WO2020024317A1 - Eu3+ ion-activated phosphate-based fluorescent material, preparation therefor and use thereof - Google Patents

Eu3+ ion-activated phosphate-based fluorescent material, preparation therefor and use thereof Download PDF

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WO2020024317A1
WO2020024317A1 PCT/CN2018/099496 CN2018099496W WO2020024317A1 WO 2020024317 A1 WO2020024317 A1 WO 2020024317A1 CN 2018099496 W CN2018099496 W CN 2018099496W WO 2020024317 A1 WO2020024317 A1 WO 2020024317A1
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ion
fluorescent material
solution
based fluorescent
activated phosphate
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Chinese (zh)
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黄彦林
秦杰
刘宣宣
米龙庆
魏东磊
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苏州大学张家港工业技术研究院
苏州大学
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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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7742—Antimonates; Arsenates
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7737—Phosphates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials

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  • the invention relates to the field of inorganic light-emitting devices, in particular to a Eu 3+ ion-activated phosphate-based fluorescent material, and preparation and application thereof.
  • white light-emitting diodes have the advantages of all-solid-state, energy saving, environmental protection, long life, low operating voltage, high luminous efficiency, good shock resistance and safety, and simple light color adjustment.
  • the most important process is to coat a blue LED chip (such as InGaN) with a yellow light-emitting fluorescent material (such as YAG: Ce 3+ ) and mix it in an epoxy resin.
  • the device can obtain white light emission according to the principle of chromaticity.
  • the red-emitting fluorescent materials developed are rare earth Eu 3 + / 2 + or Ce 3+ .
  • the rare earth-doped nitride-based red fluorescent materials have excellent fluorescent properties and can also be adapted to most practical application environments.
  • the representative red-emitting fluorescent material Y 2 O 2 S: Eu 3+ is a sulfide matrix, the preparation method is complicated, the volatilization of sulfur will cause pollution, and the luminous efficiency is low.
  • red fluorescent materials play an important role in modulating the color temperature of white light and improving its color rendering properties, etc. It is very urgent to develop novel red fluorescent materials.
  • the purpose of the present invention is to provide an Eu 3+ ion-activated phosphate-based fluorescent material and its preparation and application. It has good light absorption, high luminous efficiency, and is a non-rare-earth-based red fluorescent material.
  • the present invention provides a Eu 3+ ion-activated phosphate-based fluorescent material (rare earth Eu 3+ activated SbNb 3 (PO 4 ) 6 -based fluorescent material), which has a chemical formula of Sb 1-x Eu x Nb 3 (PO 4 ) 6 , wherein 0.001 ⁇ x ⁇ 0.1, the Eu 3+ ion-activated phosphate-based fluorescent material emits red fluorescence under the excitation of near-ultraviolet light.
  • X in the formula represents the number of moles of Eu 3+ doping.
  • x 0.01-0.1.
  • Eu 3+ is a typical red light-emitting ion.
  • the light emission spectrum is derived from the transition between energy levels in the 4f sublayer. It has obvious sharp line characteristics and high luminous chromaticity.
  • the phosphate-based fluorescent material of the present invention does not contain rare earth ions. The preparation cost is low, the matrix skeleton composed of phosphate has high rigidity, good thermal stability, and high luminous efficiency.
  • the chemical formula of the Eu 3+ ion-activated phosphate-based phosphor is Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 , Sb 0.9 Eu 0.1 Nb 3 (PO 4 ) 6 , Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 , Sb 0.99 Eu 0.01 Nb 3 (PO 4 ) 6 or Sb 0.95 Eu 0.05 Nb 3 (PO 4 ) 6 .
  • the wavelength of near-ultraviolet light is 370-410 nm.
  • the wavelength of red fluorescence is 570-720 nm (preferably, the wavelength of red fluorescence is 610-620 nm).
  • the fluorescent material of the present invention emits bright red light, the strongest wavelength of light emission is about 615 nm, and the red color is pure.
  • the present invention also discloses the application of the Eu 3+ ion-activated phosphate-based fluorescent material in the preparation of a light-emitting device, and the excitation source of the light-emitting device is near-ultraviolet light.
  • the light emitting device is various illumination display or photoluminescence chromaticity adjusting device using near-ultraviolet light as an excitation light source.
  • the present invention also provides a method for preparing the Eu 3+ ion-activated phosphate-based fluorescent material, which is prepared by a wet chemical synthetic sol-gel method, and includes the following steps:
  • the amount of the complexing agent and the molar ratio of the cations (Eu 3+ , Sb 3+ , Nb 5+ or P 5+ ) in the added solution are (1.5-2.5): 1;
  • the molar ratio of the Sb 3+ ion-containing compound, the Nb 5+ ion-containing compound, the P 5+ ion-containing compound, and the Eu 3+ ion-containing compound is 0.9-0.999: 3: 6: 0.001-0.1;
  • the precursor is calcined in an air atmosphere, the calcination temperature is 800-1000 ° C, and the calcination time is 1-10 hours to obtain the Eu 3+ ion-activated phosphate-based fluorescent material.
  • the complexing agent is citric acid or oxalic acid.
  • the compound containing Sb 3+ ions is antimony trioxide (Sb 2 O 3 ) or antimony trichloride (SbCl 3 ).
  • the compound containing Eu 3+ ions is europium oxide (Eu 2 O 3 ) or europium nitrate (Eu (NO 3 ) 3 .6H 2 O).
  • the compound containing Nb 5+ ions is niobium pentoxide (Nb 2 O 5 ) or niobium chloride (NbCl 5 ).
  • the compound containing a P 5+ ion is diammonium hydrogen phosphate or ammonium dihydrogen phosphate.
  • step (2) the reaction is performed under stirring conditions, and the reaction time is 1-3 h.
  • the calcination temperature is 850-900 ° C, and the calcination time is 3-5 hours.
  • the present invention has at least the following advantages:
  • the rare earth Eu 3 + -activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention has good light absorption in the near-ultraviolet light range of 380-410 nm. Under the excitation light of the above wavelength, the fluorescent material emits Bright red light is emitted, the strongest wavelength of light is 615 nanometers, and the red color is pure.
  • the rare earth Eu 3 + -activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention is a non-rare earth-based phosphate with abundant raw material sources and low prices. It is prepared by a wet chemical sol-gel method. Easy to operate and low sintering temperature.
  • the rare earth Eu 3+ activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention the matrix skeleton composed of phosphate has high rigidity, good thermal stability, and high luminous efficiency, and is suitable for using near-ultraviolet light as an excitation source. Various lighting displays and photoluminescence chromaticity adjustments.
  • the rare earth Eu 3+ activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention is excited by near-ultraviolet light, and the emission spectrum is derived from the transition between the energy levels in the 4f sublayer, and the main wavelength is 615 nanometers. , Has obvious sharp line spectrum characteristics, high luminous chromaticity.
  • the rare earth Eu 3+ activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention is compared with other red fluorescent materials such as sulfide Y 2 O 2 S: Eu 3+ , halide and the like as host materials.
  • the preparation process of the matrix material is simple, the products are easy to collect, there is no waste gas discharge, and the environment is friendly.
  • Example 1 is an X-ray powder diffraction pattern of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention
  • Example 2 is an electron scanning electron microscope image of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention
  • Example 3 is an excitation spectrum of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention under light monitoring at 615 nm;
  • Example 4 is a light emission spectrum diagram of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention under 395 nm light excitation;
  • Example 5 is a light emission attenuation curve of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention
  • Example 7 is an electron scanning electron microscope image of Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 prepared in Example 3 of the present invention.
