CN113897197B - Blue light emitting fluorescent material with high thermal stability and preparation method and application thereof - Google Patents
Blue light emitting fluorescent material with high thermal stability and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002612 dispersion medium Substances 0.000 claims abstract description 11
- 230000000171 quenching effect Effects 0.000 claims abstract description 9
- 238000010791 quenching Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 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 3
- 239000002609 medium Substances 0.000 claims 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 3
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- 230000006872 improvement Effects 0.000 description 7
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- 238000005204 segregation Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
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- 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
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
The invention provides a blue light emitting fluorescent material with high thermal stability, a preparation method and application thereof, wherein a high-temperature solid phase method is utilized to successfully prepare a novel blue light emitting fluorescent material Sr for the first time in a reducing atmosphere under the action of a fluxing agent and a dispersion medium x Mg 2x‑1 Al 12‑2x O 17 :yEu 2+ (SMAO: eu), wherein 0.83.ltoreq.x.ltoreq.1, 0 < y.ltoreq.2%. The fluorescent material is closer to the standard blue light emission peak value, has high color purity, very high thermal stability and luminous brightness, and particularly shows negative thermal quenching performance at 80-240 ℃; compared with the traditional commercial blue fluorescent material BAM: eu 2+ Compared with the prior art, the LED light source module is better applicable to the field of high-power LEDs, and has higher practical value and wide application prospect. In addition, the raw materials used in the invention have wide sources and low price, the preparation process is simple and easy to implement, and the product has good commercial application prospect.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a blue light emitting fluorescent material with high thermal stability, and a preparation method and application thereof.
Background
White Light Emitting Diode (WLEDs) lamps are truly environment-friendly products due to the fact that the WLEDs are free of lead, mercury and other pollutants, and have the characteristics of energy conservation and long service life, and incandescent lamps and fluorescent lamps with relatively large energy consumption have been gradually replaced. In terms of market demand, white light LEDs developed for lighting application markets will be a product item with higher future usage, but the manufacturing technology, functionality and use effect of the white light LEDs are still in the starting stage at present.
At present, two main technical schemes for realizing WLEDs are available: one is to combine multiple LED chips such as blue, cyan, green, yellow, and red light to produce a continuous spectrum by a multi-chip combination (without phosphor). The spectrum generated by the method has the advantages of high light efficiency and high color rendering, but the spectrum color temperature is unstable, the control circuit is complex, the cost is high, the application performance is poor and the like due to the different performances of the monochromatic chips and the larger light attenuation difference; and the other is to coat a plurality of fluorescent powders with different luminescent colors on the ultraviolet/near ultraviolet LED chip. Compared with a multi-chip combined LED, the scheme has the advantages of stable and uniform light color, simple manufacturing method, low cost and the like, meanwhile, the use of the ultraviolet chip supplements the part of spectrum medium-short wave ultraviolet light, and the spectrum continuity is better. However, blue fluorescent materials for ultraviolet LED excitation are currently scarce in variety, so that blue fluorescent materials become an important technique for manufacturing white LEDs.
BaMgAl is commonly adopted in the market 10 O 17 :Eu 2+ (BAM:Eu 2+ ) The white light LED is manufactured by the fluorescent powder material, and the sintering temperature of the fluorescent powder is about 1500 ℃; the thermal stability of the phosphor determines the color stability of the LED device, especially high power LEDs, which can operate at temperatures above 140 ℃. However, commercial BAM: eu 2+ The thermal stability of the ultraviolet LED device is reduced to below 90 percent at the temperature of about 150 ℃, so that the ultraviolet LED device is easy to have color drift in a working device, the color stability is poor, and the application of the ultraviolet LED device in the aspect of high-power LED devices is severely restricted.
In view of the foregoing, there is a need for a new blue light emitting fluorescent material with improved high thermal stability and a method for preparing the same, which are more suitable for high-power LEDs to solve the above problems.
