CN113549457B - Europium (III) -doped scheelite type red fluorescent powder, preparation and application - Google Patents
Europium (III) -doped scheelite type red fluorescent powder, preparation and application Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 52
- LNBHUCHAFZUEGJ-UHFFFAOYSA-N europium(3+) Chemical compound [Eu+3] LNBHUCHAFZUEGJ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000005284 excitation Effects 0.000 claims description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000008247 solid mixture Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 108010025647 phosphate-binding proteolipid Proteins 0.000 claims 1
- UNQNIRQQBJCMQR-UHFFFAOYSA-N phosphorine Chemical compound C1=CC=PC=C1 UNQNIRQQBJCMQR-UHFFFAOYSA-N 0.000 claims 1
- 238000005286 illumination Methods 0.000 abstract description 13
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
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- 241000115226 Nacaeus Species 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 9
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- 239000012856 weighed raw material Substances 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
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- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
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- 239000012190 activator Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
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- 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
- C09K11/7736—Vanadates; Chromates; Molybdates; Tungstates
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Abstract
The invention discloses europium (III) -doped white tungstenOre-type red fluorescent powder, preparation and application thereof, wherein the chemical formula of the fluorescent powder is NaCaLa 1‑x Eu x (MoO 4 ) 3 Wherein x is Eu 3+ Substituted La 3+ The mole fraction of (c). Mixing compounds containing Na, ca, la, eu and Mo, calcining in air by adopting a high-temperature solid-phase synthesis method, and carrying out heat treatment to obtain NaCaLa 1‑x (MoO 4 ) 3 :xEu 3+ And (4) red fluorescent powder. The fluorescent powder prepared by the method has better thermal stability, wider exciting light wavelength range and stronger exciting efficiency in the near ultraviolet and blue light ranges, and meets the requirement of high color reduction degree in illumination. The fluorescent powder can be combined with an ultraviolet or blue light LED chip to be applied to indoor LED illumination and indoor plant illumination.
Description
Technical Field
The invention relates to europium (III) -doped scheelite-type red fluorescent powder and a preparation method thereof, belonging to inorganic luminescent materials, belonging to the technical field of inorganic fluorescent powder materials and being applied to LED illumination.
Background
With the rapid development of human society, the demand for electric power is increasing day by day, and the awareness of environmental protection is gradually increasing. In response to climate warming, people seek sustainable energy and reduce the demand of electricity in various forms. The development of clean and sustainable energy can make up for CO brought by fossil energy 2 And the greenhouse effect caused by excessive emission. For saving electric energy, a light emitting device with high efficiency and energy saving becomes one of the hot spots of research. Fluorescent conversion light emitting diodes (pc-LEDs) have received much attention because of their characteristics of high efficiency, energy saving, long life, small size, environmental friendliness, etc. LEDs are also considered as fourth generation illumination sources (green light sources).
Conventional day-to-day lighting sources, such as incandescent lamps and fluorescent lamps, have been gradually replaced by LEDs. With the development and wide application of white light LEDs, the demand for LEDs has shifted from initial "high brightness" to compromise color temperature and color rendering index, so as to meet the requirements for white light quality in different environments. The commercial white light LED mainly adopts a blue InGaN LED chip and a yellow Y 3 Al 5 O 12 :Ce 3+ (YAG:Ce 3+ ) And (5) packaging the fluorescent powder. However, the white light obtained by the method has higher Correlated Color Temperature (CCT) due to the lack of red spectral components>4500K) And low color rendering index (Ra)<80 Preventing its use in certain environments.