  • FIG. 10 is a light emission attenuation curve of Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 prepared in Example 3 of the present invention.
  • This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 .
  • antimony trichloride SbCl 3 was weighed: 2.121 g, europium nitrate Eu (NO 3 ) 3 ⁇ 6H 2 O: 0.312 g, niobium chloride NbCl 5 : 8.1 g, ammonium dihydrogen phosphate NH 4 H 2 PO 4 : 6.9 g.
  • the above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
  • the weighed niobium chloride NbCl 5 is dissolved in a hydrofluoric acid solution, heated in a water bath at 80 ° C., and continuously stirred until completely dissolved, and then 6.75 g of a complexing agent, oxalic acid, is added and stirred at 90 ° C. to obtain a transparent solution. Recorded as B solution.
  • solution C a transparent solution, which is referred to as solution C.
  • the obtained A, B, and C solutions were slowly mixed, stirred at a temperature condition of 95 ° C. for 1 hour, and then left to stand and dried to obtain a fluffy precursor.
  • the obtained precursor was calcined in an air atmosphere, and the calcination temperature was 1000 ° C., the calcination time was 1 hour, and the mixture was naturally cooled to room temperature to obtain Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 red phosphor.
  • FIG. 1 is an X-ray powder diffraction pattern of the above product.
  • the XRD test results show that the prepared material is a pure phase substance and has no heterogeneous phase.
  • FIG. 2 is a SEM image of the above product.
  • FIG. 2 shows that the material has good crystallization performance, uniform particle size, and a size of about 100 nm.
  • FIG. 3 is an excitation spectrum obtained by monitoring the emitted light of the above product at 615 nanometers. It can be seen that the excitation source of red light emission is mainly 395 nanometers, so the phosphor can be used to prepare near-ultraviolet excited fluorescent lamps.
  • Fig. 4 is a luminescence spectrum obtained by exciting the above product with near-ultraviolet light at 395 nanometers. It can be seen from the figure that the main central luminescence wavelength of the material is in the red luminescence band of 615 nanometers.
  • Fig. 5 is the luminescence decay curve of the above product at 615 nanometers. It can be seen from the figure that the decay time of the material is 1.37 milliseconds.
  • This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.9 Eu 0.1 Nb 3 (PO 4 ) 6 .
  • antimony trioxide Sb 2 O 3 1.312 g
  • samarium Eu 2 O 3 0.176 g
  • niobium oxide Nb 2 O 5 3.987 g
  • Diammonium hydrogen phosphate (NH 4 ) 2 HPO 4 7.92 g.
  • the above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
  • solution C Dissolve 7.92 grams of the weighed diammonium hydrogen phosphate reagent in dilute nitric acid, add 17 grams of citric acid, and stir at 60 ° C to obtain a transparent solution, which is referred to as solution C.
  • the obtained A, B, and C solutions were slowly mixed, stirred at a temperature of 60 ° C. for 3 hours, and then allowed to stand and then dried to obtain a fluffy precursor.
  • the obtained precursor was calcined in an air atmosphere at a temperature of 800 ° C. for a period of 10 hours, and was naturally cooled to room temperature to obtain Sb 0.9 Eu 0.1 Nb 3 (PO 4 ) 6 red phosphor. Its structure test, surface morphology, excitation spectrum, luminescence spectrum and attenuation curve are similar to those of Example 1.
  • This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 .
  • antimony trichloride SbCl 3 was weighed: 1.77 g, europium nitrate Eu (NO 3 ) 3 ⁇ 6H 2 O: 0.107 g, and niobium chloride NbCl 5 : 6.484 g, ammonium dihydrogen phosphate NH 4 H 2 PO 4 : 5.521 g.
  • the above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
  • Dissolve antimony trichloride and thorium nitrate in a dilute nitric acid solution and continue to stir vigorously until a transparent solution is obtained after complete dissolution.
  • Weigh 1.45 g of oxalic acid into the transparent solution stir it at 80 ° C, and record it as solution A.
  • the weighed niobium chloride NbCl 5 is dissolved in a hydrofluoric acid solution, heated in a water bath at 75 ° C., and continuously stirred until completely dissolved, and then 4.32 g of a complexing agent, oxalic acid, is added and stirred at 85 ° C. to obtain a transparent solution. Recorded as B solution.
  • solution C The obtained ammonium dihydrogen phosphate NH 4 H 2 PO 4 reagent was dissolved in dilute nitric acid, 8.6 g of oxalic acid was added, and the solution was stirred at 75 ° C. to obtain a transparent solution, which is referred to as solution C.
  • the obtained A, B, and C solutions were slowly mixed, stirred at a temperature of 90 ° C. for 2 hours, and then allowed to stand and then dried to obtain a fluffy precursor.
  • the obtained precursor was calcined in an air atmosphere at a temperature of 850 ° C. for a period of 3 hours and naturally cooled to room temperature to obtain Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 red phosphor.
  • FIG. 6 is an X-ray powder diffraction pattern of the above product.
  • the XRD test results show that the prepared material is a pure phase substance without a heterogeneous phase.
  • FIG. 7 is a SEM image of the above product, and FIG. 2 shows that the material has good crystallization performance, uniform particle size, and a size between 100-150 nm.
  • FIG. 8 is an excitation spectrum chart of the above product under the monitored emission light of 615 nanometers. It can be seen that the excitation source of red light emission is mainly 395 nanometers, so the phosphor can be used to prepare near-ultraviolet excited fluorescent lamps.
  • FIG. 10 is a luminescence decay curve of the above product at 615 nanometers. It can be seen from the figure that the decay time of the material is 1.6 ms.
  • This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.99 Eu 0.01 Nb 3 (PO 4 ) 6 .
  • antimony trichloride SbCl 3 was weighed: 2.26 g, europium nitrate Eu (NO 3 ) 3 ⁇ 6H 2 O: 0.05 g, niobium chloride NbCl 5 : 8.1 g, ammonium dihydrogen phosphate NH 4 H 2 PO 4 : 6.9 g.
  • the above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
  • the weighed niobium chloride NbCl 5 is dissolved in a hydrofluoric acid solution, heated in a water bath at 70 ° C., and continuously stirred until completely dissolved, and then 5.4 g of a complexing agent, oxalic acid, is added and stirred at 80 ° C. to obtain a transparent solution. Recorded as B solution.
  • solution C The obtained ammonium dihydrogen phosphate NH 4 H 2 PO 4 reagent was dissolved in dilute nitric acid, 10.8 g of oxalic acid was added, and the solution was stirred at 70 ° C. to obtain a transparent solution, which is referred to as solution C.
  • the obtained A, B, and C solutions were slowly mixed, stirred at a temperature of 80 ° C. for 2 hours, and then allowed to stand and then dried to obtain a fluffy precursor.
  • the obtained precursor was calcined in an air atmosphere at a temperature of 900 ° C. for a period of 3 hours, and was naturally cooled to room temperature to obtain Sb 0.99 Eu 0.01 Nb 3 (PO 4 ) 6 red phosphor. Its excitation spectrum, emission spectrum and attenuation curve are similar to those of the third embodiment.
  • This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.95 Eu 0.05 Nb 3 (PO 4 ) 6 .
  • antimony trichloride SbCl 3 1.3 g
  • niobium chloride NbCl 5 4.86 g
  • ammonium dihydrogen phosphate NH 4 H 2 PO 4 4.14 g.
  • the above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
  • Dissolve the weighed niobium chloride NbCl 5 in the hydrofluoric acid solution heat it in a water bath at 80 ° C, continue to stir until completely dissolved, and then add 4.05 g of the complexing agent oxalic acid. Stir at 80 ° C to obtain a transparent solution, which is referred to as solution B.