Disclosure of Invention
The invention aims to provide a blue light emitting fluorescent material with high thermal stability, a preparation method and application thereof, and a novel blue light emitting fluorescent material Sr is successfully prepared for the first time by using a high-temperature solid phase method x Mg 2x-1 Al 12-2x O 17 :yEu 2+ (SMAO: eu); the material has abnormal negative thermal quenching property and very high thermal stabilityThe light-emitting diode has good performance and luminous brightness, can be better suitable for the field of high-power LEDs, and has wide application prospect.
To achieve the above object, the present invention provides a blue light-emitting fluorescent material with high thermal stability, the chemical composition formula of the blue light-emitting fluorescent material is Sr x Mg 2x-1 Al 12-2x O 17 :yEu 2+ Wherein x is more than or equal to 0.83 and less than or equal to 1, and y is more than 0 and less than or equal to 2 percent.
The preparation method of the blue light emitting fluorescent material with high thermal stability comprises the following steps:
s1, accurately weighing raw materials according to the molar ratio Sr, mg, eu=x, and 2x-1:12-2x:y in the blue light emitting fluorescent material, placing the raw materials in an agate mortar, wherein x is more than or equal to 0.83 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 2, adding a fluxing agent and a dispersion medium, and uniformly grinding to obtain a basic mixture;
s2, performing a high-temperature sintering process on the basic mixture prepared in the step S1 in a reducing atmosphere to obtain the high-thermal-stability blue light emitting fluorescent material Sr x Mg 2x-1 Al 12-2x O 17 :yEu 2+ 。
As a further improvement of the present invention, in step S1, the raw materials include: an oxide containing Sr or a compound capable of being converted into the oxide is used as an Sr source; an oxide containing Mg or a compound capable of being converted into the oxide is used as a Mg source; an oxide containing Al or a compound capable of being converted into the oxide is used as an Al source; an oxide or europium nitrate salt containing Eu is used as the Eu source.
As a further improvement of the invention, in the step S2, the temperature of the high-temperature sintering process is 1350-1500 ℃ and the heat preservation time is 5-7 h.
As a further improvement of the present invention, in step S1, the flux is BaF 2
As a further improvement of the present invention, the fluxing agent BaF 2 And adding the blue light emitting fluorescent material with the total mass of 2-6% of the raw materials.
As a further improvement of the present invention, in step S2, the reductionThe air atmosphere is N with the volume ratio of 9:1 2 And H 2 Is a mixed gas of (a) and (b).
As a further improvement of the present invention, in step S1, the dispersion medium is absolute ethanol.
Use of a high thermal stability blue light emitting fluorescent material according to any of the preceding claims for the manufacture of high power LEDs.
As a further improvement of the invention, the blue light-emitting fluorescent material with high thermal stability shows negative thermal quenching performance when applied at 80-240 ℃.
The beneficial effects of the invention are as follows:
(1) The invention provides a blue light emitting fluorescent material with high thermal stability, a preparation method and application thereof, wherein a novel blue light emitting fluorescent material Sr is successfully prepared for the first time in a reducing atmosphere under the action of a fluxing agent and a dispersion medium by a high-temperature solid phase method x Mg 2x-1 Al 12-2x O 17 :yEu 2+ (x is more than or equal to 0.83 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 2 percent), the material shows abnormal negative thermal quenching performance, has very high thermal stability and luminous brightness, and especially has the emission peak intensity of about 110 percent of the original intensity when applied at 140-160 ℃, and shows ultrahigh luminous intensity; compared with the traditional commercial blue fluorescent material BAM: eu 2+ Compared with the prior art, the LED light source module is better applicable to the field of high-power LEDs, and has higher practical value and wide application prospect.
(2) Eu is a blue light emitting fluorescent material with brand new chemical composition, the fluorescent material has a narrow emission peak, is closer to a standard blue light emission peak, and has high color purity and good thermal stability; and the raw materials used in the method are wide in sources and low in price, and the preparation process is simple and easy to implement, so that the method has a good commercial application prospect.
