WO2020098446A1 - 一种氟化物发光材料的表面改性方法及其制备得到的氟化物发光材料 - Google Patents

一种氟化物发光材料的表面改性方法及其制备得到的氟化物发光材料 Download PDF

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WO2020098446A1
WO2020098446A1 PCT/CN2019/111737 CN2019111737W WO2020098446A1 WO 2020098446 A1 WO2020098446 A1 WO 2020098446A1 CN 2019111737 W CN2019111737 W CN 2019111737W WO 2020098446 A1 WO2020098446 A1 WO 2020098446A1
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organic
solution
coating layer
luminescent material
phosphor
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French (fr)
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朱浩淼
黄得财
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厦门稀土材料研究所
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Definitions

  • the invention relates to the technical field of rare earth luminescent materials and lighting display, in particular to a surface modification method of fluoride luminescent materials and the prepared fluoride luminescent materials.
  • White LED is a new type of solid-state light source. Compared with traditional incandescent lamps and fluorescent lamps, it has the advantages of environmental protection, energy saving, high efficiency, and fast response.
  • the fourth-generation green light source after the light source.
  • the performance of the phosphor determines the LED's luminous efficiency, color rendering index, color temperature and service life and other technical indicators. Therefore, the phosphor has a decisive position in white LEDs and has attracted widespread attention.
  • the most commonly used method is to combine a blue LED chip (emission wavelength 440-480nm) with a yellow phosphor (such as YAG: Ce or TAG: Ce).
  • the yellow phosphor phosphor absorbs part of the blue light emitted by the blue LED chip It emits yellow light and mixes with unabsorbed blue light to form white light.
  • this method can only obtain a cool white light device with a correlated color temperature (Correlated Color) (CCT) greater than 4500K.
  • CCT Correlated Color
  • its color rendering index (Color Rendering Index, CRI) is also low, usually less than 80.
  • CRI Color Rendering Index
  • an effective method is to add an appropriate red phosphor to the white LED device to enhance the device's red light emission.
  • Fluoride materials activated by Mn 4+ ions have a narrow emission peak and a small half-width, which is currently a hot research topic for red light-emitting materials.
  • Patent document US2009 / 7497973 discloses Mn 4+ activated A 2 MF 6 (A is K, Na, Rb, etc .; M is Ti, Si, Sn, Ge, etc.) red phosphor; where the raw material is dissolved in a high concentration Hydrofluoric acid, and then heating and volatilization co-crystallization to obtain the product;
  • Patent document WO2009 / 119486 discloses the dissolution of elemental Si in a solution of hydrofluoric acid and potassium permanganate to obtain a fluoride product;
  • Patent document CN102732249A reported through First prepare the first solution containing the fluoride of metal M and the second solution containing A or the compound of A in solid form.
  • the fluoride luminescent materials have the advantages of high luminous efficiency and good thermal stability. However, these methods have not overcome the shortcomings of the fluoride luminescent material itself being easily hydrolyzed, and are prone to hydrolysis under long-term use or in a humid environment, resulting in a reduction in luminous efficiency or even failure.
  • Patent document US2007 / 0125984A1 reported that coating a layer of inorganic materials (such as TiO 2 , Al 2 O 3 , SiO 2 ) on the surface of the phosphor as a protective film to improve the moisture resistance of the phosphor; but this aqueous phase coating technology is difficult Applied to the coating of fluoride phosphor.
  • Patent document CN106479485A also publicly reports that coating a layer of potassium silicate-sodium hydroxymethylcellulose-polyethylene glycol on the surface of the phosphor particles improves the high temperature and high humidity resistance of the phosphor; but this organic coating material, It also has the disadvantage of not being resistant to high temperature and easy to decompose, which affects the long-term use efficiency of the phosphor. Therefore, it is of great practical significance to improve the moisture resistance of fluoride phosphors while prolonging the service life of white LEDs, which meets the requirements of energy saving and environmental protection.
  • the object of the present invention is to provide a surface modification method of fluoride luminescent material and the prepared fluoride luminescent material.
  • the present invention is by ion exchange, removal of the base material A x MF y: Mn 4+ Mn 4+ surface layer formed of the inorganic coating layer A x MF y clad base material A x MF y: Mn 4+ structure of Denoted as A x MF y : Mn 4+ @A x MF y , the A x MF y : Mn 4+ @A x MF y can effectively prevent the matrix material A x MF y : Mn 4+ particles inside the luminous center to transfer energy To the surface, to avoid the fluorescence quenching caused thereby, to improve the luminous efficiency of the fluoride luminescent material; then by coating the organic coating layer on the outer surface of the inorganic coating layer, a surface hydrophobic layer is formed, so that the fluor
  • a surface-modified fluoride luminescent material wherein the luminescent material includes a base material, an inorganic coating layer and an organic coating layer, the inorganic coating layer is coated on the outer surface of the base material, and the organic coating The layer is coated on the outer surface of the inorganic coating;
  • the matrix material is A x MF y : Mn 4+
  • the inorganic coating layer is A x MF y ; wherein, A is selected from one of alkali metals Li, Na, K, Rb, Cs or between them
  • A is selected from one of alkali metals Li, Na, K, Rb, Cs or between them
  • M one selected from Ti, Si, Ge, Sn, Zr, Al, Bi, Ga, In or a combination between them
  • x is the absolute value of the charge of [MF y ] ion
  • y is 4 , 5, 6 or 7
  • Mn 4+ is the luminescent center ion.
  • x is the absolute value of the charge of the [MF 6 ] ion, and y is 6.
  • the inorganic coating layer A x MF y is prepared by removing the matrix material A x MF y : Mn 4+ surface layer Mn 4+ by an ion exchange method.
  • the inorganic layer in the surface-modified fluoride luminescent material, may be a single layer or multiple layers, and the organic layer coated on the outer surface of the inorganic layer may also be a single layer or multiple layers.
  • the double-layer coating structure is that the surface of the base material is coated with an inorganic coating layer, and the outer surface of the inorganic coating layer is coated with an organic coating layer; Inorganic coating layer, the outer surface of the multilayer inorganic coating layer is coated with a single organic coating layer; or, the surface of the base material is coated with a single layer of inorganic coating layer, and the outer surface of the single inorganic coating layer is coated with a multilayer organic layer The coating layer; or, the surface of the base material is coated with multiple inorganic coating layers, and the outer surface of the multiple inorganic coating layers is coated with multiple organic coating layers.
  • composition of the multiple organic coating layers is the same or different, and preferably the composition of adjacent organic coating layers is different.
  • the inorganic coating layer and the organic coating layer are combined by chemical bonding.
  • the organic coating layer is at least one of metal phosphates, alkoxysilanes, organic carboxylic acids, or organic amines.
  • the phosphate ester in the metal phosphate ester is a phosphate monoester or a phosphate diester, such as P (O) (OH) 2 (OR), or P (O) (OH) (OR) 2 , where R is a hydrocarbon group; for example, an alkyl group (such as a C 1-20 alkyl group).
  • the phosphate ester is obtained by esterifying a phosphorus source with an alcohol, wherein the phosphorus source is selected from one of P 2 O 5 or POCl 3 or a combination thereof.
  • the alcohol is at least one selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol.
  • the metal in the metal phosphate is a metal cation, for example, one of Al, Ti, Si, Ga, and Zn ions or a combination thereof.
  • the alkoxysilane is Si (OR 1 ) 3 (R 2 ), wherein R 1 is C 1-6 alkyl, R 2 is C 1-20 alkyl, C 1- 20 alkenyl, for example selected from methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, dodecyltrimethoxy Silane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane.