  • the obtained A, B, and C solutions were slowly mixed, stirred at a temperature of 90 ° C. for 3 hours, and then allowed to stand and then dried to obtain a fluffy precursor.
  • the obtained precursor was calcined in an air atmosphere at a temperature of 860 ° C. for a period of 4 hours, and was naturally cooled to room temperature to obtain Sb 0.95 Eu 0.05 Nb 3 (PO 4 ) 6 red phosphor. Its excitation spectrum, emission spectrum and attenuation curve are similar to those of the third embodiment.

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Abstract

The present invention relates to an Eu3+ ion-activated phosphate-based fluorescent material with a chemical formula of Sb1-xEuxNb3(PO4)6, with 0.001≤x≤0.1, wherein the Eu3+ ion-activated phosphate-based fluorescent material emits red fluorescent light under near ultraviolet light excitation. The fluorescent material of the present invention is prepared by using a wet chemical sol-gel method. Same has rich raw material sources, a simple process, and a low sintering temperature. The fluorescent material of the present invention has a very good absorption of light in the near ultraviolet light region, a good heat stability and a high light-emitting efficiency, and is suitable for various lighting displays and photoluminescence chrominance adjustments in which near ultraviolet light is involved as the excitation source.

Description

Eu 3+离子激活的磷酸盐基荧光材料及其制备和应用 Eu       3+ ion-activated phosphate-based fluorescent material and preparation and application thereof      技术领域Technical field
本发明涉及无机发光器件领域，尤其涉及一种Eu 3+离子激活的磷酸盐基荧光材料及其制备和应用。 The invention relates to the field of inorganic light-emitting devices, in particular to a Eu 3+ ion-activated phosphate-based fluorescent material, and preparation and application thereof.
背景技术Background technique
在当今照明产业的发展之中，基于白光LED的半导体固态照明技术及其应用得到了快速的发展，已引起全球范围内的关注和研发热潮。与传统照明光源比，白发光二极管具有全固态、节能、环保、长寿命、工作电压低、发光效率高、抗震性及安全性好、光色调节简便等优点。目前商用白光LED制备技术中，最重要的工艺是将蓝光LED芯片(如InGaN)涂覆上黄发光荧光材料(如YAG:Ce 3+)并混合于环氧树脂中，封装在一起制成发光器件，根据色度学原理，可以得到白光发射。 In the development of today's lighting industry, semiconductor solid-state lighting technology and its applications based on white LEDs have developed rapidly, which has caused worldwide attention and a boom in research and development. Compared with traditional lighting sources, white light-emitting diodes have the advantages of all-solid-state, energy saving, environmental protection, long life, low operating voltage, high luminous efficiency, good shock resistance and safety, and simple light color adjustment. At present, in commercial white LED manufacturing technology, the most important process is to coat a blue LED chip (such as InGaN) with a yellow light-emitting fluorescent material (such as YAG: Ce 3+ ) and mix it in an epoxy resin. The device can obtain white light emission according to the principle of chromaticity.
但是，在实际的照明中，这种LED照明技术并不能满足人们的需要，主要的原因是，商用的黄色荧光材料YAG:Ce 3+缺少必要的红发光成分，从而导致最终的白发光色温偏高(>7000K)，显色指数偏低(<70)。因此，为了弥补这些不足之处，最有效的方法就是匹配一种合适的红发光荧光材料，从而弥补YAG:Ce 3+黄发光荧光材料缺失的红光部分。 However, in actual lighting, this LED lighting technology cannot meet people's needs. The main reason is that the commercial yellow fluorescent material YAG: Ce 3+ lacks the necessary red light-emitting component, resulting in a high white light color temperature. (> 7000K) and low color rendering index (<70). Therefore, in order to make up for these shortcomings, the most effective method is to match a suitable red-emitting fluorescent material, so as to make up for the missing red light portion of YAG: Ce 3+ yellow-emitting fluorescent material.
目前开发的红发光荧光材料，激活离子多为稀土Eu 3+/2+或Ce 3+。在这些荧光材料中，稀土掺杂的氮化物基红色荧光材料具有优异的荧光性能，也能适应多数实际应用环境。但是，除了由于4f-5d跃迁带来的绿光和黄光波段的再吸收缺陷，合成温度很高、需要高压环境和严苛的合成工艺等致使该荧光材料无法进行大规模商用。代表的红发光荧光材料Y 2O 2S:Eu 3+为硫化物基质，制备方法复杂，硫的挥发也会造成污染，发光效率低。另外，一些基质材料，例如钨酸盐、钼酸盐、硫化物、氮化物、钨钼酸盐等，还具有光吸收率低的缺点，不能满足高性能器件的需要。基于此，红色荧光材料在调制白光的色温及改善其显色性等方面起着重要作用，开发新颖的红色荧光材料十分紧迫。 Currently, most of the red-emitting fluorescent materials developed are rare earth Eu 3 + / 2 + or Ce 3+ . Among these fluorescent materials, the rare earth-doped nitride-based red fluorescent materials have excellent fluorescent properties and can also be adapted to most practical application environments. However, in addition to the reabsorption defects in the green and yellow light bands caused by the 4f-5d transition, the high synthesis temperature, the need for a high-pressure environment, and the severe synthesis process make the fluorescent material unavailable for large-scale commercial use. The representative red-emitting fluorescent material Y 2 O 2 S: Eu 3+ is a sulfide matrix, the preparation method is complicated, the volatilization of sulfur will cause pollution, and the luminous efficiency is low. In addition, some host materials, such as tungstate, molybdate, sulfide, nitride, and tungsten molybdate, also have the disadvantage of low light absorption and cannot meet the needs of high-performance devices. Based on this, red fluorescent materials play an important role in modulating the color temperature of white light and improving its color rendering properties, etc. It is very urgent to develop novel red fluorescent materials.
发明内容Summary of the invention
为克服现有技术中商用红色荧光材料稳定性差、光吸收效率低的不足，本发明的目的是提供一种Eu 3+离子激活的磷酸盐基荧光材料及其制备和应用，该材料对近紫外光吸收好、发光效率高，且为非稀土基质的红色荧光材料。 In order to overcome the problems of poor stability and low light absorption efficiency of commercial red fluorescent materials in the prior art, the purpose of the present invention is to provide an Eu 3+ ion-activated phosphate-based fluorescent material and its preparation and application. It has good light absorption, high luminous efficiency, and is a non-rare-earth-based red fluorescent material.
在一方面，本发明提供了一种Eu 3+离子激活的磷酸盐基荧光材料(稀土Eu 3+激活的SbNb 3(PO 4) 6基荧光材料)，其化学式为Sb 1-xEu xNb 3(PO 4) 6，其中0.001≤x≤0.1，所述Eu 3+离子激活的磷酸盐基荧光材料在近紫外光的激发下发出红色荧光。式中的x表示Eu 3+掺杂的摩尔数。优选地，x＝0.01-0.1。 In one aspect, the present invention provides a Eu 3+ ion-activated phosphate-based fluorescent material (rare earth Eu 3+ activated SbNb 3 (PO 4 ) 6 -based fluorescent material), which has a chemical formula of Sb 1-x Eu x Nb 3 (PO 4 ) 6 , wherein 0.001 ≦ x ≦ 0.1, the Eu 3+ ion-activated phosphate-based fluorescent material emits red fluorescence under the excitation of near-ultraviolet light. X in the formula represents the number of moles of Eu 3+ doping. Preferably, x = 0.01-0.1.
