CN109971475B - A kind of europium ion Eu3+ activated calcium niobate red light-emitting phosphor, preparation method and application thereof - Google Patents
A kind of europium ion Eu3+ activated calcium niobate red light-emitting phosphor, preparation method and application thereof Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000001669 calcium Chemical class 0.000 title claims description 12
- 239000000843 powder Substances 0.000 claims abstract description 60
- -1 europium ion Chemical class 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 24
- 239000011575 calcium Substances 0.000 claims abstract description 21
- 150000002500 ions Chemical class 0.000 claims abstract description 19
- 239000010955 niobium Substances 0.000 claims abstract description 13
- 230000005284 excitation Effects 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 97
- 239000002994 raw material Substances 0.000 claims description 32
- 238000000227 grinding Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001449 indium ion Inorganic materials 0.000 claims description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 229910001940 europium oxide Inorganic materials 0.000 claims description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 2
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- GMYSDEOJMBLAKZ-UHFFFAOYSA-N calcium indium Chemical compound [Ca].[In] GMYSDEOJMBLAKZ-UHFFFAOYSA-N 0.000 abstract 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical group [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000004570 mortar (masonry) Substances 0.000 description 12
- 238000005286 illumination Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 238000000695 excitation spectrum Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001748 luminescence spectrum Methods 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- 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
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/85—Packages
- H10H20/851—Wavelength conversion means
- H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
- H10H20/8512—Wavelength conversion materials
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Abstract
本发明公开了一种铕离子Eu3+激活的铌铟酸钙红发光荧光粉、制备方法及其应用，化学表达式为Ca10‑xEuxInNb5‑xTixO24，x是铕离子Eu3+和钛离子Ti4+分别掺杂取代二价钙离子Ca2+和五价铌离子Nb5+的摩尔数，x取值范围为0.05≤x≤1.0。本发明荧光粉具有非常优秀的热稳定性，在近紫外光波长区域有着很强的激发效率，在近紫外光的激发下发出主峰在613nm的红光，且发光寿命均在1.0毫秒以上，满足发光照明和显示的需要且不出现余辉，更适宜制备近紫外LED二极管芯片配合制备的白光LED照明设备。另外本发明提供的荧光粉的制备方法为固相反应合成法，合成步骤简单，实用性强。
The invention discloses a red light-emitting fluorescent powder of calcium indium niobate activated by europium ion Eu 3+ , a preparation method and application thereof. The chemical expression is Ca 10‑x Eu x InNb 5‑x Ti x O 24 , and x is europium The number of moles of ion Eu 3+ and titanium ion Ti 4+ doped to replace divalent calcium ion Ca 2+ and pentavalent niobium ion Nb 5+ respectively, and the range of x is 0.05≤x≤1.0. The phosphor powder of the present invention has excellent thermal stability, has a strong excitation efficiency in the near-ultraviolet light wavelength region, emits red light with a main peak at 613 nm under the excitation of near-ultraviolet light, and has a luminous lifetime of more than 1.0 milliseconds, satisfying It is more suitable for the preparation of near-ultraviolet LED diode chips and the preparation of white light LED lighting equipment for the needs of luminous lighting and display without afterglow. In addition, the preparation method of the phosphor provided by the present invention is a solid-phase reaction synthesis method, the synthesis steps are simple, and the practicability is strong.
Description
Technical Field
The invention belongs to the technical field of inorganic fluorescent materials, and particularly relates to a europium ion Eu3+Activated calcium niobate indate red luminescent phosphor, a preparation method and application thereof.
Background
The illumination plays a closely important role in the development of the human society, the history of human illumination undergoes very complex evolution from old torch illumination to illumination using petroleum and electricity, and the recent illumination mainly utilizes the light-emitting phenomenon of fluorescent powder. In general, luminescence refers to the fact that an object is excited by energy, electrons absorb the excited energy and transit from a ground state energy level to an excited state energy level, and then the electrons release the absorbed energy in the process of returning to the ground state energy level and radiate in the form of luminescence. In addition, with the development of society, the function of luminescent materials cannot be separated from the storage and transmission of information. The rare earth ion activated fluorescent powder is one of the most important luminescent materials, and compared with non-rare earth fluorescent powder, the rare earth activated fluorescent powder has special advantages, such as high luminous efficiency, good temperature effect, pure chromaticity and the like. Therefore, in recent years, the rare earth fluorescent materials have become more widely used and the annual usage amount is rapidly increased.