  • the organic carboxylic acid substance is R 3 COOH, and R 3 is a C 1-30 alkyl group, for example, selected from oleic acid, stearic acid, behenic acid, octacosanoic acid, Lauric acid.
  • the organic amine substance is NR 4 (R 5 ) 2 , R 4 is C 1-10 alkyl, R 5 is the same or different, and optionally H, C 1-10 alkyl ,
  • R 4 is C 1-10 alkyl
  • R 5 is the same or different, and optionally H, C 1-10 alkyl ,
  • the corresponding ones are the secondary or tertiary amines of nail amine, ethylamine, propylamine, butylamine, octylamine, and hexylamine.
  • This article also provides the preparation method of the above surface modified fluoride luminescent material, including the following steps:
  • said A is selected from one of alkali metals Li, Na, K, Rb, Cs or a combination thereof; said M is selected from Ti, Si, Ge, Sn, Zr, Al, Bi, Ga, One of In or a combination between them, x is the absolute value of the charge of [MF y ] ions, y is 4, 5, 6 or 7; Mn 4+ is the luminescent center ion.
  • the mass percentage of hydrofluoric acid in the hydrofluoric acid solution is 20-50%.
  • the saturated solution is preferably formed at 20 ° C-90 ° C.
  • step (2) the mass ratio of the matrix material A x MF y : Mn 4+ to the A x MF y compound in the saturated solution of step (1) is 10: 1-1: 5 , Preferably 1: 1.
  • step (2) the ion exchange reaction is performed at 0 ° C to 100 ° C, preferably at 25 ° C to 80 ° C.
  • the time of the ion exchange reaction is at least 30 seconds, for example at least 1 min, preferably at least 5 min.
  • step (2) the ion exchange reaction is performed under continuous stirring conditions.
  • step (2) further includes the steps of: filtering and drying the mixed solution after the ion exchange reaction is completed.
  • the organic solution is at least one of a metal phosphate solution, an alkoxysilane solution, an organic carboxylic acid substance solution, or an organic amine substance solution.
  • the preparation method is as follows:
  • organic solvent Dissolve alkoxysilane, organic carboxylic acid or organic amine in organic solvent; the organic solvent is at least one of methanol, ethanol, propanol, n-hexane or cyclohexane; or,
  • the phosphorus source is selected from one of P 2 O 5 or POCl 3 or a combination thereof;
  • the alcohol is selected from methanol, At least one of ethanol, n-propanol, isopropanol, n-butanol, and isobutanol;
  • the metal source is metal nitrate, metal sulfate, or metal oxalate, and may also be isopropanol or ethanol
  • metal organic salts such as salt, propoxide or butoxide.
  • the content of the alkoxysilane, organic carboxylic acid or organic amine in the organic solvent is at least 1 wt.%, Preferably 5 wt.%.
  • the metal source is Al (NO 3 ) 3 .9H 2 O, Zn (NO 3 ) 2 .6H 2 O, titanium butoxide, aluminum isopropoxide.
  • the mass percentage content of the metal source is at least 0.1%, and the mass percentage content of the phosphorus source is at least 10%.
  • the temperature of the heating and stirring is at least 30 ° C, preferably at least 50 ° C.
  • the inorganic coating layer A x MF y- coated A x MF y : Mn 4+ matrix material and the mass ratio of the organic solution are 5: 1-1: 20 , Preferably 1: 1-1: 5.
  • step (4) further includes the following steps: washing with an alcohol solution or acetone, and drying.
  • the A x MF y : Mn 4+ is selected from A 2 MF 6 : Mn 4+ or A 3 MF 6 : Mn 4+
  • the A 2 MF 6 : Mn 4+ is selected from K 2 TiF 6 : Mn 4+ , K 2 SiF 6 : Mn 4+ , Na 2 SiF 6 : Mn 4+ , Na 2 TiF 6 : Mn 4+ , K 2 GeF 6 : Mn 4+ , Na 2 SnF 6 : Mn 4+ , Cs 2 TiF 6 : Mn 4+ or Cs 2 SiF 6 : Mn 4+ , preferably K 2 TiF 6 : Mn 4+ , K 2 SiF 6 : Mn 4+ Or K 2 GeF 6 : Mn 4+ .
  • the A 3 MF 6 : Mn 4+ is selected from Na 3 AlF 6 : Mn 4+ , K 3 AlF 6 : Mn 4+ , Li 3 AlF 6 : Mn 4+ , Rb 3 AlF 6 : Mn 4+ , Cs 3 AlF 6 : Mn 4+ , K 2 NaAlF 6 : Mn 4+ , K 2 LiAlF 6 : Mn 4+ , also preferably Na 3 AlF 6 : Mn 4+ , K 3 AlF 6 : Mn 4+ , K 2 NaAlF 6 : Mn 4+ .
  • the A x MF y is selected from A 2 MF 6 or A 3 MF 6
  • the A 2 MF 6 is selected from K 2 TiF 6 and K 2 SiF 6 , Na 2 SiF 6 , Na 2 TiF 6 , K 2 GeF 6 , Na 2 SnF 6 , Cs 2 TiF 6 or Cs 2 SiF 6 , preferably K 2 TiF 6 , K 2 SiF 6 or K 2 GeF 6 .
  • the A 3 MF 6 is selected from Na 3 AlF 6 , K 3 AlF 6 , Li 3 AlF 6 , Rb 3 AlF 6 , Cs 3 AlF 6 , K 2 NaAlF 6 , K 2 LiAlF 6 , and is also preferably Na 3 AlF 6 , K 3 AlF 6 , K 2 NaAlF 6 .
  • the filtered product may be further washed with an organic solvent such as absolute ethanol or acetone to remove residual acid on the surface and dried.
  • an organic solvent such as absolute ethanol or acetone
  • the base material A x MF y : Mn 4+ when the base material A x MF y : Mn 4+ is mixed with the saturated hydrofluoric acid solution of the A x MF y compound, the base material A x MF y : Mn 4+ Mn 4+ and A x MF of the surface layer
  • the surface ion exchange reaction of the metal cation M in the saturated hydrofluoric acid solution of compound y results in the matrix material A x MF y : Mn 4+ surface layer without Mn 4+ , forming an inorganic coating layer A x MF y coated on the matrix material A x MF y :
  • the core-shell structure on the surface of Mn 4+ , and the size of the matrix material A x MF y : Mn 4+ does not change in this process.
  • the intermediate product prepared can effectively prevent fluorescence because the surface layer does not contain Mn 4+
  • the internal luminescence center of the powder particles transfers energy to the quenching center of the surface, improving the luminous efficiency of the phosphor.
  • the thickness of the outer surface of the phosphor particles coated by the inorganic coating layer is limited, and the water resistance is not sufficient.
  • the base material A x MF y that covers the inorganic coating layer A x MF y : Mn 4+ and an organic solution containing a metal phosphate, alkoxysilane, organic carboxylic acid or organic amine After mixing, the solution is evaporated to dryness to prepare a matrix material A x MF y : Mn 4+ , which is a surface-modified fluoride luminescent material, which is coated with the organic-inorganic coating layer of the present invention. Since the surface-modified fluoride luminescent material has no excitation center Mn 4+ at the interface between the inorganic coating layer and the organic coating layer, the luminous performance of the phosphor powder is less reduced.
  • the surface-modified Mn 4+ doped fluoride luminescent material provided by the present invention has a coating structure of an inorganic layer and an organic layer.
  • the coating structure significantly improves the corrosion resistance of the fluoride phosphor, after modification
  • the fluorescent powder has a luminous intensity and quantum efficiency retention rate of 85-95% under high temperature and high humidity environment, and can be widely used in the field of white LED backlight display.