Eu 3+是典型的红发光离子，发光光谱是来自于4f亚层中能级之间跃迁，具有明显的锐线谱特征，发光色度高，本发明的磷酸盐基荧光材料不含稀土离子，制备成本低，磷酸盐组成的基质骨架具有很高的刚性，热稳定好，发光效率高。 Eu 3+ is a typical red light-emitting ion. The light emission spectrum is derived from the transition between energy levels in the 4f sublayer. It has obvious sharp line characteristics and high luminous chromaticity. The phosphate-based fluorescent material of the present invention does not contain rare earth ions. The preparation cost is low, the matrix skeleton composed of phosphate has high rigidity, good thermal stability, and high luminous efficiency.
优选地，Eu 3+离子激活的磷酸盐基荧光材料的化学式为Sb 0.93Eu 0.07Nb 3(PO 4) 6、Sb 0.9Eu 0.1Nb 3(PO 4) 6、Sb 0.97Eu 0.03Nb 3(PO 4) 6、Sb 0.99Eu 0.01Nb 3(PO 4) 6或Sb 0.95Eu 0.05Nb 3(PO 4) 6。 Preferably, the chemical formula of the Eu 3+ ion-activated phosphate-based phosphor is Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 , Sb 0.9 Eu 0.1 Nb 3 (PO 4 ) 6 , Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 , Sb 0.99 Eu 0.01 Nb 3 (PO 4 ) 6 or Sb 0.95 Eu 0.05 Nb 3 (PO 4 ) 6 .
进一步地，近紫外光的波长为370-410nm。Further, the wavelength of near-ultraviolet light is 370-410 nm.
进一步地，红色荧光的波长为570-720nm(优选地，红色荧光的波长为610-620nm)。本发明的荧光材料在近紫外光激发下，发出明亮的红光，发光的最强波长在615nm左右，红色色度纯正。Further, the wavelength of red fluorescence is 570-720 nm (preferably, the wavelength of red fluorescence is 610-620 nm). Under the excitation of near-ultraviolet light, the fluorescent material of the present invention emits bright red light, the strongest wavelength of light emission is about 615 nm, and the red color is pure.
在另一方面，本发明还公开了上述Eu 3+离子激活的磷酸盐基荧光材料在制备发光器件中的应用，所述发光器件的激发源为近紫外光。 In another aspect, the present invention also discloses the application of the Eu 3+ ion-activated phosphate-based fluorescent material in the preparation of a light-emitting device, and the excitation source of the light-emitting device is near-ultraviolet light.
进一步地，发光器件为以近紫外光为激发光源的各种照明显示或光致发光色度调节器件。Further, the light emitting device is various illumination display or photoluminescence chromaticity adjusting device using near-ultraviolet light as an excitation light source.
在又一方面，本发明还提供了一种上述Eu 3+离子激活的磷酸盐基荧光材料的制备方法，采用湿化学合成溶胶凝胶法制备，包括以下步骤： In another aspect, the present invention also provides a method for preparing the Eu 3+ ion-activated phosphate-based fluorescent material, which is prepared by a wet chemical synthetic sol-gel method, and includes the following steps:
(1)将含有Sb 3+离子的化合物和含有Eu 3+离子的化合物溶于稀硝酸中，在络合剂的存在下在60-90℃下混匀，得到A溶液；将含有Nb 5+离子的化合物溶于氢氟酸，然后在60-90℃下与所述络合剂混匀，得到B溶液；将含有P 5+离子的化合物溶于稀硝酸中，然后在60-80℃下与所述络合剂混匀，得到C溶液； (1) Dissolve the compound containing Sb 3+ ions and the compound containing Eu 3+ ions in dilute nitric acid, mix in the presence of a complexing agent at 60-90 ° C to obtain A solution; and include Nb 5+ The ionic compound is dissolved in hydrofluoric acid, and then mixed with the complexing agent at 60-90 ° C to obtain a solution B; the compound containing P 5+ ions is dissolved in dilute nitric acid, and then at 60-80 ° C Mix with the complexing agent to obtain a C solution;
其中，络合剂的用量和所加入溶液之中阳离子(Eu 3+，Sb 3+，Nb 5+或P 5+)的摩尔比为(1.5-2.5):1； Wherein, the amount of the complexing agent and the molar ratio of the cations (Eu 3+ , Sb 3+ , Nb 5+ or P 5+ ) in the added solution are (1.5-2.5): 1;
所述含有Sb 3+离子的化合物、含有Nb 5+离子的化合物、含有P 5+离子的化合物、含有Eu 3+离子的化合物的摩尔比为0.9-0.999:3:6:0.001-0.1； The molar ratio of the Sb 3+ ion-containing compound, the Nb 5+ ion-containing compound, the P 5+ ion-containing compound, and the Eu 3+ ion-containing compound is 0.9-0.999: 3: 6: 0.001-0.1;
(2)将所述A溶液、B溶液和C溶液混匀后在60-95℃下反应，反应完全后干燥产物，得到前驱体；(2) the A solution, the B solution and the C solution are mixed and reacted at 60-95 ° C; after the reaction is completed, the product is dried to obtain a precursor;
(3)将所述前驱体在空气气氛中煅烧，煅烧温度为800-1000℃，煅烧时间为1-10小时，得到所述Eu 3+离子激活的磷酸盐基荧光材料。 (3) The precursor is calcined in an air atmosphere, the calcination temperature is 800-1000 ° C, and the calcination time is 1-10 hours to obtain the Eu 3+ ion-activated phosphate-based fluorescent material.
进一步地，在步骤(1)中，络合剂为柠檬酸或草酸。Further, in step (1), the complexing agent is citric acid or oxalic acid.
进一步地，在步骤(1)中，含有Sb 3+离子的化合物为三氧化二锑(Sb 2O 3)或三氯化锑(SbCl 3)。 Further, in step (1), the compound containing Sb 3+ ions is antimony trioxide (Sb 2 O 3 ) or antimony trichloride (SbCl 3 ).
进一步地，在步骤(1)中，含有Eu 3+离子的化合物为氧化铕(Eu 2O 3)或硝酸铕(Eu(NO 3) 3·6H 2O)。 Further, in step (1), the compound containing Eu 3+ ions is europium oxide (Eu 2 O 3 ) or europium nitrate (Eu (NO 3 ) 3 .6H 2 O).
进一步地，在步骤(1)中，所述含有Nb 5+离子的化合物为五氧化二铌(Nb 2O 5)或氯化铌(NbCl 5)。 Further, in step (1), the compound containing Nb 5+ ions is niobium pentoxide (Nb 2 O 5 ) or niobium chloride (NbCl 5 ).
进一步地，在步骤(1)中，所述含有P 5+离子的化合物为磷酸氢二铵或磷酸二氢铵。 Further, in step (1), the compound containing a P 5+ ion is diammonium hydrogen phosphate or ammonium dihydrogen phosphate.
进一步地，在步骤(2)中，在搅拌条件下反应，反应时间为1-3h。Further, in step (2), the reaction is performed under stirring conditions, and the reaction time is 1-3 h.
优选地，在步骤(3)中，煅烧温度为850-900℃，煅烧时间为3-5小时。Preferably, in step (3), the calcination temperature is 850-900 ° C, and the calcination time is 3-5 hours.
借由上述方案，本发明至少具有以下优点：With the above solution, the present invention has at least the following advantages:
1、本发明的稀土Eu 3+激活的SbNb 3(PO 4) 6基荧光材料，在380-410纳米近紫外光区间有很好的光吸收，在上述波长的激发光下，该荧光材料发射出明亮的红光，发光的最强波长在615纳米，红色色度纯正。 1. The rare earth Eu 3 + -activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention has good light absorption in the near-ultraviolet light range of 380-410 nm. Under the excitation light of the above wavelength, the fluorescent material emits Bright red light is emitted, the strongest wavelength of light is 615 nanometers, and the red color is pure.