The rare earth luminescent material hasThe rare earth luminescent material-based pc-LED has the characteristics of narrow luminescent band, high luminescent efficiency, adjustable luminescent spectrum and the like, and can obtain light with specific spectral characteristics. Increasing the red spectral composition in a white LED can significantly improve the pc-LED color rendering index and reduce the correlated color temperature. In the red light-emitting phosphor, eu 3+ The ion activated red fluorescent powder can be obtained from near ultraviolet light under excitation 5 D 0 → 7 F J (J =1,2,3,4; center wavelength about 615 nm) characteristic transition. Thus Eu 3+ The ions are very important activators for red phosphors. However, the existing red fluorescent powder generally has the characteristics of poor thermal stability, low luminous efficiency and narrow wavelength range of exciting light, so that the practical use requirement of people on high-quality white light cannot be met. Meanwhile, there are commercially available red light emitting phosphors (e.g., caAlSiN) 3 :Eu 2+ ) The preparation process of (a) is more demanding in terms of operation and equipment, for example, high temperature, high pressure, or under a specific calcining atmosphere, which raises the production cost. Therefore, it is of great significance to develop a red light emitting phosphor having high luminous efficiency and thermal stability and being easy to prepare.
Disclosure of Invention
In order to solve the above-mentioned defects in the prior art, the present invention provides a Eu 3+ The ion-activated scheelite-type near ultraviolet/blue light excited red fluorescent powder has high color purity, high luminescent quantum efficiency, good thermal stability and good excitation light wavelength range; another aspect of the present invention provides the above Eu 3+ The specific preparation method of the ion-activated scheelite-type red fluorescent powder has the advantages of simple preparation process, low equipment requirement and convenient operation.
The invention is mainly realized by the following technical scheme.
In one aspect of the present invention, a Eu is provided 3+ The ion activated scheelite type red fluorescent powder has a chemical general formula of NaCaLa 1-x Eu x (MoO 4 ) 3 X is Eu 3+ Substituted La 3+ The value of the mole fraction of (a) is in the range of 0 to 1.
In another aspect of the present invention, a method for preparing europium (III) -doped scheelite-type red phosphor is provided, which comprises the following steps:
(1) Mixing Na compound, ca compound, la compound, eu compound and Mo compound according to the molar ratio 1:1 (1-x) of the chemical formula x:3, wherein x is 0-1; fully grinding to obtain a uniformly mixed solid mixture;
(2) Placing the solid mixture in a furnace, calcining in an air atmosphere, and then cooling to room temperature along with the furnace;
(3) Fully grinding the calcined mixture, putting the mixture into the furnace again, and carrying out high-temperature heat treatment, wherein the sample is cooled to room temperature along with the furnace;
(4) Fully grinding the sample cooled to room temperature again to obtain NaCaLa 1-x Eu x (MoO 4 ) 3 Solid powder samples.
With respect to the above technical solutions, the present invention has a further preferable solution:
preferably, the Na-containing compound + The compound is NaHCO 3 、Na 2 O、Na 2 CO 3 NaOH and NaNO 3 One or more of (a).
The Ca-containing compound is CaCO 3 、Ca(OH) 2 CaO and Ca (NO) 3 ) 2 One or more of (a).
The La-containing compound is La 2 O 3 、La(NO 3 ) 3 And La 2 (CO 3 ) 3 One or more of (a).
The Eu-containing compound is europium oxide Eu 2 O 3 、Eu(NO 3 ) 3 ·6H 2 O and Eu 2 (CO 3 ) 3 One or more of (a).
The Mo-containing compound is (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O、MoO 3 MoC and MoO 2 One or more of (a).
Preferably, in the steps (2) and (3), the temperature is increased at a rate of 2 to 5 ℃/min.
In the step (2), calcining is carried out for 4-8 hours at 500-600 ℃ in an air atmosphere.
In the step (3), high-temperature heat treatment is carried out for 8-24 hours at 850-1100 ℃.
On the other hand, the invention provides europium (III) doped fluorescent powder prepared by the method, which can excite red light under the excitation of a light source with the wavelength of 250-550 nm.
In another aspect of the invention, the prepared europium (III) doped fluorescent powder is applied to a near ultraviolet/blue light excited white light LED chip. The near ultraviolet and blue light excited white light LED chip is an InGaN semiconductor chip; the wavelength range of the near ultraviolet luminescence peak value is 350-425nm; the peak wavelength range of blue light emission is 425-500nm.