  • the inorganic coating layer provided by the present invention has the same composition as the phosphor matrix material.
  • the inorganic coating layer may be one or more layers. After the inorganic coating layer is coated, the surface of the phosphor powder is reduced Defects, luminous intensity and quantum yield of phosphors have been improved by 5% -15%.
  • the organic coating layer provided by the present invention avoids directly on the surface of the A 2 MF 6 : Mn 4+ phosphor base material, preventing the direct contact between the organic coating layer and Mn 4+ and reducing the luminous intensity of the material And quantum yield.
  • the organic layer may be one or more layers. After the organic coating layer is coated, the luminous intensity of the phosphor decreases by less than 3%. It can be seen that the modified material of the present invention improves the corrosion resistance and resistance of the material. While being wet, the luminescent properties of the fluoride luminescent material are also maintained.
  • the surface modification method provided by the present invention has low preparation temperature, short time, and easy process control, and is suitable for large-scale industrial preparation. At the same time, it has a wide range of application, and this method can be used for surface modification of phosphors with similar moisture resistance.
  • Example 1 (C) of the present invention is a scanning electron micrograph of K 2 TiF 6 : Mn 4+ @K 2 TiF 6 @ metal phosphate phosphor in Example 1 (C) of the present invention.
  • FIG. 7 is a graph showing the change in luminous intensity after encapsulating the phosphor and silica gel of Example 1 and Preparation Example 1 of the present invention at 85 ° C. and 85% humidity.
  • FIG. 8 is a graph showing the change in luminous intensity after the phosphor and silica gel encapsulated in Example 2 and Preparation Example 2 of the present invention are aged at 85 ° C. and 85% humidity.
  • FIG. 9 is a graph showing the change in luminous intensity after encapsulating the phosphor and silica gel of Example 3 and Preparation Example 2 of the present invention at 85 ° C. and 85% humidity.
  • FIG. 10 is a schematic structural view of the surface-modified phosphor according to a preferred solution of the present invention.
  • X-ray powder diffractometer (DMAX 2500PC, Rigaku) was used for phase analysis; field emission scanning electron microscope (FE-SEM, Hitachi SU1510) was used to observe the shape of the sample; FLS980 (Edinburgh Instrument) fluorescence spectrometer was used to characterize the sample fluorescence spectrum .
  • the chemical formula of fluoride phosphor is A 2 MF 6 : Mn 4+ .
  • A is selected from one of alkali metals Li, Na, K, Rb, Cs or a combination thereof;
  • M is selected from one of Ti, Si, Ge, Sn, Zr, Al, Bi, Ga, In Species or a combination of them;
  • Mn 4+ is the luminescent center ion; the preparation process is based on the stoichiometric ratio of Mn 4+ doped fluoride phosphor material, and the oxide or salt or acid containing M element is dissolved at a concentration of 20-50% HF solution, then add A fluoride, stir for 1-10min, add A 2 MnF 6 , continue to stir for 30-90min, let stand, the resulting precipitate is filtered, washed and dried to obtain fluoride red fluorescence Powder A 2 MF 6 .
  • a saturated solution of K 2 TiF 6 in 49% HF solution was obtained by adding K 2 TiF 6 compound to 10 ml of 49% HF solution until it was no longer dissolved, and filtering the undissolved K 2 TiF 6 . Subsequently, the saturated solution was added to a container containing 1 g of K 2 TiF 6 : Mn 4+ phosphor obtained in Preparation Example 1, stirring was continued at room temperature, stirring was stopped after 30 min, vacuum suction filtration and washing with acetone 3 times , To remove residual HF, and finally dried in an oven at 70 °C for 4h, to obtain the inorganic coating layer K 2 TiF 6 coated matrix material K 2 TiF 6 : Mn 4+ , denoted as K 2 TiF 6 : Mn 4+ @K 2 TiF 6 phosphor; the excitation and emission spectra of the product and the internal fluorescence quantum yield were measured by FLS980 fluorescence spectrometer. Table 2 shows the important luminescence performance parameters of the prepared phosphor.
  • Figures 4-6 are scanning electron micrographs of the phosphors prepared in (A), (B), and (C) in Example 1. It can be seen from the figure that the surface of the sample after inorganic coating alone is smooth, and the particle size does not change. There is a small amount of fine material on the surface of the sample after organic coating.
  • a saturated solution of K 2 SiF 6 in 49% HF solution was obtained by adding K 2 SiF 6 compound to 10 ml of 49% HF solution until it was no longer dissolved, and filtering the undissolved K 2 SiF 6 . Subsequently, the saturated solution was added to a container containing 1 g of K 2 SiF 6 : Mn 4+ phosphor obtained in Preparation Example 2, and stirring was continued at room temperature.
  • a saturated solution of K 2 GeF 6 in a 49% HF solution was obtained by adding K 2 GeF 6 compound to 10 ml of 49% HF solution until it was no longer dissolved, and filtering the undissolved K 2 GeF 6 . Subsequently, the saturated solution was added to the container containing the K 2 GeF 6 : Mn 4+ phosphor obtained in Preparation Example 3, and stirring was continued at room temperature.
  • Fig. 7, Fig. 8 and Fig. 9 are graphs showing the results of changes in the luminous intensity of the phosphor after aging under the conditions of 85 ° C and 85% relative humidity. It can be seen from FIG. 7 that the moisture resistance of the phosphor modified by the inorganic-organic layer coating of the present invention has been greatly improved. After 240 h, the luminous intensity of the phosphor prepared in Example 1 (C) is still Remain 92%. However, the luminous intensity of the inorganic-coated fluoride phosphor (Example 1 (A)) is only 83%, and the luminous intensity of the un-surface-modified fluoride phosphor (prepared in Preparation Example 1) is only 59%. It can be seen that the inorganic-organic layer coating obtains more excellent effects than the organic layer coating alone or the inorganic layer coating alone. The aging test results of the other examples and the preparation examples are similar (see FIG. 8 and FIG. 9).