2、本发明的稀土Eu 3+激活的SbNb 3(PO 4) 6基荧光材料，是一种非稀土基质的磷酸盐，原料来源丰富，价格低，采用湿化学溶胶凝胶法制备，制备工艺易操作，烧结温度低。 2. The rare earth Eu 3 + -activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention is a non-rare earth-based phosphate with abundant raw material sources and low prices. It is prepared by a wet chemical sol-gel method. Easy to operate and low sintering temperature.
3、本发明的稀土Eu 3+激活的SbNb 3(PO 4) 6基荧光材料，磷酸盐组成的基质骨架具有很高的刚性，热稳定好，发光效率高，适合于以近紫外光为激发源的各种照明显示和光致发光色度调节。 3. The rare earth Eu 3+ activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention, the matrix skeleton composed of phosphate has high rigidity, good thermal stability, and high luminous efficiency, and is suitable for using near-ultraviolet light as an excitation source. Various lighting displays and photoluminescence chromaticity adjustments.
4、本发明的稀土Eu 3+激活的SbNb 3(PO 4) 6基荧光材料，在近紫外光的激发下，发光光谱是来自于4f亚层中能级之间跃迁，主波长为615纳米，具有明显的锐线谱特征，发光色度高。 4. The rare earth Eu 3+ activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention is excited by near-ultraviolet light, and the emission spectrum is derived from the transition between the energy levels in the 4f sublayer, and the main wavelength is 615 nanometers. , Has obvious sharp line spectrum characteristics, high luminous chromaticity.
5、本发明的稀土Eu 3+激活的SbNb 3(PO 4) 6基荧光材料与其它硫化物Y 2O 2S:Eu 3+、卤化物等为基质材料的红色荧光材料相比，本发明基质材料的制备过程简单，产物易收集，无废水废气排放，环境友好。 5. The rare earth Eu 3+ activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention is compared with other red fluorescent materials such as sulfide Y 2 O 2 S: Eu 3+ , halide and the like as host materials. The preparation process of the matrix material is simple, the products are easy to collect, there is no waste gas discharge, and the environment is friendly.
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。The above description is only an overview of the technical solutions of the present invention. In order to understand the technical means of the present invention more clearly and can be implemented according to the contents of the description, the following describes in detail the preferred embodiments of the present invention and the accompanying drawings.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是本发明实施例1所制备的Sb 0.93Eu 0.07Nb 3(PO 4) 6的X射线粉末衍射图谱； 1 is an X-ray powder diffraction pattern of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention;
图2是本发明实施例1所制备的Sb 0.93Eu 0.07Nb 3(PO 4) 6的电子扫描电镜图； 2 is an electron scanning electron microscope image of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention;
图3是本发明实施例1所制备的Sb 0.93Eu 0.07Nb 3(PO 4) 6在615nm光监测下的激发光谱图； 3 is an excitation spectrum of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention under light monitoring at 615 nm;
图4是本发明实施例1所制备的Sb 0.93Eu 0.07Nb 3(PO 4) 6在395nm光激发下的发光光谱图； 4 is a light emission spectrum diagram of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention under 395 nm light excitation;
图5是本发明实施例1所制备的Sb 0.93Eu 0.07Nb 3(PO 4) 6的发光衰减曲线； 5 is a light emission attenuation curve of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention;
图6是本发明实施例3所制备的Sb 0.97Eu 0.03Nb 3(PO 4) 6的X射线粉末衍射图谱； 6 is an X-ray powder diffraction pattern of Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 prepared in Example 3 of the present invention;
图7是本发明实施例3所制备的Sb 0.97Eu 0.03Nb 3(PO 4) 6的电子扫描电镜图； 7 is an electron scanning electron microscope image of Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 prepared in Example 3 of the present invention;
图8是本发明实施例3所制备的Sb 0.97Eu 0.03Nb 3(PO 4) 6在615nm光监测下的激发光谱图； 8 is an excitation spectrum of Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 prepared in Example 3 of the present invention under 615 nm light monitoring;
图9是本发明实施例3所制备的Sb 0.97Eu 0.03Nb 3(PO 4) 6在395nm光激发下的发光光谱图； 9 is a light emission spectrum diagram of Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 prepared in Example 3 of the present invention under 395 nm light excitation;
图10是本发明实施例3所制备的Sb 0.97Eu 0.03Nb 3(PO 4) 6的发光衰减曲线。 FIG. 10 is a light emission attenuation curve of Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 prepared in Example 3 of the present invention.
具体实施方式detailed description
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. The following examples are used to illustrate the present invention, but not to limit the scope of the present invention.
实施例1：Example 1:
本实施例提供了一种Eu 3+离子激活的磷酸盐基荧光粉，其化学式为Sb 0.93Eu 0.07Nb 3(PO 4) 6。根据化学式中Sb、Eu、Nb和P元素的化学计量比，分别称取三氯化锑SbCl 3：2.121克，硝酸铕Eu(NO 3) 3·6H 2O：0.312克，氯化铌NbCl 5：8.1克，磷酸二氢铵NH 4H 2PO 4：6.9克。按照以下方法制备上述Eu 3+离子激活的磷酸盐基荧光粉： This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 . According to the stoichiometric ratios of the elements Sb, Eu, Nb and P in the chemical formula, antimony trichloride SbCl 3 was weighed: 2.121 g, europium nitrate Eu (NO 3 ) 3 · 6H 2 O: 0.312 g, niobium chloride NbCl 5 : 8.1 g, ammonium dihydrogen phosphate NH 4 H 2 PO 4 : 6.9 g. The above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
将三氯化锑和硝酸铕溶解于稀硝酸溶液中，不断强烈搅拌，直至完全溶解后得到透明的溶液，然后称取2.25克草酸加入该透明溶液，于90℃下搅拌，记作A溶液。将称取的氯化铌NbCl 5溶解于氢氟酸溶液中，在80℃下水浴加热，不断搅拌至完全溶解，再加入6.75克的络合剂草酸，在90℃下搅拌，得到透明溶液，记作B溶液。将称取的磷酸二氢铵NH 4H 2PO 4试剂6.9克溶于稀硝酸中，再加入13.5克的草酸，80℃下搅拌得到透明溶液，记作C溶液。将得到的A、B、C溶液缓慢混合，在95℃的温度条件下搅拌1小时后，静置后烘干，得到蓬松的前驱体。将得到的前驱体在空气气氛中煅烧，煅烧温度为1000℃，煅烧时间为1小时，自然冷却到室温，得到Sb 0.93Eu 0.07Nb 3(PO 4) 6红色荧光粉。 Dissolve antimony trichloride and thorium nitrate in a dilute nitric acid solution and continue to stir vigorously until a transparent solution is obtained after complete dissolution. Then, weigh 2.25 grams of oxalic acid into the transparent solution, stir at 90 ° C, and record it as solution A. The weighed niobium chloride NbCl 5 is dissolved in a hydrofluoric acid solution, heated in a water bath at 80 ° C., and continuously stirred until completely dissolved, and then 6.75 g of a complexing agent, oxalic acid, is added and stirred at 90 ° C. to obtain a transparent solution. Recorded as B solution. 6.9 g of the weighed ammonium dihydrogen phosphate NH 4 H 2 PO 4 reagent was dissolved in dilute nitric acid, then 13.5 g of oxalic acid was added, and the solution was stirred at 80 ° C. to obtain a transparent solution, which is referred to as solution C. The obtained A, B, and C solutions were slowly mixed, stirred at a temperature condition of 95 ° C. for 1 hour, and then left to stand and dried to obtain a fluffy precursor. The obtained precursor was calcined in an air atmosphere, and the calcination temperature was 1000 ° C., the calcination time was 1 hour, and the mixture was naturally cooled to room temperature to obtain Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 red phosphor.