(3) When the novel basic mixture of the blue light emitting fluorescent material is prepared, a small amount of fluxing agent and dispersion medium are added. The fluxing agent adopts BaF 2 Can promote the formation and growth of the SMAO-Eu material crystal at high temperature, and is beneficial to the stability of the crystal structure. The dispersion medium adopts absolute ethyl alcohol, so that the raw materials can be quickly and uniformly mixed, the fluorescent material with serious component segregation is prevented from being prepared after high-temperature sintering, the uniformity and stability of the crystal structure are further prevented from being influenced, and the service performance is reduced; and the absolute ethyl alcohol volatilizes faster, can not bring other impurities, and can ensure the purity of the crystal material.
Drawings
FIG. 1 shows Sr produced in example 1 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ Excitation spectrum and emission spectrum of the material.
FIG. 2 shows Sr produced in example 1 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ Emission spectrum contrast plot of the material versus commercial BAM: eu material.
FIG. 3 shows Sr produced in example 1 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ Emission intensity contrast plot of the material versus commercial BAM: eu material.
FIG. 4 shows Sr produced in example 1 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ And an emission spectrum trend graph of the material along with temperature.
FIG. 5 shows Sr produced in example 1 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ Thermal quenching performance of the material is compared with that of a commercial BAM-Eu material.
FIG. 6 shows Sr of different Eu contents prepared in examples 1 to 6 0.83 Mg 0.66 Al 10.34 O 17 :yEu 2+ XRD diffraction peak pattern of the material.
FIG. 7 shows Sr of different Eu contents prepared in examples 1 to 6 0.83 Mg 0.66 Al 10.34 O 17 :yEu 2+ Emission spectrum of the material.
FIG. 8 shows the molar ratios of Sr to Mg to Al elements of the various Sr-Mg to Al elements prepared in examples 1, 7 and comparative examples 1-4 x Mg 2x-1 Al 12- 2x O 17 :0.01Eu 2+ XRD results pattern of the material.
FIG. 9 shows Sr produced in example 1 and examples 8 to 12 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ XRD diffraction peak pattern of the material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
A blue light-emitting fluorescent material with high thermal stability has a chemical composition formula of Sr x Mg 2x-1 Al 12-2x O 17 :yEu 2+ Wherein x is more than or equal to 0.83 and less than or equal to 1, and y is more than 0 and less than or equal to 2 percent.
Particularly, the material shows abnormal negative thermal quenching performance, has very high thermal stability and luminous brightness, and especially has an emission peak intensity of about 110% of the original intensity when applied at 140-160 ℃ and higher luminous intensity. Because of the defects in the crystal of the material, electrons enter into the defect energy level, are released again into the excited state after the temperature is increased, and return to the ground state to emit light, so that the light emission is enhanced. Compared with the traditional commercial blue fluorescent material BAM: eu 2+ Compared with the prior art, the blue light emitting fluorescent material can be better suitable for the fields of manufacturing and application of high-power LEDs, and has higher practical value and wide application prospect.
The preparation method of the blue light emitting fluorescent material with high thermal stability comprises the following steps:
s1, accurately weighing raw materials according to the molar ratio Sr, mg and Al in the blue light emitting fluorescent material, wherein Eu=x, 2x-1:12-2x and y, placing the raw materials in an agate mortar, wherein x is more than or equal to 0.83 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 2, adding a fluxing agent and a dispersion medium, and uniformly grinding to obtain a basic mixture;
specifically, in step S1, the raw materials include: an oxide containing Sr or a compound capable of being converted into the oxide is used as an Sr source; an oxide containing Mg or a compound capable of being converted into the oxide is used as a Mg source; an oxide containing Al or a compound capable of being converted into the oxide is used as an Al source; an oxide or europium nitrate salt containing Eu is used as the Eu source.