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Abstract

一种氟化物发光材料的表面改性方法及其制备得到的氟化物发光材料，所述材料是将无机包覆层A xMF y包覆的基体材料A xMF y:Mn 4+与含有金属磷酸酯或烷氧基硅烷或有机羧酸类物质或有机胺类物质的有机溶液混合，通过将溶液蒸干，制备得到有机包覆层-无机包覆层共同包覆的表面改性的氟化物发光材料。该包覆方法显著提高了氟化物荧光粉的耐湿性，改性后荧光粉在高温高湿环境下其发光强度和量子效率保持率达到85-95％，可广泛用于白光LED背光源显示领域。该无机包覆后，减少了荧光粉的表面缺陷，荧光粉的发光强度及量子产率有5％-15％的提升。有机包覆层包覆后，荧光粉的发光强度降低量<3％。提供的表面改性方法制备温度低、时间短、工艺易控制，适合工业大规模制备。

Description

一种氟化物发光材料的表面改性方法及其制备得到的氟化物发光材料
本申请要求2018年11月13日向中国国家知识产权局提交的专利申请号为2018113489870，发明名称为“一种氟化物发光材料的表面改性方法及其制备得到的氟化物发光材料”的在先申请的优先权，该在先申请的全文通过引用的方式结合于本申请中。
技术领域
本发明涉及稀土发光材料和照明显示技术领域，尤其是涉及一种氟化物发光材料的表面改性方法及其制备得到的氟化物发光材料。
背景技术
白光LED作为一种新型的固态光源，与传统的白炽灯和荧光灯等光源相比，它具有环保、节能、高效、响应快等优点，被誉为继白炽灯、荧光灯和高压气体放电灯三大光源之后的第四代绿色光源。在LED光源中，荧光粉的性能决定了LED的发光效率、显色指数、色温及使用寿命等技术指标，因此，荧光粉在白光LED中具有举足轻重的地位，受到广泛关注。目前最常用的方法是将蓝光LED芯片(发光波长440-480nm)与黄光荧光粉(如YAG:Ce或TAG:Ce)相结合，结合后黄光荧光粉吸收部分蓝光LED芯片发出的蓝光后发射出黄光，并与未被吸收的蓝光混合形成白光。但是采用这种方式只能获得相关色温(Correlated Color Temperature，CCT)大于4500K的冷白光器件，同时，其显色指数(Color Rendering Index，CRI)也较低，通常小于80。其主要原因在于常用的黄光荧光粉发射光谱中的红光成份不足，导致难以获得低色温、暖色调以及高显色指数的白光LED器件，而这正是白光LED能在室内获得应用的关键。要想实现这一目标，一个有效的办法就是在白光LED器件中添加适当的红光荧光粉，增强器件的红光发射。
Mn 4+离子激活的氟化物材料具有窄的发射峰，半峰宽小，是目前红光发光材料的研究热点。专利文献US2009/7497973公开了Mn 4+激活的A 2MF 6(A为K，Na，Rb等；M为Ti，Si，Sn，Ge等)红光荧光粉；其中通过将原料溶解在高浓度氢氟酸中， 然后加热挥发共结晶得到产物；专利文献WO2009/119486公开了将单质Si溶解在氢氟酸和高锰酸钾的溶液中，反应得到氟化物产物；专利文献CN102732249A公开报道了通过先制备含有金属M的氟化物的第一种溶液和含有A的第二种溶液或固体形式的A的化合物，将两者混合，经反应后生成沉淀，得到产物；上述提及的这些方法制备的氟化物发光材料都具有发光效率高，热稳定性好的优点。但这些方法都没有克服氟化物发光材料自身易水解的缺点，在长期使用或潮湿环境下容易水解，导致发光效率降低甚至失效。专利文献US2007/0125984A1报道了在荧光粉表面包覆一层无机材料(如TiO 2、Al 2O 3、SiO 2)作为保护膜，提高荧光粉的抗湿性；但这种水相包覆技术难以运用到氟化物荧光粉的包覆上。专利文献CN106479485A同样公开报道在荧光粉颗粒表面包覆一层硅酸钾-羟甲基纤维素钠-聚乙二醇混合物，提高荧光粉的耐高温高湿性能；但这种有机包覆材料，同样具有不耐高温易分解的缺点，影响荧光粉长期使用的效率。因此，提高氟化物荧光粉抗湿性能，同时延长白光LED的使用寿命，符合节能环保的要求，具有重大的现实意义。
发明内容
由于Mn 4+掺杂的氟化物红色荧光粉的抗湿性差，在潮湿环境下易发生水解，导致红色荧光粉效率下降甚至失效，降低LED的使用寿命。为了改善氟化物红色荧光粉的抗湿性，需要对荧光粉材料进行表面改性，在荧光粉材料的表面包覆无机薄层和有机薄层，形成具有耐湿性能的保护层。
为了解决现有技术的不足，本发明的目的在于提供一种氟化物发光材料的表面改性方法及其制备得到的氟化物发光材料。本发明通过离子交换法，除去基体材料A xMF y:Mn 4+表面层的Mn 4+，形成了无机包覆层A xMF y包覆基体材料A xMF y:Mn 4+的结构，记为A xMF y:Mn 4+@A xMF y，该A xMF y:Mn 4+@A xMF y可有效防止基体材料A xMF y:Mn 4+颗粒内部发光中心将能量传递到表面，避免由此引起的荧光淬灭，提高氟化物发光材料的发光效率；再通过在无机包覆层外表面包覆有机包覆层，形成表面疏水层，达到在不明显降低氟化物发光材料发光效率的基础上，有效提高氟化物发光材料在高温高湿环境下的稳定性。该方法具有制备工艺简单、原料来源广泛以及氢氟酸消耗量小的特点，适于工业化大规模制备。
本发明的目的通过以下技术方案实现：
一种表面改性的氟化物发光材料，其中，所述发光材料包括基体材料、无机包 覆层和有机包覆层，所述无机包覆层包覆在基体材料外表面，所述有机包覆层包覆在无机包覆层外表面；
所述基体材料为A xMF y:Mn 4+，所述无机包覆层为A xMF y；其中，A选自碱金属Li、Na、K、Rb、Cs中的一种或它们之间的组合；M选自Ti、Si、Ge、Sn、Zr、Al、Bi、Ga、In中的一种或它们之间的组合，x为[MF y]离子的电荷的绝对值，y为4、5、6或7；Mn 4+为发光中心离子。
根据本发明的实施方式，优选地，x为[MF 6]离子的电荷的绝对值，y为6。
根据本发明的实施方式，优选地，所述无机包覆层A xMF y是通过离子交换法除去基体材料A xMF y:Mn 4+表面层的Mn 4+制备得到的。
根据本发明的实施方式，所述表面改性的氟化物发光材料中，所述无机层可为单层或多层，无机层外表面包覆的有机层也可以为单层或多层。示例性地，双层包覆结构为基体材料表面包覆一层无机包覆层，无机包覆层外表面包覆一层有机包覆层；多层包覆结构可为基体材料表面包覆多层无机包覆层，多层无机包覆层外表面包覆单层有机包覆层；或者，基体材料表面包覆单层无机包覆层，单层无机包覆层外表面包覆多层有机包覆层；或者，基体材料表面包覆多层无机包覆层，多层无机包覆层外表面包覆多层有机包覆层。
所述多层有机包覆层的组成相同或不同，优选相邻的有机包覆层的组成不同。
根据本发明的实施方式，所述无机包覆层和有机包覆层通过化学键结合。
根据本发明的实施方式，所述有机包覆层为金属磷酸酯、烷氧基硅烷、有机羧酸类物质或有机胺类物质中的至少一种。
根据本发明的实施方式，所述金属磷酸酯中的磷酸酯为磷酸单酯、或磷酸二酯，例如P(O)(OH) 2(OR)、或P(O)(OH)(OR) 2，其中，R为烃基；例如烷基(如C 1-20烷基)。