图1是上述产物的X射线粉末衍射图谱，XRD测试结果表明，所制备的材料为纯相物质，没有杂相。FIG. 1 is an X-ray powder diffraction pattern of the above product. The XRD test results show that the prepared material is a pure phase substance and has no heterogeneous phase.
图2是上述产物的SEM图，图2表明，该材料结晶性能良好，粒径均匀，尺寸在100纳米左右。FIG. 2 is a SEM image of the above product. FIG. 2 shows that the material has good crystallization performance, uniform particle size, and a size of about 100 nm.
图3是上述产物在监测发射光615纳米下得到的激发光谱图，从中可以看出，红色发光的激发来源主要为395纳米，因此该荧光粉可用于制备近紫外光激发荧光灯。FIG. 3 is an excitation spectrum obtained by monitoring the emitted light of the above product at 615 nanometers. It can be seen that the excitation source of red light emission is mainly 395 nanometers, so the phosphor can be used to prepare near-ultraviolet excited fluorescent lamps.
图4是上述产物以近紫外光395纳米激发得到的发光光谱图，从图中可看出，该材料主要的中心发光波长在615纳米的红色发光波段，计算其色度为x＝0.66，y＝0.32。其中，x表示红原色的比例，y表示绿原色的比例。Fig. 4 is a luminescence spectrum obtained by exciting the above product with near-ultraviolet light at 395 nanometers. It can be seen from the figure that the main central luminescence wavelength of the material is in the red luminescence band of 615 nanometers. The calculated chromaticity is x = 0.66, y = 0.32. Among them, x represents the ratio of red primary colors, and y represents the ratio of green primary colors.
图5是上述产物615纳米的发光衰减曲线，从图中可看出，该材料衰减时间为1.37毫秒。Fig. 5 is the luminescence decay curve of the above product at 615 nanometers. It can be seen from the figure that the decay time of the material is 1.37 milliseconds.
实施例2：Example 2:
本实施例提供了一种Eu 3+离子激活的磷酸盐基荧光粉，其化学式为Sb 0.9Eu 0.1Nb 3(PO 4) 6。根据化学式中Sb、Eu、Nb和P元素的化学计量比，分别称取三氧化锑Sb 2O 3：1.312克，氧化铕Eu 2O 3：0.176克，氧化铌Nb 2O 5：3.987克，磷酸氢二铵(NH 4) 2HPO 4：7.92克。按照以下方法制备上述Eu 3+离子激活的磷酸盐基荧光粉： This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.9 Eu 0.1 Nb 3 (PO 4 ) 6 . According to the stoichiometric ratios of the elements Sb, Eu, Nb and P in the chemical formula, antimony trioxide Sb 2 O 3 : 1.312 g, samarium Eu 2 O 3 : 0.176 g, niobium oxide Nb 2 O 5 : 3.987 g, Diammonium hydrogen phosphate (NH 4 ) 2 HPO 4 : 7.92 g. The above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
将氧化锑和氧化铕溶解于稀硝酸溶液中，不断强烈搅拌，直至完全溶解后得到透明的溶液，称取2.878克柠檬酸加入该透明溶液，于60℃下搅拌，记作A溶液。将称取的氧化铌溶解于氢氟酸溶液中，在60℃下水浴加热，不断搅拌至完全溶解，再加入8.64克的络合剂柠檬酸，在60℃下搅拌，得到透明溶液，记作B溶液。将称取的磷酸氢二铵试剂7.92克溶于稀硝酸中，再加入17克的柠檬酸，60℃下搅拌得到透明溶液，记作C溶液。将得到的A、B、C溶液缓慢混合，在60℃的温度条件下搅拌3小时后，静置后烘干，得到蓬松的前驱体。将得到的前驱体在空气气氛中煅烧，温度为800℃，时间为10小时，自然冷却到室温，得到Sb 0.9Eu 0.1Nb 3(PO 4) 6红色荧光粉。其结构测试、表面形貌、激发光谱、发光光谱和衰减曲线与实施例1相似。 Dissolve antimony oxide and thorium oxide in a dilute nitric acid solution and continue to stir vigorously until a transparent solution is obtained after complete dissolution. Weigh 2.878 grams of citric acid into the transparent solution, stir it at 60 ° C, and record it as solution A. The weighed niobium oxide was dissolved in a hydrofluoric acid solution, heated in a water bath at 60 ° C, and continuously stirred until completely dissolved. Then, 8.64 g of a complexing agent, citric acid, was added, and the mixture was stirred at 60 ° C to obtain a transparent solution. B solution. Dissolve 7.92 grams of the weighed diammonium hydrogen phosphate reagent in dilute nitric acid, add 17 grams of citric acid, and stir at 60 ° C to obtain a transparent solution, which is referred to as solution C. The obtained A, B, and C solutions were slowly mixed, stirred at a temperature of 60 ° C. for 3 hours, and then allowed to stand and then dried to obtain a fluffy precursor. The obtained precursor was calcined in an air atmosphere at a temperature of 800 ° C. for a period of 10 hours, and was naturally cooled to room temperature to obtain Sb 0.9 Eu 0.1 Nb 3 (PO 4 ) 6 red phosphor. Its structure test, surface morphology, excitation spectrum, luminescence spectrum and attenuation curve are similar to those of Example 1.
实施例3：Example 3:
本实施例提供了一种Eu 3+离子激活的磷酸盐基荧光粉，其化学式为Sb 0.97Eu 0.03Nb 3(PO 4) 6。根据化学式中Sb、Eu、Nb和P元素的化学计量比，分别称取三氯化锑SbCl 3：1.77克，硝酸铕Eu(NO 3) 3·6H 2O：0.107克，氯化铌NbCl 5：6.484克，磷酸二氢铵NH 4H 2PO 4：5.521克。按照以下方法制备上述Eu 3+离子激活的磷酸盐基荧光粉： This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 . According to the stoichiometric ratios of the elements Sb, Eu, Nb and P in the chemical formula, antimony trichloride SbCl 3 was weighed: 1.77 g, europium nitrate Eu (NO 3 ) 3 · 6H 2 O: 0.107 g, and niobium chloride NbCl 5 : 6.484 g, ammonium dihydrogen phosphate NH 4 H 2 PO 4 : 5.521 g. The above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
将三氯化锑和硝酸铕溶解于稀硝酸溶液中，不断强烈搅拌，直至完全溶解后得到透明的溶液，称取1.45克草酸加入该透明溶液，于80℃下搅拌，记作A溶液。将称取的氯化铌NbCl 5溶解于氢氟酸溶液中，在75℃下水浴加热，不断搅拌至完全溶解，再加入4.32克的络合剂草酸，在85℃下搅拌，得到透明溶液，记作B溶液。将称取的磷酸二氢铵NH 4H 2PO 4试剂溶于稀硝酸中，再加入8.6克的草酸，75℃下搅拌得到透明溶液，记作C溶液。将得到的A、B、C溶液缓慢混合，在90℃的温度条件下搅拌2小时后，静置后烘干，得到蓬松的前驱体。将得到的前驱体在空气气氛中煅烧，温度为850℃，时间为3小时，自然冷却到室温，得到 Sb 0.97Eu 0.03Nb 3(PO 4) 6红色荧光粉。 Dissolve antimony trichloride and thorium nitrate in a dilute nitric acid solution, and continue to stir vigorously until a transparent solution is obtained after complete dissolution. Weigh 1.45 g of oxalic acid into the transparent solution, stir it at 80 ° C, and record it as solution A. The weighed niobium chloride NbCl 5 is dissolved in a hydrofluoric acid solution, heated in a water bath at 75 ° C., and continuously stirred until completely dissolved, and then 4.32 g of a complexing agent, oxalic acid, is added and stirred at 85 ° C. to obtain a transparent solution. Recorded as B solution. The weighed ammonium dihydrogen phosphate NH 4 H 2 PO 4 reagent was dissolved in dilute nitric acid, 8.6 g of oxalic acid was added, and the solution was stirred at 75 ° C. to obtain a transparent solution, which is referred to as solution C. The obtained A, B, and C solutions were slowly mixed, stirred at a temperature of 90 ° C. for 2 hours, and then allowed to stand and then dried to obtain a fluffy precursor. The obtained precursor was calcined in an air atmosphere at a temperature of 850 ° C. for a period of 3 hours and naturally cooled to room temperature to obtain Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 red phosphor.