Among the development and application of red, blue and green phosphors, the red emitting phosphor plays a very important role, for example, in a white LED lighting device, one of the main disadvantages of light emission is lack of red emitting component, and thus, has high color temperature (CCT)>4500K) And a color rendering index difference (Ra < 80), and thus exhibits luminescence, and in order to overcome this disadvantage, a main solution is to add a certain amount of a red luminescent component. In the red-emitting rare earth phosphor, Eu3+Is the most important active ion, and the luminescence is mainly from the sharp line spectrum of energy level transition in the 4f sublayer, so the luminescence has very pure chromaticity. Eu (Eu)3+The fluorescent powder is a spectrum probe ion, the light-emitting characteristic of the spectrum probe ion and the splitting of the 4f orbit in a crystal field have a close relationship, different substrates can emit light differently, and therefore, the selection of the substrates is very important in the design of the red light-emitting fluorescent powder.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a europium ion Eu3+The activated calcium niobate indate red luminescent phosphor has strong excitation efficiency in a near ultraviolet wavelength region, emits red light with a main peak at 613nm under the excitation of near ultraviolet light, has the luminescent life of more than 1.0 millisecond, meets the requirements of luminescent illumination and display, does not generate afterglow, and is more suitable for preparing white light LED (light-emitting diode) lighting equipment prepared by matching near ultraviolet LED chips; in addition, the preparation method of the fluorescent powder provided by the invention is a solid-phase reaction synthesis method, and has the advantages of simple synthesis steps and strong practicability.
In order to achieve the purpose, the technical scheme of the invention is to design a europium ion Eu3+Activated calcium niobate indium acid red luminescent phosphor powder with a chemical expression of Ca10-xEuxInNb5-xTixO24X is europium ion Eu3+And titanium ion Ti4+Respectively doped with substituted divalent calcium ions Ca2+And pentavalent niobium ion Nb5+The value range of x is more than or equal to 0.05 and less than or equal to 1.0.
In order to facilitate the preparation and implementation of the fluorescent powder, a europium ion Eu is provided3+The preparation method of the activated calcium niobate indate red luminescent phosphor utilizes a solid-phase reaction method to prepare the europium ion Eu3+The activated calcium niobate indate red luminescent phosphor comprises the following steps:
s1: weighing according to the chemical expression Ca10-xEuxInNb5-xTixO24Weighing the following raw materials in stoichiometric ratio: containing Ca ions2+Compound of (1), Eu ion-containing Eu3+Compound of (2) and In containing indium ion3+Compound of (2), Nb ion-containing Nb5+Compound of (2) containing titanium ion Ti4+X is more than or equal to 0.05 and less than or equal to 1.0;
s2: pre-calcining, namely grinding the raw materials weighed in the step S1 to obtain raw material mixture powder, extruding the raw material mixture powder into blocks, placing the blocks in an air atmosphere for pre-calcining, wherein the pre-calcining temperature is 850-1100 ℃, and the pre-calcining time is 2-10 hours to obtain a pre-calcined product;
s3: performing secondary calcination, namely naturally cooling and grinding the pre-calcination product obtained in the step S2 to obtain pre-calcination product powder, extruding the pre-calcination product powder into blocks, and placing the blocks in an air atmosphere for secondary calcination, wherein the secondary calcination temperature is 1100-1350 ℃, and the secondary calcination time is 2-10 hours to obtain a secondary calcination product;
s4: post-treatment, namely naturally cooling and grinding the secondary calcined product in the step S3 to obtain europium ion Eu3+Activated calcium niobate indate red luminescent phosphor powder products.