根据本发明的实施方式，所述磷酸酯是通过将磷源与醇酯化后得到的，其中，所述磷源选自P 2O 5或POCl 3中的一种或它们之间的组合。所述醇选自甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇中的至少一种。
根据本发明的实施方式，所述金属磷酸酯中的金属为金属阳离子，例如为Al、Ti、Si、Ga、Zn离子中的一种或它们之间的组合。
根据本发明的实施方式，所述烷氧基硅烷为Si(OR 1) 3(R 2)，其中，R 1为C 1-6烷基，R 2为C 1-20烷基、C 1-20烯基，例如选自甲基三甲氧基硅烷、乙基三甲氧基硅烷、正丙基三甲氧基硅烷、正辛基三甲氧基硅烷、乙烯基三甲氧基硅烷、十二烷基三甲氧基硅 烷、十六烷基三甲氧基硅烷、十八烷基三甲氧基硅烷。
根据本发明的实施方式，所述有机羧酸类物质为R 3COOH，R 3为C 1-30烷基，例如选自油酸、硬脂酸、二十二烷酸、二十八酸、月桂酸。
根据本发明的实施方式，所述有机胺类物质为NR 4(R 5) 2，R 4为C 1-10烷基，R 5相同或不同，任选的为H，C 1-10烷基，例如选自甲胺、乙胺、丙胺、丁胺、辛胺、己胺或相应的二级胺或三级胺。所述的相应的是指甲胺、乙胺、丙胺、丁胺、辛胺、己胺的二级胺或三级胺。
本文还提供上述表面改性的氟化物发光材料的制备方法，包括如下步骤：
(1)将A xMF y化合物溶于氢氟酸溶液中形成饱和溶液；
(2)将基体材料A xMF y:Mn 4+与步骤1)的饱和溶液混合，进行离子交换反应，制备得到离子交换后的无机包覆层A xMF y包覆的A xMF y:Mn 4+基体材料，记为A xMF y:Mn 4+@A xMF y；
(3)配制有机溶液；
(4)将步骤(2)的无机包覆层A xMF y包覆的A xMF y:Mn 4+基体材料与步骤(3)的有机溶液混合，加热搅拌直至有机溶剂蒸干，制备得到表面改性的氟化物发光材料，记为A xMF y:Mn 4+@A xMF y@有机层；
其中，所述A选自碱金属Li、Na、K、Rb、Cs中的一种或它们之间的组合；所述M选自Ti、Si、Ge、Sn、Zr、Al、Bi、Ga、In中的一种或它们之间的组合，x为[MF y]离子的电荷的绝对值，y为4、5、6或7；Mn 4+为发光中心离子。
根据本发明的实施方式，步骤(1)中，所述氢氟酸溶液中氢氟酸的质量百分比为20-50％。
根据本发明的实施方式，步骤(1)中，所述饱和溶液优选在20℃-90℃下形成。
根据本发明的实施方式，步骤(2)中，所述基体材料A xMF y:Mn 4+与步骤(1)的饱和溶液中的A xMF y化合物质量比为10:1-1:5，优选为1:1。
根据本发明的实施方式，步骤(2)中，所述离子交换反应是在0℃-100℃下进行，优选为在25℃-80℃下进行。
根据本发明的实施方式，步骤(2)中，所述离子交换反应的时间为至少30秒，例如为至少1min，优选为至少5min。
根据本发明的实施方式，步骤(2)中，所述离子交换反应是在持续搅拌条件下进行的。
根据本发明的实施方式，步骤(2)还包括如下步骤：将离子交换反应结束后的混合液过滤，干燥处理。
根据本发明的实施方式，步骤(3)中，所述有机溶液为金属磷酸酯溶液、烷氧基硅烷溶液、有机羧酸类物质溶液或有机胺类物质溶液中的至少一种，上述溶液的制备方法例如为：
将烷氧基硅烷或有机羧酸类物质或有机胺类物质溶于有机溶剂中；所述有机溶剂为甲醇、乙醇、丙醇、正己烷或环己烷中的至少一种；或者，
将金属源、磷源与醇混合，反应得到金属磷酸酯溶液；其中，所述磷源选自P 2O 5或POCl 3中的一种或它们之间的组合；所述醇选自甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇中的至少一种；所述金属源为金属硝酸盐或金属硫酸盐或金属草酸盐，也可以为异丙醇盐或乙醇盐或丙醇盐或丁醇盐等金属有机盐的一种或多种。
根据本发明的实施方式，步骤(3)中，烷氧基硅烷或有机羧酸类物质或有机胺类物质在有机溶剂中的含量至少为1wt.％，优选为5wt.％。
根据本发明的实施方式，优选地，所述金属源为Al(NO 3) 3·9H 2O、Zn(NO 3) 2·6H 2O、丁醇钛、异丙醇铝。
根据本发明的实施方式，金属磷酸酯的有机溶液中，金属源的质量百分含量至少为0.1％，磷源的质量百分含量至少为10％。
根据本发明的实施方式，步骤(4)中，所述加热搅拌的温度至少为30℃，优选为至少50℃。
根据本发明的实施方式，步骤(4)中，所述无机包覆层A xMF y包覆的A xMF y:Mn 4+基体材料与有机溶液的质量比为5:1-1:20，优选为1:1-1:5。
根据本发明的实施方式，步骤(4)中，还包括如下步骤：用醇溶液或丙酮洗涤、干燥。
根据本发明的实施方式，步骤(2)中，优选地，所述A xMF y:Mn 4+选自A 2MF 6:Mn 4+或A 3MF 6:Mn 4+，所述A 2MF 6:Mn 4+选自K 2TiF 6:Mn 4+、K 2SiF 6:Mn 4+、Na 2SiF 6:Mn 4+、Na 2TiF 6:Mn 4+、K 2GeF 6:Mn 4+、Na 2SnF 6:Mn 4+、Cs 2TiF 6:Mn 4+或Cs 2SiF 6:Mn 4+，还优选为K 2TiF 6:Mn 4+、K 2SiF 6:Mn 4+或K 2GeF 6:Mn 4+。
优选地，所述A 3MF 6:Mn 4+选自Na 3AlF 6:Mn 4+、K 3AlF 6:Mn 4+、Li 3AlF 6:Mn 4+、Rb 3AlF 6:Mn 4+、Cs 3AlF 6:Mn 4+、K 2NaAlF 6:Mn 4+、K 2LiAlF 6:Mn 4+，还优选为Na 3AlF 6:Mn 4+、K 3AlF 6:Mn 4+、K 2NaAlF 6:Mn 4+。
根据本发明的实施方式，步骤(1)中，优选地，所述A xMF y选自A 2MF 6或A 3MF 6，所述A 2MF 6选自K 2TiF 6、K 2SiF 6、Na 2SiF 6、Na 2TiF 6、K 2GeF 6、Na 2SnF 6、Cs 2TiF 6或Cs 2SiF 6，还优选为K 2TiF 6、K 2SiF 6或K 2GeF 6。
优选地，所述A 3MF 6选自Na 3AlF 6、K 3AlF 6、Li 3AlF 6、Rb 3AlF 6、Cs 3AlF 6、K 2NaAlF 6、K 2LiAlF 6，还优选为Na 3AlF 6、K 3AlF 6、K 2NaAlF 6。
根据本发明的实施方式，步骤(2)和(4)中，经过滤后的产物可进一步用有机溶剂如无水乙醇或丙酮进行洗涤，以去除表面残余的酸液，并进行干燥。