In particular, the fluxing agent is BaF 2 ，BaF 2 Adding the blue light emitting fluorescent material with the total mass of 2-6% of the total mass of the raw materials; baF as fluxing agent 2 Can promote the formation and growth of the SMAO-Eu material crystal at high temperature, and is beneficial to the stability of the crystal structure. The dispersion medium is absolute ethyl alcohol, and the absolute ethyl alcohol can enable the raw materials to be mixed rapidly and uniformly, so that the fluorescent material with serious component segregation is prevented from being prepared after high-temperature sintering, further the uniformity and stability of the crystal structure are prevented from being influenced, and the service performance is reduced; and the absolute ethyl alcohol volatilizes faster, can not bring other impurities, and can ensure the purity of the crystal material.
S2, the basic mixture prepared in the step S1 is subjected to a reducing atmosphere (N with the volume ratio of 9:1 2 And H 2 The mixed gas) is subjected to a high-temperature sintering process, the temperature is 1350-1500 ℃, and the heat preservation time is 5-7 h, so that the blue light emitting fluorescent material with high thermal stability is obtained; wherein, a small amount of H in the reducing atmosphere 2 Is capable of converting Eu in a raw material 3+ Reduction to Eu 2+ So as to ensure that the preparation of the novel blue light emitting fluorescent material SMAO: eu is successful.
The novel blue light emitting fluorescent material SMAO: eu prepared by the high-temperature solid phase method is a blue light emitting fluorescent material with brand-new chemical composition, and the fluorescent material has a narrow emission peak, is closer to a standard blue light emission peak, and has high color purity and good thermal stability; and the raw materials used in the method are wide in sources and low in price, and the preparation process is simple and easy to implement, so that the method has a good commercial application prospect.
The application of the blue light emitting fluorescent material with high thermal stability, which is applicable to the fields of high-power LED manufacture and application.
Example 1
Example 1 provides a blue light emitting fluorescent material with high thermal stability and a preparation method thereof, comprising the following steps:
s1, accurately weighing raw materials (including SrCO) according to the molar ratio Sr, mg, al, eu=x, 2x-1:12-2x y of each element in the blue light emitting fluorescent material 3 、MgCO 3 、Al 2 O 3 And europium oxide) in an agate mortar, where x=0.83 and y=1%, while adding 5% of the fluxing agent BaF 2 And absolute ethyl alcohol as a dispersion medium, and grinding uniformly to obtain a basic mixture;
s2, the basic mixture prepared in the step S1 is subjected to a reducing atmosphere (45 sccm of N 2 And 5sccm of H 2 Mixed gas) is subjected to high-temperature sintering process at 1400 ℃ for 6 hours to obtain the blue light-emitting fluorescent material Sr with high thermal stability 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ 。
Referring to FIGS. 1-2, FIG. 1 shows Sr produced in example 1 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ The excitation spectrum and the emission spectrum of the material show that Sr in the excitation spectrum shown in figure 1 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ The material shows stronger absorption within the range of 250-450 nm, and the optimal excitation peak is positioned near 334nm, so that the material is suitable for ultraviolet LED excitation. Under 334nm excitation, the sample emission peak shows blue light emission with a main peak at 458nm, and is attributed to 5d-4f transition emission generated by Eu occupying Sr position. FIG. 2 shows Sr produced in example 1 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ Emission spectrum comparison (normalization) of materials and commercial BAM: eu materials, from which it can be seen that Sr 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ The main emission peak (indicated by the dotted line) of the material is closer to the standard blue emission peak 460nm.
Referring to FIG. 3, FIG. 3 shows Sr produced in example 1 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ As can be seen from the graph of the emission intensity of the material versus the commercial BAM: eu material, sr is present at the respective optimum excitation wavelength 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ The highest intensity of the emission peak of the material can reach about 92% of the commercial powder BAM: eu, and the integral intensity of the emission peak can reach 109% of the BAM: eu, so that the material has very high luminous brightness.