The fluorescent powder emits red light with the central wavelength of 615nm under the excitation of near ultraviolet and blue light wavelengths, can be combined with a near ultraviolet or blue light LED chip to prepare red light or white light LED illumination, and is respectively used for indoor plant illumination and indoor white light illumination.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
(1) The invention selects Eu 3+ Is a luminescent center due to its special characteristics 5 D 0 → 7 F J (J =1,2,3,4) can emit red light, can meet the requirement of a white light device on red spectrum composition, and solves the problem that the white light device lacks red spectrum components.
(2) The substrate of the invention is NaCaLa 1-x Eu x (MoO 4 ) 3 The crystal lattice of the matrix is composed of multiple ions (Na) + ，Ca 2+ ，La 3 + ) And (4) polyhedron composition. Usually, when Eu 3+ Gradually increasing concentration, eu 3+ With Eu 3+ The distance between the two is gradually shortened to enable Eu 3+ The energy transfer is increased, the concentration quenching is increased, and finally the fluorescence intensity is reduced. The coexistence of multiple cations in the invention can effectively reduce Eu 3+ With Eu 3+ The energy transfer process between the samples makes the samples reach Eu 3+ The red light emitting fluorescent powder with high fluorescence efficiency is finally obtained by high doping of the concentration.
(3) Because the selected matrix is a scheelite type compound, the matrix contains La 3+ Can be Eu-substituted 3+ The red luminescent phosphor powder has the advantages of avoiding the influence of charge compensation on the stable running and the luminous efficiency of the material, obtaining the red luminescent phosphor powder with high luminous efficiency and higher thermal stability, and meeting the requirement of thermal stability.
(4) Eu provided by the invention 3+ The doped scheelite type red fluorescent powder has excellent luminous performance, high quantum efficiency, high color purity and good stability. Has stronger excitation efficiency in the range of near ultraviolet and blue light, can emit red light (with the central emission wavelength of 615 nm) with the color purity higher than 90 percent, and meets the requirement of high color reduction degree in illumination.
(5) Eu obtained by the invention 3+ The ion-activated scheelite-type red phosphor exhibits strong excitation efficiency in the near ultraviolet (optimally 395 nm) and blue light wavelength (optimally 466 nm), and thus the Eu 3+ The ion-activated fluorescent powder is suitable for being combined with a near ultraviolet or blue light LED chip to prepare white light LED lighting equipment and indoor plant lighting, the range of excitation spectrum of the fluorescent powder is widened, and the application of a sample is expanded.
(6) The invention adopts a solid-phase synthesis method, calcinates under the set temperature and process conditions, carries out high-temperature heat treatment, can directly synthesize a target product in the air, does not need complex and harsh preparation conditions of high temperature and high pressure, and can obtain the scheelite type near ultraviolet/blue light excited red fluorescent powder with good thermal stability, high luminous efficiency and wide excitation light wavelength range.
The method has the advantages of convenient operation, low equipment requirement and simple synthesis process; the preparation process is energy-saving and environment-friendly, and the matrix material has no pollution to the environment.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention:
FIG. 1 shows NaCaEu (MoO) in example 4 4 ) 3 NaCaLa in example 2 0.6 Eu 0.4 (MoO 4 ) 3 Sample and substrate NaCaLa (MoO) 4 ) 3 XRD pattern of (a).
FIG. 2 shows Eu in example 1 3+ Doped NaCaLa 0.4 Eu 0.6 (MoO 4 ) 3 SEM photograph of red phosphor;
FIG. 3 shows NaCaLa in example 1 0.4 Eu 0.6 (MoO 4 ) 3 NaCaLa in example 2 0.6 Eu 0.4 (MoO 4 ) 3 NaCaLa in example 3 0.8 Eu 0.2 (MoO 4 ) 3 And NaCaEu (MoO) in example 4 4 ) 3 Excitation spectrum of the fluorescent powder under 615nm monitoring.