Further preferably, the calcium ion Ca is contained2+The compound of (A) is calcium carbonate CaCO3Or calcium nitrate Ca (NO)3)2One of (1); the Eu ion containing europium3+Is europium oxide Eu2O3Or europium nitrate Eu (NO) hexahydrate3)3·6H2One of O; in containing indium ions3+The compound of (A) is indium oxide In2O3(ii) a The Nb ions are contained5+The compound of (A) is niobium oxide Nb2O5(ii) a The titanium ion-containing Ti4+The compound of (A) is titanium oxide TiO2。
In order to facilitate the application and popularization of the fluorescent powder, the europium ion Eu is provided3+The activated calcium niobate indate red luminescent phosphor is applied to preparing an LED lighting or display device with a near ultraviolet semiconductor chip as an excitation light source.
Further preferably, the fluorescent powder is used for preparing a light-emitting diode, a tricolor fluorescent lamp or a field emission display which takes a near ultraviolet semiconductor chip as an excitation light source.
The invention has the advantages and beneficial effects that:
1. the matrix of the fluorescent powder is made of (Nb, In, Ti) O6The fluorescent powder has excellent thermal stability and is suitable for preparing high-power lighting equipment.
2. With Eu3+Ion co-doped Ti4+The ions not only play a role in compensating for Eu3+The charge imbalance caused by the doping of the ions also increases the disturbance of the crystal lattice in the matrix, so that Eu is enabled3+The forbidden transition of ions is fully broken to realize Eu3+The effective red luminous efficiency of the ions is improved, and the cleanliness and the red luminous intensity of the fluorescent powder are improved.
3. Compared with the existing commercial red fluorescent powder, e.g. Y2O3:Eu3+，Y2O2S:Eu3+The fluorescent powder has strong excitation efficiency in a near ultraviolet wavelength region, emits red light with a main peak at 613nm under the excitation of near ultraviolet light, has the light-emitting service life of more than 1.0 millisecond, meets the requirements of light-emitting illumination and display, does not generate afterglow, and is more suitable for preparing white light LED illumination equipment prepared by matching a near ultraviolet LED chip.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a phosphor prepared according to the protocol of example 1;
FIG. 2 is an SEM image of a phosphor prepared according to the technical scheme of example 1;
FIG. 3 is a photoluminescence spectrum of phosphor light prepared according to the embodiment of example 1;
FIG. 4 is a luminescence decay curve of the phosphor prepared according to the technical scheme of example 1 at a monitoring wavelength of 613 nm;
FIG. 5 is a graph showing the emission decay at a monitoring wavelength of 613nm of a phosphor prepared according to the embodiment of example 4.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
Preparation of Ca9.2Eu0.8InNb4.2Ti0.8O24The method comprises the following steps:
s1: weighing according to the chemical expression Ca9.2Eu0.8InNb4.2Ti0.8O24(x is 0.8) weighing the following raw materials in stoichiometric ratio: CaCO3: 9.2 g; eu (Eu)2O3: 1.408 g; in2O3: 1.388 g; nb2O5: 5.582 g; TiO 22: 0.64 g;
s2: pre-calcining, namely putting the raw materials weighed in the step S1 into an agate mortar for grinding to obtain raw material mixture powder, extruding the raw material mixture powder into blocks, placing the blocks in an air atmosphere for pre-calcining, wherein the pre-calcining temperature is 850 ℃, and the pre-calcining time is 10 hours to obtain a pre-calcined product;
s3: secondary calcination, namely naturally cooling the pre-calcination product in the step S2, putting the pre-calcination product into an agate mortar for secondary grinding to obtain pre-calcination product powder, extruding the pre-calcination product powder into blocks, and placing the blocks in an air atmosphere for secondary calcination, wherein the secondary calcination temperature is 1350 ℃ and the secondary calcination time is 2 hours to obtain a secondary calcination product;
s4: post-treatment, namely naturally cooling and grinding the secondary calcined product in the step S3 to obtain europium ionsEu3+Activated calcium niobate indate red luminescent phosphor powder products.