Referring to FIGS. 4-5, FIG. 4 shows Sr produced in example 1 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ And an emission spectrum trend graph of the material along with temperature. As can be seen from FIG. 4, the novel Sr produced by the present invention 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ The material has very abnormal negative temperature quenching behavior. When the temperature is increased from room temperature to about 140 ℃, the emission peak intensity is gradually increased, and when the temperature is increased to about 140 ℃, the emission peak intensity reaches 111% of the initial intensity. FIG. 5 shows Sr produced in example 1 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ As can be seen from FIG. 5, the emission intensity of BAM: eu has decreased to 91% of the initial intensity when the temperature reaches 140 ℃. When the temperature reaches 230 ℃, sr 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ The emission peak intensity of the material can still keep 106% of its initial intensity, while the intensity of BAM: eu has been reduced to 86%. Thermal stability test found that Sr 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ Compared with BAM: eu, the material has excellent thermal stability, and is more suitable for manufacturing and application of high-power ultraviolet LEDs.
Examples 2 to 6
Examples 2-6 provide a blue light-emitting fluorescent material with high thermal stability and a preparation method thereof, and compared with example 1, the difference is that in examples 2-6, in step S1, raw materials are accurately weighed according to Sr: mg: al: eu=x: 2x-1:12-2x: y, wherein x=0.83, y=0.25%, 0.5%, 0.75%, 1.5%, 2%, respectively, and the rest is substantially the same as example 1, and a description thereof is omitted.
Referring to FIGS. 6 to 7, FIG. 6 shows Sr with different Eu contents prepared in examples 1 to 6 0.83 Mg 0.66 Al 10.34 O 17 :yEu 2+ XRD diffraction peak patterns of the materials are shown in the patterns, and all samples are better matched with standard cards by XRD and are single-phase samples. FIG. 7 shows Sr of different Eu contents prepared in examples 1 to 6 0.83 Mg 0.66 Al 10.34 O 17 :yEu 2+ An emission spectrum of the material; as can be seen from the figure, eu is in Sr x Mg 2x-1 Al 12-2x O 17 :yEu 2+ The optimum doping concentration in the material is 1.5%.
Example 7
Embodiment 7 provides a blue light emitting fluorescent material with high thermal stability and a preparation method thereof, and compared with embodiment 1, the difference is that in embodiment 7, in step S1, raw materials are accurately weighed according to Sr: mg: al: eu=x: 2x-1:12-2x:y, wherein x=1, y=1%, and the rest is substantially the same as embodiment 1, and details are not repeated here.
Comparative examples 1 to 4
Comparative examples 1 to 4 provide a blue light-emitting fluorescent material with high thermal stability and a method for preparing the same, which are different from example 1 in that in step S1, the comparative examples 1 to 4 accurately weigh raw materials according to Sr: mg: al: eu=x: 2x-1:12-2x: y, wherein x is 0.5, 0.75, 1.25, 1.5, y=1%, respectively, and the remainder are substantially the same as example 1, and are not described herein.
Referring to FIG. 8, FIG. 8 shows the Sr of examples 1, 7 and comparative examples 1-4 in different mole ratios of Sr-Mg-Al elements x Mg 2x-1 Al 12-2x O 17 :0.01Eu 2+ As can be seen from the XRD result diagram of the material, when x is more than or equal to 0.83 and less than or equal to 1, the XRD of the sample can keep a stable single phase; in comparative examples 1 to 4, samples were taken when x > 1 and x < 0.83The phase change occurs, and the novel blue light emitting fluorescent material cannot be obtained.
Examples 8 to 12
Examples 8 to 12 provide a blue light-emitting fluorescent material having high thermal stability and a method for producing the same, which are different from example 1 in that examples 8 to 12 are provided with a flux BaF added in step S1 2 The amounts of (a) are 0, 2%, 3%, 4%, 6% (x in fig. 9), respectively, and the remainder are substantially the same as those of example 1, and are not described in detail herein.
Referring to FIG. 9, FIG. 9 shows Sr produced in example 1 and examples 8 to 12 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ The XRD diffraction peak diagram of the material can be determined from the graph, and the sample is BaF under the conditions of sintering temperature of 1400 ℃ and heat preservation time of 6h 2 The crystal structure of the sample obtained at an addition level of 5% is the best. XRD test results show that Sr 0.83 Mg 0.67 Al 10.33 O 17 :0.01Eu 2+ Has a typical trigonal system and is well matched with a standard PDF card (ICSD # 82105), and the prepared Sr 0.83 Mg 0.66 Al 10.34 O 17 :0.01Eu 2+ Is a single phase sample.