图6是上述产物的X射线粉末衍射图谱，XRD测试结果表明，所制备的材料为纯相物质，没有杂相。FIG. 6 is an X-ray powder diffraction pattern of the above product. The XRD test results show that the prepared material is a pure phase substance without a heterogeneous phase.
图7是上述产物的SEM图，图2表明，该材料结晶性能良好，粒径均匀，尺寸在100-150纳米之间。FIG. 7 is a SEM image of the above product, and FIG. 2 shows that the material has good crystallization performance, uniform particle size, and a size between 100-150 nm.
图8是上述产物在监测发射光615纳米下得到的激发光谱图，从中可以看出，红色发光的激发来源主要为395纳米，因此该荧光粉可用于制备近紫外光激发荧光灯。FIG. 8 is an excitation spectrum chart of the above product under the monitored emission light of 615 nanometers. It can be seen that the excitation source of red light emission is mainly 395 nanometers, so the phosphor can be used to prepare near-ultraviolet excited fluorescent lamps.
图9是上述产物以近紫外光395纳米激发得到的发光光谱图，从图中可看出，该材料主要的中心发光波长在615纳米的红色发光波段，计算其色度得x＝0.656，y＝0.323。FIG. 9 is a luminescence spectrum obtained when the above product is excited by near-ultraviolet light at 395 nanometers. It can be seen from the figure that the main central luminescence wavelength of the material is in the red luminescence band of 615 nanometers. The calculated chromaticity is x = 0.656, y = 0.323.
图10是上述产物615纳米的发光衰减曲线，从图中可看出，该材料衰减时间为1.6毫秒。FIG. 10 is a luminescence decay curve of the above product at 615 nanometers. It can be seen from the figure that the decay time of the material is 1.6 ms.
实施例4：Example 4:
本实施例提供了一种Eu 3+离子激活的磷酸盐基荧光粉，其化学式为Sb 0.99Eu 0.01Nb 3(PO 4) 6。根据化学式中Sb、Eu、Nb和P元素的化学计量比，分别称取三氯化锑SbCl 3：2.26克，硝酸铕Eu(NO 3) 3·6H 2O：0.05克，氯化铌NbCl 5：8.1克，磷酸二氢铵NH 4H 2PO 4：6.9克。按照以下方法制备上述Eu 3+离子激活的磷酸盐基荧光粉： This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.99 Eu 0.01 Nb 3 (PO 4 ) 6 . According to the stoichiometric ratios of the elements Sb, Eu, Nb and P in the chemical formula, antimony trichloride SbCl 3 was weighed: 2.26 g, europium nitrate Eu (NO 3 ) 3 · 6H 2 O: 0.05 g, niobium chloride NbCl 5 : 8.1 g, ammonium dihydrogen phosphate NH 4 H 2 PO 4 : 6.9 g. The above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
将三氯化锑和硝酸铕溶解于稀硝酸溶液中，不断强烈搅拌，直至完全溶解后得到透明的溶液，称取1.8克草酸加入该透明溶液，于75℃下搅拌，记作A溶液。将称取的氯化铌NbCl 5溶解于氢氟酸溶液中，在70℃下水浴加热，不断搅拌至完全溶解，再加入5.4克的络合剂草酸，在80℃下搅拌，得到透明溶液，记作B溶液。将称取的磷酸二氢铵NH 4H 2PO 4试剂溶于稀硝酸中，再加入10.8克的草酸，70℃下搅拌得到透明溶液，记作C溶液。将得到的A、B、C溶液缓慢混合，在80℃的温度条件下搅拌2小时后，静置后烘干，得到蓬松的前驱体。将得到的前驱体在空气气氛中煅烧，温度为900℃，时间为3小时，自然冷却到室温，得到Sb 0.99Eu 0.01Nb 3(PO 4) 6红色荧光粉。其激发光谱、发光光谱和衰减曲线与实施例3相似。 Dissolve antimony trichloride and thorium nitrate in a dilute nitric acid solution and continue to stir vigorously until a clear solution is obtained after complete dissolution. Weigh 1.8 grams of oxalic acid into the transparent solution, stir at 75 ° C, and record it as solution A. The weighed niobium chloride NbCl 5 is dissolved in a hydrofluoric acid solution, heated in a water bath at 70 ° C., and continuously stirred until completely dissolved, and then 5.4 g of a complexing agent, oxalic acid, is added and stirred at 80 ° C. to obtain a transparent solution. Recorded as B solution. The weighed ammonium dihydrogen phosphate NH 4 H 2 PO 4 reagent was dissolved in dilute nitric acid, 10.8 g of oxalic acid was added, and the solution was stirred at 70 ° C. to obtain a transparent solution, which is referred to as solution C. The obtained A, B, and C solutions were slowly mixed, stirred at a temperature of 80 ° C. for 2 hours, and then allowed to stand and then dried to obtain a fluffy precursor. The obtained precursor was calcined in an air atmosphere at a temperature of 900 ° C. for a period of 3 hours, and was naturally cooled to room temperature to obtain Sb 0.99 Eu 0.01 Nb 3 (PO 4 ) 6 red phosphor. Its excitation spectrum, emission spectrum and attenuation curve are similar to those of the third embodiment.
实施例5：Example 5:
本实施例提供了一种Eu 3+离子激活的磷酸盐基荧光粉，其化学式为Sb 0.95Eu 0.05Nb 3(PO 4) 6。根据化学式中Sb、Eu、Nb和P元素的化学计量比，分别称取三氯化锑SbCl 3：1.3克，硝酸铕Eu(NO 3) 3·6H 2O：0.134，氯化铌NbCl 5：4.86克，磷酸二氢铵NH 4H 2PO 4：4.14克。按照以下方法制备上述Eu 3+离子激活的磷酸盐基荧光粉： This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.95 Eu 0.05 Nb 3 (PO 4 ) 6 . According to the stoichiometric ratios of the elements Sb, Eu, Nb and P in the chemical formula, antimony trichloride SbCl 3 : 1.3 g, europium nitrate Eu (NO 3 ) 3 · 6H 2 O: 0.134, niobium chloride NbCl 5 : 4.86 g, ammonium dihydrogen phosphate NH 4 H 2 PO 4 : 4.14 g. The above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
将三氯化锑SbCl 3和硝酸铕Eu(NO 3) 3·6H 2O溶解于稀硝酸溶液中，不断强烈搅拌，直至完全溶解后得到透明的溶液，称取1.29克草酸加入该透明溶液，于90℃下搅拌，记作A溶 液；将称取的氯化铌NbCl 5溶解于氢氟酸溶液中，在80℃下水浴加热，不断搅拌至完全溶解，再加入4.05克的络合剂草酸，在80℃下搅拌，得到透明溶液，记作B溶液；将称取的磷酸二氢铵NH 4H 2PO 4试剂溶于稀硝酸中，再加入8.1克的草酸，75℃下搅拌得到透明溶液，记作C溶液。 Dissolve antimony trichloride SbCl 3 and europium nitrate Eu (NO 3 ) 3 · 6H 2 O in a dilute nitric acid solution, and continue to stir vigorously until a transparent solution is obtained after complete dissolution. Weigh 1.29 grams of oxalic acid into the transparent solution. Stir at 90 ° C and record it as solution A. Dissolve the weighed niobium chloride NbCl 5 in the hydrofluoric acid solution, heat it in a water bath at 80 ° C, continue to stir until completely dissolved, and then add 4.05 g of the complexing agent oxalic acid. Stir at 80 ° C to obtain a transparent solution, which is referred to as solution B. Dissolve the weighed ammonium dihydrogen phosphate NH 4 H 2 PO 4 reagent in dilute nitric acid, add 8.1 g of oxalic acid, and stir at 75 ° C to obtain transparency. Solution, denoted as C solution.