FIG. 4 shows NaCaLa in example 1 0.4 Eu 0.6 (MoO 4 ) 3 NaCaLa in example 2 0.6 Eu 0.4 (MoO 4 ) 3 NaCaLa in example 3 0.8 Eu 0.2 (MoO 4 ) 3 And NaCaEu (MoO) in example 4 4 ) 3 An emission spectrum of the fluorescent powder under 395nm excitation; the inset is an enlarged view of the spectrum in the 610-620nm range.
FIG. 5 shows NaCaLa in example 1 0.4 Eu 0.6 (MoO 4 ) 3 NaCaLa in example 2 0.6 Eu 0.4 (MoO 4 ) 3 NaCaLa in example 3 0.8 Eu 0.2 (MoO 4 ) 3 And NaCaEu (MoO) in example 4 4 ) 3 An emission spectrum of the fluorescent powder under 466nm excitation; the inset is an enlarged view of the spectrum in the 610-620nm range.
FIG. 6 shows Eu in example 1 3+ Doped NaCaLa 0.4 Eu 0.6 (MoO 4 ) 3 Fluorescence decay lifetime map of red phosphor.
FIG. 7 shows Eu in example 1 3+ Doped NaCaLa 0.4 Eu 0.6 (MoO 4 ) 3 Thermal stability of red phosphor.
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific embodiments, wherein the exemplary embodiments and descriptions of the present invention are provided to explain the present invention without limiting the invention thereto.
The embodiment of the invention provides a preparation method of europium (III) -doped scheelite-type red fluorescent powder, which comprises the following steps:
(1) According to the chemical formula NaCaLa 1-x Eu x (MoO 4 ) 3 The Na-containing compound (NaHCO) is added according to the atomic stoichiometric ratio of 1:1 (1-x): x:3 3 、Na 2 O、Na 2 CO 3 NaOH and NaNO 3 One or more of) a Ca-containing compound (CaCO) 3 、Ca(OH) 2 CaO and Ca (NO) 3 ) 2 One or more of) La-containing compound (La) 2 O 3 、La(NO 3 ) 3 And La 2 (CO 3 ) 3 One or more of), a Eu-containing compound (Eu) 2 O 3 、Eu(NO 3 ) 3 ·6H 2 O and Eu 2 (CO 3 ) 3 One or more of) and a Mo-containing compound ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O、MoO 3 MoC and MoO 2 One or more of) x is 0 to 1; and fully grinding to obtain a uniformly mixed solid mixture. Preferably, eu 3+ The optimum concentration of the ion-activated scheelite-type red phosphor is x =1.0, and the phosphor has excellent properties such as luminous intensity, color purity, quantum efficiency, and the like.
Wherein, eu in the general formula 3+ Substituted La 3+ The locus, wherein the value range of x is 0-1; fluorescent powder NaCaLa 1-x Eu x (MoO 4 ) 3 The particle size distribution of (A) is in the range of 2 to 8 μm.
(2) And (3) putting the solid mixture into a furnace, heating to 500-600 ℃ at the speed of 2-5 ℃/min, calcining for 4-8 hours in an air atmosphere, and then cooling to room temperature along with the furnace.
(3) And fully grinding the calcined sample, putting the sample into the furnace again, heating the sample to 850-1100 ℃ at the speed of 2-5 ℃/min, carrying out high-temperature heat treatment for 8-24 hours, and then cooling the sample to room temperature along with the furnace.
(4) Fully grinding the obtained sample again to obtain NaCaLa 1-x Eu x (MoO 4 ) 3 Solid powder samples.
The invention is further illustrated by the following different examples.
Example 1
(1) 0.0840g NaHCO 3 was weighed according to atomic stoichiometric ratio 1 3 、0.1001g CaCO 3 、0.0652g La 2 O 3 、0.1056g Eu 2 O 3 And 0.5297g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 A compound of O;
(2) Placing the weighed raw materials in a mortar for fully grinding to obtain a uniformly mixed solid mixture;
(3) Placing the uniformly mixed mixture in a furnace, and pre-calcining the mixture for 5 hours at 550 ℃ in an air atmosphere; the heating rate is 5 ℃ per minute;
(4) After the heat treatment is finished, the sample is cooled to the room temperature along with the furnace, and the sample cooled to the room temperature is fully ground by using the mortar again.