Referring to the attached figure 1, the X-ray powder diffraction pattern of the phosphor prepared according to the technical scheme of the embodiment 1, and XRD test results show that the phosphor prepared in the embodiment 1 is a single phase and no other impurities exist;
referring to the attached figure 2, the SEM image of the fluorescent powder prepared according to the technical scheme of the embodiment 1 shows that the crystallization performance is good;
referring to fig. 3, the photoluminescence spectrum of the phosphor prepared according to the technical scheme of example 1, wherein the excitation spectrum indicates that the excitation source of red light is mainly in the near-ultraviolet region, that is, the phosphor prepared in example 1 can be well matched with the emission of the near-ultraviolet LED chip; the luminescence spectrum showed that the phosphor prepared in example 1 emitted red luminescence with a very pure chromaticity and a central luminescence wavelength of 613 nm;
referring to fig. 4, the luminescence decay curve of the phosphor prepared according to the technical scheme of the embodiment 1 under the monitoring wavelength of 613nm has the luminescence life of 1.51 milliseconds, and can meet the requirements of luminescence illumination and display without afterglow.
Example 2
Preparation of Ca9.95Eu0.05InNb4.95Ti0.05O24The method comprises the following steps:
s1: weighing according to the chemical expression Ca9.95Eu0.05InNb4.95Ti0.05O24(x is 0.05) weighing the following raw materials in stoichiometric ratio: ca (NO)3)2: 27.741 g; eu (NO)3)2: 0.287 g; in2O3: 2.359 g; nb2O5: 11.18 g; TiO 22: 0.068 g;
s2: pre-calcining, namely putting the raw materials weighed in the step S1 into an agate mortar for grinding to obtain raw material mixture powder, extruding the raw material mixture powder into blocks, and placing the blocks in an air atmosphere for pre-calcining, wherein the pre-calcining temperature is 1100 ℃, and the pre-calcining time is 2 hours to obtain a pre-calcined product;
s3: secondary calcination, namely naturally cooling the pre-calcination product in the step S2, putting the pre-calcination product into an agate mortar for secondary grinding to obtain pre-calcination product powder, extruding the pre-calcination product powder into blocks, and placing the blocks in an air atmosphere for secondary calcination, wherein the secondary calcination temperature is 1100 ℃, and the secondary calcination time is 10 hours to obtain a secondary calcination product;
s4: post-treatment, namely naturally cooling and grinding the secondary calcined product in the step S3 to obtain europium ion Eu3+Activated calcium niobate indate red luminescent phosphor powder products.
The test result shows that: the main structure, excitation spectrum, luminescence spectrum and luminescence lifetime of the phosphor product prepared in example 2 are similar to those of the phosphor prepared in example 1.
Example 3
Preparation of Ca8.8Eu1.2InNb3.8Ti1.2O24The method comprises the following steps:
s1: weighing according to the chemical expression Ca8.8Eu1.2InNb3.8Ti1.2O24(x is 1.2) weighing the following raw materials in stoichiometric ratio: CaCO3: 6.16 g; eu (Eu)2O3: 1.478 g; in2O3: 0.9716 g; nb2O5: 3.535 g; TiO 22: 0.672 g;
s2: pre-calcining, namely putting the raw materials weighed in the step S1 into an agate mortar for grinding to obtain raw material mixture powder, extruding the raw material mixture powder into blocks, placing the blocks in an air atmosphere for pre-calcining, wherein the pre-calcining temperature is 880 ℃, and the pre-calcining time is 3 hours to obtain a pre-calcined product;
s3: secondary calcination, namely naturally cooling the pre-calcination product in the step S2, putting the pre-calcination product into an agate mortar for secondary grinding to obtain pre-calcination product powder, extruding the pre-calcination product powder into blocks, and placing the blocks in an air atmosphere for secondary calcination, wherein the secondary calcination temperature is 1300 ℃, and the secondary calcination time is 6 hours to obtain a secondary calcination product;
s4: post-treatment, namely naturally cooling and grinding the secondary calcined product in the step S3 to obtain europium ion Eu3+Activated calcium niobate indate red luminescent phosphor product。
The test result shows that: the main structure, excitation spectrum, luminescence spectrum and luminescence lifetime of the phosphor product prepared in example 3 are similar to those of the phosphor prepared in example 1.