本发明中，当基体材料A xMF y:Mn 4+与A xMF y化合物的饱和氢氟酸溶液混合时，基体材料A xMF y:Mn 4+表面层的Mn 4+和A xMF y化合物的饱和氢氟酸溶液中金属阳离子M发生表面离子交换反应，使得基体材料A xMF y:Mn 4+表面层没有Mn 4+，形成无机包覆层A xMF y包覆在基体材料A xMF y:Mn 4+表面的核壳结构，且此过程基体材料A xMF y:Mn 4+颗粒尺寸没有变化，制备得到的中间产物由于表面层不含有Mn 4+，可以有效防止荧光粉颗粒内部发光中心将能量传递到表面的猝灭中心，提高荧光粉的发光效率。但该无机包覆层包覆后的荧光粉颗粒外表面的厚度有限，耐水性不够充足。
本发明中，将无机包覆层A xMF y包覆的基体材料A xMF y:Mn 4+与含有金属磷酸酯或烷氧基硅烷或有机羧酸类物质或有机胺类物质的有机溶液混合，通过将溶液蒸干，制备得到本发明的有机-无机包覆层共同包覆的基体材料A xMF y:Mn 4+，即表面改性的氟化物发光材料。该表面改性的氟化物发光材料由于无机包覆层和有机包覆层之间的界面没有激发中心Mn 4+，荧光粉的发光性能降低少。
有益效果：
(1)本发明提供的表面改性后的Mn 4+掺杂氟化物发光材料具有无机层和有机层包覆结构，该包覆结构显著提高了氟化物荧光粉的耐蚀性，改性后荧光粉在高温高湿环境下其发光强度和量子效率保持率达到85-95％，可广泛用于白光LED背光源显示领域。
(2)本发明提供的无机包覆层，其成分与荧光粉基质材料相同，该无机包覆层可以是一层或多层，所述无机包覆层包覆后，减少了荧光粉的表面缺陷，荧光粉的发光强度及量子产率有5％-15％的提升。
(3)本发明提供的有机包覆层，避开了直接在A 2MF 6:Mn 4+荧光粉基体材料表面进行，防止了有机包覆层与Mn 4+的直接接触而降低材料发光强度和量子产率。该有 机层可以是一层或多层，所述有机包覆层包覆后，荧光粉的发光强度降低量仅小于3％，可见，本发明所述改性材料在提高材料的耐腐蚀、抗湿性的同时，还保持了氟化物发光材料的发光性能。
(4)本发明提供的表面改性方法制备温度低、时间短、工艺易控制，适合工业大规模制备。同时适用范围广，类似抗湿性差的荧光粉表面改性均可采用该方法。
附图说明
图1本发明实施例1中(C)的K 2TiF 6:Mn 4+@K 2TiF 6@金属磷酸酯荧光粉的XRD衍射图谱。
图2本发明实施例2中(C)的K 2SiF 6:Mn 4+@K 2SiF 6@金属磷酸酯荧光粉的XRD衍射图谱。
图3本发明实施例3中(C)的K 2GeF 6:Mn 4+@K 2GeF 6@金属磷酸酯荧光粉的XRD衍射图谱。
图4本发明实施例1中(A)的K 2TiF 6:Mn 4+荧光粉的扫描电镜图。
图5本发明实施例1中(B)的K 2TiF 6:Mn 4+@K 2TiF 6荧光粉的扫描电镜图。
图6本发明实施例1中(C)的K 2TiF 6:Mn 4+@K 2TiF 6@金属磷酸酯荧光粉的扫描电镜图。
图7本发明实施例1和制备例1的荧光粉与硅胶封装后样品在85℃，85％湿度环境下老化后，发光强度的变化图。
图8本发明实施例2和制备例2的荧光粉与硅胶封装后样品在85℃，85％湿度环境下老化后，发光强度的变化图。
图9本发明实施例3和制备例2的荧光粉与硅胶封装后样品在85℃，85％湿度环境下老化后，发光强度的变化图。
图10本发明一个优选方案所述的表面改性的荧光粉的结构示意图。
具体实施方式
下文将结合具体实施例对本发明的制备方法做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中 所用的试剂、材料等，如无特殊说明，均可从商业途径得到。
仪器和设备
采用X射线粉末衍射仪(DMAX 2500PC,Rigaku)进行物相分析；采用场发射扫描电镜(FE-SEM,Hitachi SU1510)对样品形貌观察；用FLS980型(Edinburgh Instrument)荧光光谱仪对样品荧光光谱表征。
本发明具体实施例中氟化物荧光粉的化学通式为A 2MF 6:Mn 4+。其中，A选自碱金属Li，Na，K，Rb，Cs中的一种或它们之间的组合；M选自Ti，Si，Ge，Sn，Zr，Al、Bi、Ga、In中的一种或它们之间的组合；Mn 4+为发光中心离子；其制备过程按Mn 4+掺杂氟化物荧光粉材料的化学式计量比，将含M元素的氧化物或盐或酸溶于浓度为20-50％的HF溶液中，然后加入A的氟化物，搅拌1-10min，加入A 2MnF 6，继续搅拌30-90min，静置，所得沉淀经过过滤、洗涤、干燥，得到氟化物红色荧光粉A 2MF 6。
制备例1-3：A 2MF 6:Mn 4+荧光粉的制备
制备例1-3合成方法一致，仅仅在原料种类和用量有区别，具体参数如下述表1所示。以制备例1的K 2MF 6:Mn 4+荧光粉为例，首先将K 2MnF 6溶解在氢氟酸溶液中，搅拌1-10min后，将A 2MF 6粉末加入到溶液中，室温下继续搅拌30-90min，最后过滤，再用丙酮进行清洗，出去任何残留的HF，放入烘箱中70℃干燥4h，得到最终粉末。通过FLS980型(Edinburgh Instrument)荧光光谱仪对产物的激发和发射光谱以及荧光量子产率和吸收效率进行测试，结果如表2所示。
表1.制备例1-3合成技术参数
Figure PCTCN2019111737-appb-000001
实施例1：
(A)改性的K 2TiF 6:Mn 4+@K 2TiF 6荧光粉的制备
通过向10ml 49％HF溶液中加入K 2TiF 6化合物，直至不再溶解为止，过滤未溶解的K 2TiF 6，获得K 2TiF 6在49％HF溶液中的饱和溶液。随后将该饱和溶液加入到装有1g制备例1中获得的K 2TiF 6:Mn 4+荧光粉的容器中，在室温下持续搅拌，30min后停止 搅拌，进行真空抽滤并用丙酮洗涤3次，除去残留HF，最后在烘箱中70℃干燥4h，获得无机包覆层K 2TiF 6包覆的基体材料K 2TiF 6:Mn 4+，记为K 2TiF 6:Mn 4+@K 2TiF 6荧光粉；通过FLS980型荧光光谱仪测量了产物的激发和发射光谱以及内荧光量子产率，表2给出了所制备的荧光粉的重要发光性能参数。
(B)改性的K 2TiF 6:Mn 4+@金属磷酸酯荧光粉的制备
通过向10ml乙醇溶液中加入0.0350g的P 2O 5，持续搅拌，在向溶液中添加0.1468g的Al(NO 3) 3·9H 2O，Al:P的摩尔比为1:1，溶液加热至70℃并不断搅拌，将制备例1中的K 2TiF 6:Mn 4+荧光粉1g放入溶液中，加热搅拌直至溶液蒸干。随后用丙酮洗涤数次，放入烘箱中，140℃下干燥4小时，获得荧光粉体，记为K 2TiF 6:Mn 4+@金属磷酸酯荧光粉。表2给出了所制备荧光粉的重要发光性能参数。
(C)改性的K 2TiF 6:Mn 4+@K 2TiF 6@金属磷酸酯荧光粉的制备
通过向10ml乙醇溶液中加入0.0350g的P 2O 5，持续搅拌，在向溶液中添加0.1468g的Al(NO 3) 3·9H 2O，Al:P的摩尔比为1:1，溶液加热至70℃并不断搅拌，将1g的实施例1中(A)制备的K 2TiF 6:Mn 4+@K 2TiF 6荧光粉放入溶液中，加热搅拌直至溶液蒸干。随后用丙酮洗涤数次，放入烘箱中，140℃下干燥4小时，获得荧光粉体，记为K 2TiF 6:Mn 4+@K 2TiF 6@金属磷酸酯荧光粉。X射线粉末衍射表明产物仍为纯相的K 2TiF 6(图1)，没有其他杂相引入。表2给出了所制备荧光粉的重要发光性能参数。