(5) The ground sample was placed in an oven and heated to 900 ℃ at a rate of 5 ℃ per minute and held for 10 hours.
(6) Cooling the calcined sample to room temperature along with the furnace, and fully grinding the sample by using a mortar to obtain NaCaLa 0.4 Eu 0.6 (MoO 4 ) 3 Solid powder samples.
Example 2
(1) 0.0530g of Na is weighed according to the atomic stoichiometric ratio of 1 2 CO 3 、0.0561g CaO、0.1374g La 2 (CO 3 ) 3 、0.0968g Eu 2 (CO 3 ) 3 And 0.3239g MoC compound;
(2) Placing the weighed raw materials in a mortar for full grinding to obtain a uniformly mixed solid mixture;
(3) Placing the uniformly mixed mixture in a furnace, and pre-calcining the mixture for 5 hours at 600 ℃ in an air atmosphere; the heating rate is 3 ℃ per minute;
(4) After the heat treatment is finished, the sample is cooled to the room temperature along with the furnace, and the sample cooled to the room temperature is fully ground by using the mortar again.
(5) The ground sample was placed in a furnace and heated to 1100 ℃ at a rate of 3 ℃ per minute and held for 8 hours.
(6) Cooling the calcined sample to room temperature along with the furnace, and fully grinding the sample by using a mortar to obtain NaCaLa 0.6 Eu 0.4 (MoO 4 ) 3 Solid powder samples.
Example 3
(1) 0.0310g of Na is weighed according to the atomic stoichiometric ratio 1 2 O、0.0741g Ca(OH) 2 、0.3464g La(NO 3 ) 3 、0.0892g Eu(NO 3 ) 3 ·6H 2 O, and 0.4320g MoO 3 A compound;
(2) Placing the weighed raw materials in a mortar for fully grinding to obtain a uniformly mixed solid mixture;
(3) Placing the uniformly mixed mixture in a furnace, and pre-calcining the mixture for 6 hours at 500 ℃ in an air atmosphere; the heating rate is 4 ℃ per minute;
(4) After the heat treatment is finished, the sample is cooled to the room temperature along with the furnace, and the sample cooled to the room temperature is fully ground by the mortar again.
(5) The ground sample was placed in an oven and heated to 950 ℃ at a rate of 4 ℃ per minute and held for 18 hours.
(6) Cooling the calcined sample to room temperature along with the furnace, and fully grinding the sample by using a mortar to obtain NaCaLa 0.8 Eu 0.2 (MoO 4 ) 3 Solid powder samples.
Example 4
(1) Weighing 0.0850g of NaNO according to the atomic stoichiometric ratio of 1 3 、0.1641g Ca(NO 3 ) 2 、0.2420g Eu 2 (CO 3 ) 3 And 0.3838g MoO 2 A compound;
(2) Placing the weighed raw materials in a mortar for full grinding to obtain a uniformly mixed solid mixture;
(3) Placing the uniformly mixed mixture in a furnace, and pre-calcining for 4 hours at 580 ℃ in an air atmosphere; the rate of temperature rise is 2 ℃ per minute;
(4) After the heat treatment is finished, the sample is cooled to the room temperature along with the furnace, and the sample cooled to the room temperature is fully ground by using the mortar again.
(5) The ground sample was placed in an oven and heated to 850 ℃ at a rate of 2 ℃ per minute and held for 24 hours.
(6) Cooling the calcined sample to room temperature along with the furnace, and fully grinding the sample by using a mortar to obtain NaCaEu (MoO) 4 ) 3 Solid powder samples.
The effect of the red phosphors prepared in examples 1-4 of the present invention is further illustrated by the accompanying drawings.