Example 4
Preparation of Ca9.4Eu0.6InNb4.4Ti0.6O24The method comprises the following steps:
s1: weighing according to the chemical expression Ca9.4Eu0.6InNb4.4Ti0.6O24(x is 0.6) weighing the following raw materials in stoichiometric ratio: CaCO3: 10.34 g; eu (Eu)2O3: 1.1616 g; in2O3: 1.527 grams; nb2O5: 6.432 g; TiO 22: 0.528 g;
s2: pre-calcining, namely putting the raw materials weighed in the step S1 into an agate mortar for grinding to obtain raw material mixture powder, extruding the raw material mixture powder into blocks, placing the blocks in an air atmosphere for pre-calcining, wherein the pre-calcining temperature is 900 ℃, and the pre-calcining time is 4 hours to obtain a pre-calcined product;
s3: secondary calcination, namely naturally cooling the pre-calcined product in the step S2, putting the pre-calcined product into an agate mortar for secondary grinding to obtain pre-calcined product powder, extruding the pre-calcined product powder into blocks, and placing the blocks in an air atmosphere for secondary calcination, wherein the secondary calcination temperature is 1250 ℃, and the secondary calcination time is 9 hours to obtain a secondary calcined product;
s4: post-treatment, namely naturally cooling and grinding the secondary calcined product in the step S3 to obtain europium ion Eu3+Activated calcium niobate indate red luminescent phosphor powder products.
The test result shows that: the main structure, excitation spectrum and luminescence spectrum of the phosphor product prepared in example 4 were similar to those of the phosphor prepared in example 1.
Referring to fig. 5, the luminescent decay curve of the phosphor prepared according to the technical scheme of the embodiment 4 under the monitoring wavelength of 613nm has the luminescent lifetime of 1.15 milliseconds, and can meet the requirements of luminescent illumination and display without afterglow.
Example 5
Preparation of Ca9EuInNb4TiO24The method comprises the following steps:
s1: weighing according to the chemical expression Ca9EuInNb4TiO24Weighing raw materials according to the stoichiometric ratio of each element in (x ═ 1): ca (NO)3)2: 10.332 g; eu (NO)3)2: 2.366 g; in2O3: 0.9716 g; nb2O5: 3.722 g; TiO 22: 0.56 g;
s2: pre-calcining, namely putting the raw materials weighed in the step S1 into an agate mortar for grinding to obtain raw material mixture powder, extruding the raw material mixture powder into blocks, and placing the blocks in an air atmosphere for pre-calcining, wherein the pre-calcining temperature is 1000 ℃, and the pre-calcining time is 4 hours to obtain a pre-calcined product;
s3: performing secondary calcination, namely naturally cooling the pre-calcination product in the step S2, putting the pre-calcination product into an agate mortar, grinding again to obtain pre-calcination product powder, extruding the pre-calcination product powder into blocks, and placing the blocks in an air atmosphere for secondary calcination, wherein the secondary calcination temperature is 1320 ℃, and the secondary calcination time is 5 hours to obtain a secondary calcination product;
s4: post-treatment, namely naturally cooling and grinding the secondary calcined product in the step S3 to obtain europium ion Eu3+Activated calcium niobate indate red luminescent phosphor powder products.
The test result shows that: the main structure, excitation spectrum, luminescence spectrum and luminescence lifetime of the phosphor product prepared in example 5 are similar to those of the phosphor prepared in example 4.
