤荧光粉产生绿光。产生的可见光的颜色取决于荧光粉材料的特定成分。
应当理解的是，以上实施例仅用以说明本发明的技术方案，而非对其限制， 其部分细节可通过相应设计变更以其它的形式来实现。对本领域技术人员来说，可以对上述实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改和替换，都应属于本发明所附权利要求的保护范围。
Claims (10)
- 一种锰卤荧光粉材料，其特征在于：所述荧光粉为含有锰离子(Mn2+)和卤素离子的AnMnXn+2荧光粉，其中：n＝1时，AMnX3为红色荧光粉，其Mn2+为八面体配位；n＝3时，A3MnX5为绿色荧光粉，其Mn2+为四面体配位；A为正一价无机阳离子、正一价有机阳离子或者其中几种阳离子的混合；X为F-、Cl-、Br-和I-其中的一种或者几种的阴离子混合；所述荧光粉材料包括AMnX3和A3MnX5中的至少一种。
- 根据权利要求1所述的锰卤荧光粉材料，其特征在于：所述无机阳离子为铵离子NH4+、铯离子Cs+、铷离子Rb+、钾离子K+、钠离子Na+或锂离子Li+，所述有机阳离子为甲胺CH3NH3+、甲脒CH2(NH2)2+、胍CH(NH2)3+、吡啶(C5H6N+)、乙胺CH3CH2CH2NH3+、丙胺CH3CH2CH2NH3+、丁胺CH3CH2CH2CH2NH3+、戊胺CH3CH2CH2CH2CH2NH3+或者有机胺CH3(CH2)nNH3+(n＝0-20)。
- 一种如权利要求1或2所述的锰卤荧光粉材料的制备方法，其特征在于：包括步骤：(1)前驱体混合溶液的制备：将A盐、锰盐以及卤源加入到有机溶剂中充分混合；其中A盐是乙酸铯，碳酸铯或油酸铯；锰盐是乙酸锰、碳酸锰、硝酸锰、硫酸锰或溴化锰；卤源是卤硅烷或氢卤酸；有机溶剂是正己烷、乙醇、异丙醇、丙酮、乙酸乙酯、二甲亚砜或者是以上溶剂的混合溶剂；(2)反应：将前驱体混合溶液超声反应1分钟至1小时；(3)纯化：将反应得到的荧光粉离心分离，并加热烘干保存。
- 根据权利要求3所述的锰卤荧光粉材料的超声反应制备方法，其特征在于：制备AMnX3红色荧光粉时，其中A盐和锰盐的摩尔比为0.5:1至1.5:1，锰盐和卤源的摩尔比优选为1:2至1:4。
- 根据权利要求3所述的锰卤荧光粉材料的超声反应制备方法，其特征在于：制备A3MnX5的绿色荧光粉时，其中A盐和锰盐的摩尔比为2:1至4:1，锰盐和卤源的摩尔比为1:4至1:6。
- 根据权利要求3所述的锰卤荧光粉材料的超声反应制备方法，其特征在 于：有机溶剂为丙酮或异丙醇。
- 一种利用如权利要求1或2所述的锰卤荧光粉材料的发光装置，该发光装置还包括光源，其特征在于：所述荧光粉与光源辐射耦合将光源辐射能量转化为可见光，所述光源包括蓝光LED、紫外光、x射线或γ射线，其辐射能量范围在2.5eV至2.5MeV之间。
- 根据权利要求7所述的发光装置，其特征在于：所述发光装置为白光LED照明装置，所述荧光粉材料包括AMnX3红色荧光粉和A3MnX5绿色荧光粉中的至少一种，所述光源为蓝光LED。
- 根据权利要求7所述的发光装置，其特征在于：所述发光装置为显示器背光源装置，所述荧光粉材料包括AMnX3红色荧光粉和A3MnX5绿色荧光粉中的至少一种，所述光源为蓝光LED。
- 根据权利要求7所述的发光装置，其特征在于：所述发光装置为医用探测器，所述光源为x射线或γ射线。
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