将得到的A、B、C溶液缓慢混合，在90℃的温度条件下搅拌3小时后，静置后烘干，得到蓬松的前驱体。将得到的前驱体在空气气氛中煅烧，温度为860℃，时间为4小时，自然冷却到室温，得到Sb 0.95Eu 0.05Nb 3(PO 4) 6红色荧光粉。其激发光谱、发光光谱和衰减曲线与实施例3相似。 The obtained A, B, and C solutions were slowly mixed, stirred at a temperature of 90 ° C. for 3 hours, and then allowed to stand and then dried to obtain a fluffy precursor. The obtained precursor was calcined in an air atmosphere at a temperature of 860 ° C. for a period of 4 hours, and was naturally cooled to room temperature to obtain Sb 0.95 Eu 0.05 Nb 3 (PO 4 ) 6 red phosphor. Its excitation spectrum, emission spectrum and attenuation curve are similar to those of the third embodiment.
以上所述仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。The above are only preferred embodiments of the present invention, and are not intended to limit the present invention. It should be noted that for those skilled in the art, several improvements can be made without departing from the technical principles of the present invention. And modifications, these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种Eu 3+离子激活的磷酸盐基荧光材料，其特征在于：其化学式为Sb 1-xEu xNb 3(PO 4) 6，其中0.001≤x≤0.1，所述Eu 3+离子激活的磷酸盐基荧光材料在近紫外光的激发下发出红色荧光。 A Eu 3+ ion-activated phosphate-based fluorescent material, characterized in that its chemical formula is Sb 1-x Eu x Nb 3 (PO 4 ) 6 , where 0.001 ≦ x ≦ 0.1, the Eu 3+ ion-activated Phosphate-based fluorescent materials emit red fluorescence when excited by near-ultraviolet light.
  2. 根据权利要求1所述的Eu 3+离子激活的磷酸盐基荧光材料，其特征在于：所述近紫外光的波长为370-410nm。 The Eu 3+ ion-activated phosphate-based fluorescent material according to claim 1, wherein the wavelength of the near-ultraviolet light is 370-410 nm.
  3. 根据权利要求1所述的Eu 3+离子激活的磷酸盐基荧光材料，其特征在于：所述红色荧光的波长为570-720nm。 The Eu 3+ ion-activated phosphate-based fluorescent material according to claim 1, wherein the wavelength of the red fluorescence is 570-720 nm.
  4. 权利要求1-3中任一项所述的Eu 3+离子激活的磷酸盐基荧光材料在制备发光器件中的应用，所述发光器件的激发源为近紫外光。 The application of the Eu 3+ ion-activated phosphate-based fluorescent material according to any one of claims 1 to 3 in the preparation of a light emitting device, wherein the excitation source of the light emitting device is near-ultraviolet light.
  5. 一种权利要求1-3中任一项所述的Eu 3+离子激活的磷酸盐基荧光材料的制备方法，其特征在于，包括以下步骤： A method for preparing an Eu 3+ ion-activated phosphate-based fluorescent material according to any one of claims 1-3, comprising the following steps:
    (1)将含有Sb 3+离子的化合物和含有Eu 3+离子的化合物溶于稀硝酸中，在络合剂的存在下在60-90℃下混匀，得到A溶液；将含有Nb 5+离子的化合物溶于氢氟酸，然后在60-90℃下与所述络合剂混匀，得到B溶液；将含有P 5+离子的化合物溶于稀硝酸中，然后在60-80℃下与所述络合剂混匀，得到C溶液； (1) Dissolve the compound containing Sb 3+ ions and the compound containing Eu 3+ ions in dilute nitric acid, mix in the presence of a complexing agent at 60-90 ° C to obtain A solution; and include Nb 5+ The ionic compound is dissolved in hydrofluoric acid, and then mixed with the complexing agent at 60-90 ° C to obtain a solution B; the compound containing P 5+ ions is dissolved in dilute nitric acid, and then at 60-80 ° C Mix with the complexing agent to obtain a C solution;
    其中，所述络合剂的用量和所加入溶液之中阳离子的摩尔比为1.5-2.5:1；Wherein, the amount of the complexing agent and the molar ratio of cations in the added solution are 1.5-2.5: 1;
    所述含有Sb 3+离子的化合物、含有Nb 5+离子的化合物、含有P 5+离子的化合物、含有Eu 3+离子的化合物的摩尔比为0.9-0.999:3:6:0.001-0.1； The molar ratio of the Sb 3+ ion-containing compound, the Nb 5+ ion-containing compound, the P 5+ ion-containing compound, and the Eu 3+ ion-containing compound is 0.9-0.999: 3: 6: 0.001-0.1;
    (2)将所述A溶液、B溶液和C溶液混匀后在60-95℃下反应，反应完全后干燥产物，得到前驱体；(2) the A solution, the B solution and the C solution are mixed and reacted at 60-95 ° C; after the reaction is completed, the product is dried to obtain a precursor;
    (3)将所述前驱体在空气气氛中煅烧，煅烧温度为800-1000℃，得到所述Eu 3+离子激活的磷酸盐基荧光材料。 (3) The precursor is calcined in an air atmosphere, and the calcination temperature is 800-1000 ° C to obtain the Eu 3+ ion-activated phosphate-based fluorescent material.
  6. 根据权利要求5所述的制备方法，其特征在于：在步骤(1)中，所述络合剂为柠檬酸或草酸。The method according to claim 5, wherein in step (1), the complexing agent is citric acid or oxalic acid.
  7. 根据权利要求5所述的制备方法，其特征在于：在步骤(1)中，所述含有Sb 3+离子的化合物为三氧化二锑或三氯化锑。 The preparation method according to claim 5, wherein in the step (1), the compound containing Sb 3+ ions is antimony trioxide or antimony trichloride.
  8. 根据权利要求5所述的制备方法，其特征在于：在步骤(1)中，所述含有Eu 3+离子的化合物为氧化铕或硝酸铕。 The method according to claim 5, wherein in step (1), the compound containing Eu 3+ ions is osmium oxide or osmium nitrate.
  9. 根据权利要求5所述的制备方法，其特征在于：在步骤(1)中，所述含有Nb 5+离子的化合物为五氧化二铌或氯化铌。 The preparation method according to claim 5, wherein in the step (1), the compound containing Nb 5+ ions is niobium pentoxide or niobium chloride.
  10. 根据权利要求5所述的制备方法，其特征在于：在步骤(1)中，所述含有P 5+离子的化合物为磷酸氢二铵或磷酸二氢铵。 The preparation method according to claim 5, wherein in step (1), the compound containing P 5+ ions is diammonium phosphate or diammonium phosphate.
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