(D)改性的K 2TiF 6:Mn 4+@K 2TiF 6@十八烷基三甲氧基硅烷荧光粉的制备
通过向50ml正己烷中加入2.5ml十八烷基三甲氧基硅烷，持续搅拌30min，将1g的实施例1中(A)制备的K 2TiF 6:Mn 4+@K 2TiF 6荧光粉放入溶液中，溶液加热至70℃并不断搅拌至溶液蒸干。随后用正己烷洗涤数次，放入烘箱中，150℃下干燥4小时，获得荧光粉体，记为K 2TiF 6:Mn 4+@K 2TiF 6@十八烷基三甲氧基硅烷荧光粉。表2给出了所制备荧光粉的重要发光性能参数。
图4-图6为实施例1中(A)、(B)和(C)制备的荧光粉的扫描电镜图，从图中看出单独无机包覆后的样品表面光滑，颗粒尺寸没有变化。有机包覆后样品表面有少量细小物质。
实施例2
(A)改性的K 2SiF 6:Mn 4+@K 2SiF 6荧光粉的制备
通过向10ml 49％HF溶液中加入K 2SiF 6化合物，直至不再溶解为止，过滤未溶解 的K 2SiF 6，获得K 2SiF 6在49％HF溶液中的饱和溶液。随后将该饱和溶液加入到装有1g制备例2中获得的K 2SiF 6:Mn 4+荧光粉的容器中，在室温下持续搅拌，该过程中，以0.5ml/min的速度往溶液中滴加乙醇，30min后停止搅拌，进行真空抽滤并用丙酮洗涤3次，除去残留HF，最后在烘箱中70℃干燥4h，获得K 2SiF 6:Mn 4+@K 2SiF 6荧光粉；通过FLS980型荧光光谱仪测量了产物的激发和发射光谱以及内荧光量子产率，表2给出了所制备荧光粉的重要发光性能参数。
(B)改性的K 2SiF 6:Mn 4+@金属磷酸酯荧光粉的制备
通过向10ml乙醇溶液中加入0.0350g的P 2O 5，持续搅拌，在向溶液中添加0.1468g的Al(NO 3) 3·9H 2O，Al:P的摩尔比为1:1，溶液加热至70℃并不断搅拌，将制备例2中的K 2SiF 6:Mn 4+荧光粉1g放入溶液中，加热搅拌直至溶液蒸干。随后用丙酮洗涤数次，放入烘箱中，140℃下干燥4小时，获得荧光粉体。表2给出了所制备荧光粉的重要发光性能参数。
(C)改性的K 2SiF 6:Mn 4+@K 2SiF 6@金属磷酸酯荧光粉的制备
通过向10ml乙醇溶液中加入0.0350g的P 2O 5，持续搅拌，在向溶液中添加0.1468g的Al(NO 3) 3·9H 2O，Al:P的摩尔比为1:1，溶液加热至70℃并不断搅拌，将1g实施例2中(A)得到的K 2SiF 6:Mn 4+@K 2SiF 6荧光粉放入溶液中，加热搅拌直至溶液蒸干。随后用丙酮洗涤数次，放入烘箱中，140℃下干燥4小时，获得荧光粉体。X射线粉末衍射表明产物仍为纯相K 2SiF 6(图2)，没有其他杂相引入。表2给出了所制备荧光粉的重要发光性能参数。
(D)改性的K 2SiF 6:Mn 4+@K 2SiF 6@十六烷基三甲氧基硅烷荧光粉的制备
通过向50ml正己烷中加入5ml十六烷基三甲氧基硅烷，持续搅拌30min，将1g的实施例2中(A)制备的K 2SiF 6:Mn 4+@K 2SiF 6荧光粉放入溶液中，溶液加热至70℃并不断搅拌至溶液蒸干。随后用正己烷洗涤数次，放入烘箱中，150℃下干燥4小时，获得荧光粉体，记为K 2SiF 6:Mn 4+@K 2SiF 6@十六烷基三甲氧基硅烷荧光粉。表2给出了所制备荧光粉的重要发光性能参数。
实施例3
(A)改性的K 2GeF 6:Mn 4+@K 2GeF 6荧光粉的制备
通过向10ml 49％HF溶液中加入K 2GeF 6化合物，直至不再溶解为止，过滤未溶解的K 2GeF 6，获得K 2GeF 6在49％HF溶液中的饱和溶液。随后将该饱和溶液加入到装 有制备例3中获得的K 2GeF 6:Mn 4+荧光粉的容器中，在室温下持续搅拌，该过程中，以0.5ml/min的速度往溶液中滴加乙醇，30min后停止搅拌，进行真空抽滤并用丙酮洗涤3次，除去残留HF，最后在烘箱中70℃干燥4h，获得K 2GeF 6:Mn 4+@K 2GeF 6荧光粉；通过FLS980型荧光光谱仪测量了产物的激发和发射光谱以及内荧光量子产率，表2给出了所制备荧光粉的重要发光性能参数。
(B)改性的K 2GeF 6:Mn 4+@金属磷酸酯荧光粉的制备
通过向10ml乙醇溶液中加入0.0350g的P 2O 5，持续搅拌，在向溶液中添加0.1468g的Al(NO 3) 3·9H 2O，Al:P的摩尔比为1:1，溶液加热至70℃并不断搅拌，将1g制备例3中的K 2GeF 6:Mn 4+荧光粉放入溶液中，加热搅拌直至溶液蒸干。随后用丙酮洗涤数次，放入烘箱中，140℃下干燥4小时，获得荧光粉体。表2给出了所制备荧光粉的重要发光性能参数。
(C)改性的K 2GeF 6:Mn 4+@K 2GeF 6@金属磷酸酯荧光粉的制备
通过向10ml乙醇溶液中加入0.0350g的P 2O 5，持续搅拌，在向溶液中添加0.1468g的Al(NO 3) 3·9H 2O，Al:P的摩尔比为1:1，溶液加热至70℃并不断搅拌，将1g实施例3中(A)得到的K 2GeF 6:Mn 4+@K 2GeF 6荧光粉放入溶液中，加热搅拌直至溶液蒸干。随后用丙酮洗涤数次，放入烘箱中，140℃下干燥4小时，获得荧光粉体。X射线粉末衍射表明产物仍为纯相K 2GeF 6(图3)，没有其他杂相引入。表2给出了所制备荧光粉的重要发光性能参数。
(D)改性的K 2GeF 6:Mn 4+@K 2GeF 6@十二烷基三甲氧基硅烷荧光粉的制备
通过向50ml正己烷中加入5ml十二烷基三甲氧基硅烷，持续搅拌30min，将1g的实施例3中(A)制备的K 2GeF 6:Mn 4+@K 2GeF 6荧光粉放入溶液中，溶液加热至70℃并不断搅拌至溶液蒸干。随后用正己烷洗涤数次，放入烘箱中，150℃下干燥4小时，获得荧光粉体，记为K 2GeF 6:Mn 4+@K 2GeF 6@十二烷基三甲氧基硅烷荧光粉。表2给出了所制备荧光粉的重要发光性能参数。
表2.样品老化发光性能参数
Figure PCTCN2019111737-appb-000002
Figure PCTCN2019111737-appb-000003
由表2中可以看出，单独的无机包覆表面改性后提高了荧光粉的量子产率和亮度，但吸收率有略微降低；单独的有机包覆，荧光粉的发光亮度和量子产率降低明显；经过无机-有机层包覆后，与未包覆的荧光粉相比，其量子产率基本不变或略微增加。
实施例4：稳定性测试
分别取制备例1-3、实施例1-3中所制备的荧光粉样品各0.1g，与硅胶(A胶B胶)混合均匀，封装在定制好的聚四氟模具中，通过脱泡、硬化，获得荧光粉胶片。将胶片放置于85℃、85％相对湿度的恒温恒湿试验箱中老化，每隔24h对样品的光谱和量子效率进行测试，评估荧光粉的高温高湿稳定性。