FIG. 1 shows NaCaEu (MoO) in example 4 4 ) 3 NaCaLa in example 2 0.6 Eu 0.4 (MoO 4 ) 3 Sample and substrate NaCaLa (MoO) 4 ) 3 XRD pattern of (a). XRD contrast analysis shows that XRD diffraction peak and CaMoO of the sample 4 The standard card of (1) is well matched, indicating that NaCaEu (MoO) 4 ) 3 And NaCaLa 0.6 Eu 0.4 (MoO 4 ) 3 Phosphor powder is shown to react with scheelite CaMoO 4 The same crystal structure belonging to the tetragonal system, I4 1 A space group. Thus, naCaEu (MoO) 4 ) 3 And NaCaLa 0.6 Eu 0.4 (MoO 4 ) 3 The fluorescent powder is scheelite type fluorescent powder.
FIG. 2 shows NaCaLa in example 1 0.4 Eu 0.6 (MoO 4 ) 3 Scanning electron microscope photograph of the phosphor. As can be seen from the figure, the phosphor has an irregular morphology with particle sizes mainly distributed in the range of 2-8 μm.
FIG. 3 shows NaCaLa in example 1 0.4 Eu 0.6 (MoO 4 ) 3 NaCaLa in example 2 0.6 Eu 0.4 (MoO 4 ) 3 NaCaLa in example 3 0.8 Eu 0.2 (MoO 4 ) 3 And NaCaEu (MoO) in example 4 4 ) 3 Excitation spectrum of fluorescent powder under 615nm monitoringDrawing. As can be seen from the figure, the optimum excitation wavelength was 395nm for all samples, and the excitation spectrum showed Eu 3+ Characteristic sharp excitation peak. The excitation spectrum contains two characteristic excitation peaks: broad excitation band and sharp excitation peak; the wide excitation band is the charge transfer band of O-Eu and O-Mo in the sample, and the sharp excitation peak is derived from Eu 3+ Characteristic transition of (2). The optimal excitation wavelength is 395nm and is derived from 7 F 0 → 5 L 6 Transition; the secondary excitation peak is at 466nm and is derived from 7 F 0 → 5 D 2 Transition; the excitation peak at 536nm is derived from 7 F 0 → 5 D 1 And transition shows that the fluorescent powder can be matched with an ultraviolet LED chip or a blue LED chip to be applied to LED illumination.
FIG. 4 shows NaCaLa in example 1 0.4 Eu 0.6 (MoO 4 ) 3 NaCaLa in example 2 0.6 Eu 0.4 (MoO 4 ) 3 NaCaLa in example 3 0.8 Eu 0.2 (MoO 4 ) 3 And NaCaEu (MoO) in example 4 4 ) 3 An emission spectrum of the fluorescent powder under 395nm excitation; the inset is an enlarged view of the spectrum in the 610-620nm range. As can be seen from the figure, all samples showed strong sharp emission peak in the wavelength range of 575-725nm, and the optimal emission wavelength was 615nm, which is originated from 5 D 0 → 7 F 2 Transition; 615nm relatively strong peak emission shows that the half-peak width of the sample is narrow, namely the color purity of the sample is high, and NaCaLa is excited under 395nm 0.4 Eu 0.6 (MoO 4 ) 3 The purity of the sample is up to 96%, which indicates that the sample can be used as near ultraviolet excited red light emitting fluorescent powder for indoor illumination.
FIG. 5 shows NaCaLa in example 1 0.4 Eu 0.6 (MoO 4 ) 3 NaCaLa in example 2 0.6 Eu 0.4 (MoO 4 ) 3 NaCaLa in example 3 0.8 Eu 0.2 (MoO 4 ) 3 And NaCaEu (MoO) in example 4 4 ) 3 Emission spectrum of the fluorescent powder under 466nm excitation. The inset is the spectral power in the range of 610-620nmAnd (4) large drawing. Comparing with FIG. 4, it can be seen that there is almost no change in the emission band of the sample under 466nm excitation, and the optimal excitation peak is at 615nm ((R)) 5 D 0 → 7 F 2 Transition), under 466nm excitation, naCaLa 0.4 Eu 0.6 (MoO 4 ) 3 The quantum efficiency of the sample is as high as 98.3%, which indicates that the sample can be used as red light emitting fluorescent powder excited by blue light for indoor illumination.