In summary, the invention provides a blue light emitting fluorescent material with high thermal stability, a preparation method and application thereof, and a novel blue light emitting fluorescent material Sr is successfully prepared for the first time in a reducing atmosphere under the action of a fluxing agent and a dispersion medium by a high-temperature solid phase method x Mg 2x-1 Al 12-2x O 17 :yEu 2+ (x is more than or equal to 0.83 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 2%), the fluorescent material has a narrow emission peak, is closer to the standard blue light emission peak, and has high color purity and good thermal stability; and the raw materials used in the method are wide in sources and low in price, and the preparation process is simple and easy to implement, so that the method has a good commercial application prospect. Sr of the invention x Mg 2x-1 Al 12-2x O 17 :yEu 2+ Material Sr was prepared at x=0.83, y=1% 0.83 Mg 0.67 Al 10.33 O 17 :0.01Eu 2+ The material shows abnormal negative thermal quenching performance, has very high thermal stability and luminous brightness,especially when applied at 140-160 ℃, the emission peak intensity is about 110% of the original intensity, and the ultra-high thermal stability is shown; compared with the traditional commercial blue fluorescent material BAM: eu 2+ Compared with the prior art, the LED light source module is better applicable to the field of high-power LEDs, and has higher practical value and wide application prospect.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. A blue light-emitting fluorescent material with high thermal stability is characterized in that the chemical composition formula of the blue light-emitting fluorescent material is Sr x Mg 2x-1 Al 12-2x O 17 :yEu 2+ Wherein x= 0.83,0 < y.ltoreq.2%; the blue light emitting fluorescent material with high thermal stability shows negative thermal quenching performance when applied at the temperature of 80-240 ℃; the preparation method of the blue light emitting fluorescent material with high thermal stability comprises the following steps:
s1, accurately weighing raw materials according to the molar ratio Sr: mg: al: eu=x: 2x-1:12-2x: y in the blue light emitting fluorescent material, placing the raw materials in an agate mortar, wherein x= 0.83,0 < y is less than or equal to 2%, adding a fluxing agent and a dispersing medium at the same time, and uniformly grinding to obtain a basic mixture;
s2, performing a high-temperature sintering process on the basic mixture prepared in the step S1 in a reducing atmosphere to obtain the high-thermal-stability blue light emitting fluorescent material Sr x Mg 2x-1 Al 12-2x O 17 :yEu 2+ The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the high-temperature sintering process is 1350-1500 ℃, and the heat preservation time is 5-7 h.
2. The high thermal stability blue light emitting phosphor of claim 1, wherein in step S1, the raw materials comprise: an oxide containing Sr or a compound capable of being converted into the oxide is used as an Sr source; an oxide containing Mg or a compound capable of being converted into the oxide is used as a Mg source; an oxide containing Al or a compound capable of being converted into the oxide is used as an Al source; an oxide or europium nitrate salt containing Eu is used as the Eu source.
3. The high thermal stability blue light emitting phosphor of claim 1, wherein in step S1, the flux is BaF 2 。
4. The high thermal stability blue light emitting phosphor of claim 3, wherein said flux BaF 2 And adding the blue light emitting fluorescent material with the total mass of 2-6% of the raw materials.
5. The high thermal stability blue light emitting phosphor of claim 3, wherein in step S2, the reducing atmosphere is N in a volume ratio of 9:1 2 And H 2 Is a mixed gas of (a) and (b).
6. The high thermal stability blue light emitting phosphor of claim 1, wherein in step S1, the dispersion medium is absolute ethanol.
7. Use of a high thermal stability blue light emitting fluorescent material according to any one of claims 1-6 for the manufacture of high power LEDs.
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