Example 6
Preparation of Ca9.8Eu0.2InNb4.8Ti0.2O24The method comprises the following steps:
s1: weighing according to the chemical expression Ca9.8Eu0.2InNb4.8Ti0.2O24(x is 0.2) weighing the following raw materials in stoichiometric ratio: CaCO3: 12.74 g; eu (Eu)2O3: 0.457 g; in2O3: 1.804 g; nb2O5：8.293 g; TiO 22: 0.208 g;
s2: pre-calcining, namely putting the raw materials weighed in the step S1 into an agate mortar for grinding to obtain raw material mixture powder, extruding the raw material mixture powder into blocks, placing the blocks in an air atmosphere for pre-calcining, wherein the pre-calcining temperature is 1050 ℃, and the pre-calcining time is 3 hours to obtain a pre-calcined product;
s3: secondary calcination, namely naturally cooling the pre-calcination product in the step S2, putting the pre-calcination product into an agate mortar for secondary grinding to obtain pre-calcination product powder, extruding the pre-calcination product powder into blocks, and placing the blocks in an air atmosphere for secondary calcination, wherein the secondary calcination temperature is 1300 ℃, and the secondary calcination time is 6 hours to obtain a secondary calcination product;
s4: post-treatment, namely naturally cooling and grinding the secondary calcined product in the step S3 to obtain europium ion Eu3+Activated calcium niobate indate red luminescent phosphor powder products.
The test result shows that: the main structure, excitation spectrum, emission spectrum and emission lifetime of the phosphor product prepared in example 6 were similar to those of the phosphor prepared in example 4.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. Europium ion Eu3+The activated calcium niobate indate red luminescent phosphor is characterized in that the chemical expression is Ca10- xEuxInNb5-xTixO24X is europium ion Eu3+And titanium ion Ti4+Respectively doped with substituted divalent calcium ions Ca2+And pentavalent niobium ion Nb5+The value range of x is more than or equal to 0.05 and less than or equal to 1.0.
2. Europium ion Eu3+The preparation method of the activated calcium niobate indate red luminescent phosphor is characterized in that the activated calcium niobate indate red luminescent phosphor is prepared by a solid-phase reaction methodThe europium ion Eu of claim 13+The activated calcium niobate indate red luminescent phosphor comprises the following steps:
s1: weighing according to the chemical expression Ca10-xEuxInNb5-xTixO24Weighing the following raw materials in stoichiometric ratio: containing Ca ions2+Compound of (1), Eu ion-containing Eu3+Compound of (2) and In containing indium ion3+Compound of (2), Nb ion-containing Nb5+Compound of (2) containing titanium ion Ti4+X is more than or equal to 0.05 and less than or equal to 1.0;
s2: pre-calcining, namely grinding the raw materials weighed in the step S1 to obtain raw material mixture powder, extruding the raw material mixture powder into blocks, placing the blocks in an air atmosphere for pre-calcining, wherein the pre-calcining temperature is 850-1100 ℃, and the pre-calcining time is 2-10 hours to obtain a pre-calcined product;
s3: performing secondary calcination, namely naturally cooling and grinding the pre-calcination product obtained in the step S2 to obtain pre-calcination product powder, extruding the pre-calcination product powder into blocks, and placing the blocks in an air atmosphere for secondary calcination, wherein the secondary calcination temperature is 1100-1350 ℃, and the secondary calcination time is 2-10 hours to obtain a secondary calcination product;
s4: post-treatment, namely naturally cooling and grinding the secondary calcined product in the step S3 to obtain europium ion Eu3+Activated calcium niobate indate red luminescent phosphor powder products.
3. The Eu ion Eu according to claim 23+The preparation method of the activated calcium niobate indate red luminescent phosphor is characterized in that the red luminescent phosphor contains calcium ions Ca2+The compound of (A) is calcium carbonate CaCO3Or calcium nitrate Ca (NO)3)2One of (1); the Eu ion containing europium3+Is europium oxide Eu2O3Or europium nitrate Eu (NO) hexahydrate3)3·6H2One of O; in containing indium ions3+The compound of (A) is indium oxide In2O3(ii) a The Nb ions are contained5+The compound of (A) is niobium oxide Nb2O5(ii) a The titanium ion-containing Ti4+The compound of (A) is titanium oxide TiO2。
4. The Eu ion according to claim 13+The activated calcium niobate indate red luminescent fluorescent powder is characterized by being used for preparing an LED lighting or display device which takes a near ultraviolet semiconductor chip as an excitation light source.
5. The europium ion Eu of claim 43+The activated calcium niobate indate red luminescent fluorescent powder is characterized by being used for preparing a light-emitting diode, a tricolor fluorescent lamp or a field emission display which takes a near ultraviolet semiconductor chip as an excitation light source.
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