FIG. 6 shows NaCaLa 0.4 Eu 0.6 (MoO 4 ) 3 Fluorescence decay lifetime map of the phosphor. It can be seen from the figure that the luminescence lifetime of the sample is 0.445 ms, the fluorescence decay lifetime of the phosphor belongs to the millisecond level, and the afterglow phenomenon in the luminescence illumination and display application can be effectively avoided.
FIG. 7 shows NaCaLa 0.4 Eu 0.6 (MoO 4 ) 3 According to the stability chart of the fluorescent powder, the luminous intensity of a sample still keeps 54% of the original intensity when the luminous intensity is 403K, and the fluorescent powder has better thermal stability.
From the above examples 1-4, it can be seen that the invention successfully obtains the red light emitting phosphor with high color purity, high color rendering index and good thermal stability in the air without high pressure environment by only adopting the solid phase synthesis method, and can make up the deficiency of the red light spectrum in the commercial white light device and improve the color rendering index. The excitation spectrum range of the fluorescent powder is wide, and the fluorescent powder can be combined with near ultraviolet and blue light chips to obtain white light, so that the application range of the fluorescent powder is widened.
The purpose is to explain the present invention, the present invention is not limited to the above embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts, and these substitutions and modifications are all within the protection scope of the present invention.
Claims (8)
1. A preparation method of europium (III) -doped scheelite-type red fluorescent powder is characterized by comprising the following steps:
(1) According to the chemical formula NaCaLa 0.4 Eu 0.6 (MoO 4 ) 3 Mixing a Na-containing compound, a Ca-containing compound, a La-containing compound, a Eu-containing compound, and a Mo-containing compound in an atomic stoichiometric ratio of 1.4;
(2) Placing the solid mixture in a furnace, and heating at a rate of 5 ℃/min; at 550 o Calcining for 5 hours in an air atmosphere under C, and then cooling to room temperature along with the furnace;
(3) Fully grinding the calcined sample, putting the sample into the furnace again, and heating at the speed of 5 ℃/min; at 900 o C, carrying out high-temperature heat treatment for 10 hours, and then cooling to room temperature along with the furnace;
(4) Fully grinding the obtained sample again to obtain NaCaLa with the particle size distribution of 2-8 mu m 0.4 Eu 0.6 (MoO 4 ) 3 A solid powder sample;
under 395nm excitation, naCaLa 0.4 Eu 0.6 (MoO 4 ) 3 The purity of the luminescent color of the sample is up to 96 percent; naCaLa under the excitation of 466nm 0.4 Eu 0.6 (MoO 4 ) 3 The quantum efficiency of the sample is as high as 98.3%, the luminescent lifetime is 0.445 milliseconds, and the luminescent intensity is still 54% of the original intensity when 403K.
2. The method of claim 1, wherein the Na-containing compound is NaHCO 3 、Na 2 O、Na 2 CO 3 NaOH and NaNO 3 One or more of (a).
3. The method of claim 1, wherein the Ca-containing compound is CaCO 3 、Ca(OH) 2 CaO and Ca (NO) 3 ) 2 One or more of (a).
4. The method of claim 1, wherein the europium (III) -doped scheelite-type red phosphorIn that the La-containing compound is La 2 O 3 、La(NO 3 ) 3 And La 2 (CO 3 ) 3 One or more of (a).
5. The method of claim 1, wherein the Eu (III) -doped scheelite-type red phosphor is Eu (Eu) oxide 2 O 3 、Eu(NO 3 ) 3 ·6H 2 O and Eu 2 (CO 3 ) 3 One or more of (a).
6. The method of claim 1, wherein the Mo-containing compound is (NH) 4 ) 6 Mo 7 O 24 •4H 2 O、MoO 3 MoC and MoO 2 One or more of (a).
7. A europium (III) -doped scheelite-type red phosphor prepared based on the method of any one of claims 1 to 6.
8. The europium (III) -doped scheelite-type red phosphor of claim 7 applied to a near ultraviolet/blue light excited white LED chip.
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