图7，图8和图9为上述荧光粉在85℃、85％相对湿度的条件下老化后发光强度变化结果图。由图7中可以看到，本发明经过无机-有机层包覆改性的荧光粉抗湿性能得到了很大的提高，240h后，实施例1中(C)所制备的荧光粉发光强度仍然保持92％。而无机包覆的氟化物荧光粉(实施例1中(A))发光强度仅为83％，未表面改性的氟化物荧光粉(制备例1所制备的)的发光强度仅剩59％。可见无机-有机层包覆与单独有机层包覆或单独无机层包覆相比获得了更加优良的效果。其他实施例和制备例的老化测试结果类似(见图8、图9)。
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种表面改性的氟化物发光材料，其中，所述发光材料包括基体材料、无机包覆层和有机包覆层，所述无机包覆层包覆在基体材料外表面，所述有机包覆层包覆在无机包覆层外表面；
    所述基体材料为A xMF y:Mn 4+，所述无机包覆层为A xMF y；其中，A选自碱金属Li、Na、K、Rb、Cs中的一种或它们之间的组合；所述M选自Ti、Si、Ge、Sn、Zr、Al、Bi、Ga、In中的一种或它们之间的组合，x为[MF y]离子的电荷的绝对值，y为4、5、6或7；Mn 4+为发光中心离子。
  2. 根据权利要求1所述的表面改性的氟化物发光材料，其中，x为[MF 6]离子的电荷的绝对值，y为6。
  3. 根据权利要求1或2所述的表面改性的氟化物发光材料，其中，所述无机层可为单层或多层，无机层外表面包覆的有机层也可以为单层或多层。
  4. 根据权利要求1-3任一项所述的表面改性的氟化物发光材料，其中，所述有机包覆层为金属磷酸酯、烷氧基硅烷、有机羧酸类物质或有机胺类物质中的至少一种。
  5. 根据权利要求1-4任一项所述的表面改性的氟化物发光材料，其中，所述金属磷酸酯中的磷酸酯为磷酸单酯、或磷酸二酯，例如P(O)(OH) 2(OR)、或P(O)(OH)(OR) 2，其中，R为烃基；
    优选地，所述磷酸酯是通过将磷源与醇酯化后得到的，其中，所述磷源选自P 2O 5或POCl 3中的一种或它们之间的组合；所述醇选自甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇中的至少一种；
    优选地，所述金属磷酸酯中的金属为Al、Ti、Si、Ga、Zn离子中的一种或它们之间的组合；
    优选地，所述烷氧基硅烷为Si(OR 1) 3(R 2)，其中，R 1为C 1-6烷基，R 2为C 1-20烷基、C 1-20烯基，例如选自甲基三甲氧基硅烷、乙基三甲氧基硅烷、正丙基三甲氧基硅烷、正辛基三甲氧基硅烷、乙烯基三甲氧基硅烷、十二烷基三甲氧基硅烷、十六烷基三甲氧基硅烷、十八烷基三甲氧基硅烷；
    优选地，所述有机羧酸类物质为R 3COOH，R 3为C 1-30烷基，例如选自油酸、硬脂酸、二十二烷酸、二十八酸、月桂酸；
    优选地，所述有机胺类物质为NR 4(R 5) 2，R 4为C 1-10烷基，R 5相同或不同，任选的为H，C 1-10烷基，例如选自甲胺、乙胺、丙胺、丁胺、辛胺、己胺或相应的二级胺或三级胺。
  6. 权利要求1-5任一项所述的表面改性的氟化物发光材料的制备方法，包括如下步骤：
    (1)将A xMF y化合物溶于氢氟酸溶液中形成饱和溶液；
    (2)将基体材料A xMF y:Mn 4+与步骤1)的饱和溶液混合，进行离子交换反应，制备得到离子交换后的无机包覆层A xMF y包覆的A xMF y:Mn 4+基体材料，记为A xMF y:Mn 4+@A xMF y；
    (3)配制有机溶液；
    (4)将步骤(2)的无机包覆层A xMF y包覆的A xMF y:Mn 4+基体材料与步骤(3)的有机溶液混合，加热搅拌直至有机溶剂蒸干，制备得到表面改性的氟化物发光材料，记为A xMF y:Mn 4+@A xMF y@有机层；
    其中，所述A选自碱金属Li、Na、K、Rb、Cs中的一种或它们之间的组合；所述M选自Ti、Si、Ge、Sn、Zr、Al、Bi、Ga、In中的一种或它们之间的组合，x为[MF y]离子的电荷的绝对值，y为4、5、6或7；Mn 4+为发光中心离子。
  7. 根据权利要求6所述的制备方法，其中，步骤(2)中，所述基体材料A xMF y:Mn 4+与步骤(1)的饱和溶液中的A xMF y化合物质量比为10:1-1:5，优选为1:1；
    优选地，步骤(2)中，所述离子交换反应是在0℃-100℃下进行，优选为在25℃-80℃下进行。
  8. 根据权利要求6或7所述的制备方法，其中，步骤(3)中，所述有机溶液为金属磷酸酯溶液、烷氧基硅烷溶液、有机羧酸类物质溶液或有机胺类物质溶液中的至少一种，上述溶液的制备方法例如为：
    将烷氧基硅烷或有机羧酸类物质或有机胺类物质溶于有机溶剂中；所述有机溶剂为甲醇、乙醇、丙醇、正己烷或环己烷中的至少一种；或者，
    将金属源、磷源与醇混合、酯化，得到金属磷酸酯溶液；其中，所述磷源选自P 2O 5或POCl 3中的一种或它们之间的组合；所述醇选自甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇中的至少一种；所述金属源为金属硝酸盐或金属硫酸盐或金属草酸盐，也可以为异丙醇盐或乙 醇盐或丙醇盐或丁醇盐等金属有机盐的一种或多种；优选地，所述金属源为Al(NO 3) 3·9H 2O、Zn(NO 3) 2·6H 2O、丁醇钛、异丙醇铝。
  9. 根据权利要求6-8任一项所述的制备方法，其中，步骤(4)中，所述加热搅拌的温度至少为30℃，优选为至少50℃；
    优选地，步骤(4)中，所述无机包覆层A xMF y包覆的A xMF y:Mn 4+基体材料与有机溶液的质量比为5:1-1:20，优选为1:1-1:5。
  10. 根据权利要求6-9任一项所述的方法，其中，步骤(2)中，所述A xMF y:Mn 4+选自A 2MF 6:Mn 4+或A 3MF 6:Mn 4+，
    所述A 2MF 6:Mn 4+选自K 2TiF 6:Mn 4+、K 2SiF 6:Mn 4+、Na 2SiF 6:Mn 4+、Na 2TiF 6:Mn 4+、K 2GeF 6:Mn 4+、Na 2SnF 6:Mn 4+、Cs 2TiF 6:Mn 4+或Cs 2SiF 6:Mn 4+；
    所述A 3MF 6:Mn 4+选自Na 3AlF 6:Mn 4+、K 3AlF 6:Mn 4+、Li 3AlF 6:Mn 4+、Rb 3AlF 6:Mn 4+、Cs 3AlF 6:Mn 4+、K 2NaAlF 6:Mn 4+、K 2LiAlF 6:Mn 4+；
    优选地，步骤(1)中，所述A xMF y选自A 2MF 6或A 3MF 6，
    所述A 2MF 6选自K 2TiF 6、K 2SiF 6、Na 2SiF 6、Na 2TiF 6、K 2GeF 6、Na 2SnF 6、Cs 2TiF 6或Cs 2SiF 6；
    所述A 3MF 6选自Na 3AlF 6、K 3AlF 6、Li 3AlF 6、Rb 3AlF 6、Cs 3AlF 6、K 2NaAlF 6、K 2LiAlF 6。
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