CN107353900A - A kind of niobates fluorescent material, its preparation method and light emitting diode - Google Patents
A kind of niobates fluorescent material, its preparation method and light emitting diode Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 5
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 8
- -1 rare-earth ions Chemical class 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000523 sample Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 238000000695 excitation spectrum Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000000295 emission spectrum Methods 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000002284 excitation--emission spectrum Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006101 laboratory sample Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
- C09K11/7744—Chalcogenides
- C09K11/7746—Chalcogenides with alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
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- C—CHEMISTRY; METALLURGY
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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
- C09K11/7759—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing samarium
- C09K11/776—Chalcogenides
- C09K11/7761—Chalcogenides with alkaline earth metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
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Abstract
The present invention provides a kind of niobates fluorescent material, has following chemical formula：Sr5‑xNb4O15：xR3+, R3+For Tb3+, Sm3+Or Eu3+；0.005≤x≤0.5.By adjusting proportioning of the different doping with rare-earth ions in matrix, to modulate Sr5‑xNb4O15：xR3+The emission wavelength of fluorescent material.Tb provided by the invention3+/Sm3+/Eu3+Doping niobates fluorescent material can improve the luminescent properties of white light LED luminescent device, have that colour gamut is wide, low energy consumption, it is pollution-free the advantages that.By adjusting the concentration of each doping with rare-earth ions, the fluorescent material sends green glow, yellowish-white light and orange light respectively under ultraviolet or near ultraviolet excitated.Fluorescent material preparation method of the present invention is simple, can volume production, cost is low, pollution-free, can meet the production application requirement of LED field, has wide practical use in illumination, display screen etc..
Description
Technical field
The invention belongs to rare earth luminescent material technical field, more particularly to a kind of niobates fluorescent material, its preparation method and
Light emitting diode.
Background technology
LED (Light Emitting Diode) is a kind of semiconductor light emitting for converting electrical energy into luminous energy
Device.InGaN bases LED pipe can launch ultraviolet or near ultraviolet (370-410nm), be made available for white light LEDs.White light LEDs have
Luminous efficiency is high, energy-conserving and environment-protective, small volume, the advantages that long lifespan, overcomes that traditional lamp source luminous efficiency is low, and service life is short,
The shortcomings of dustiness is high, it is described as forth generation lighting source.With the popularization of low-carbon economy idea, white light LEDs are with energy-efficient
The advantages of become important light source.
LED realizes that white light has three kinds of methods using fluorescent material：The first implementation method is that green is coated on blue LED die
And red fluorescence powder, green glow that the blue light sent by chip and fluorescent material are sent and feux rouges is compound obtains white light；It is but this
The effective conversion efficiency of fluorescent material used in method is relatively low, and especially the efficiency of red fluorescence powder needs raising by a relatively large margin.
Second method is that the yellow fluorescent powder that can be stimulated by blue light is applied on blue LED die, what chip was sent
Blue light obtains white light with the gold-tinted complementation that fluorescent material is sent.The shortcomings that one principle of this method is exactly Ce in the fluorophor3+
The emission spectrum of ion does not have continuous spectrum characteristic, and colour rendering is poor, it is difficult to meets the requirement of low colour temperature illumination.
The third implementation method is that the fluorescent material of three primary colours or multiple color is applied on purple light or ultraviolet leds chip,
Realized using the long wave ultraviolet light (370nm-380nm) or purple light (380nm-410nm) of the chip emission come excitated fluorescent powder
White light emission, this method colour rendering is more preferable compared with first two, but the commercial red and green emitting phosphor of mesh is mostly sulfide systems, pollution
Degree is high, and the universal luminous efficiency of red fluorescence powder is low, and heat endurance is poor.
Nowadays LED has had different colors, and such as GaAllnP is red, green glow, while LED is also provided with superelevation
Brightness, and it is also more and more extensive on the research of white light LEDs, the market demand is also expanding day by day, but for instantly, also lacks
Colour gamut is wider, can be by ultraviolet or near ultraviolet excitated single-phase phosphor, while red fluorescence powder also generally existing luminous efficiency
It is not high, the problem of heat endurance difference.Therefore, researching and developing such fluorescent material for complying with the market demand has value and significance.
The content of the invention
It is an object of the invention to provide a kind of niobates fluorescent material, its preparation method and light emitting diode, in the present invention
Niobates fluorescent material can be in ultraviolet or near ultraviolet excitated emitted green light, yellowish-white light and orange light, and orange red emitting phosphor
Luminous efficiency is high, and heat endurance is good.
The present invention provides a kind of niobates fluorescent material, has following chemical formula：
Sr5-xNb4O15：xR3+,
R3+For Tb3+, Sm3+Or Eu3+；0.005≤x≤0.5.
Preferably, 0.01≤x≤0.4.
Preferably, the excitation wavelength of the niobates fluorescent material is 200~400nm.
The present invention provides a kind of preparation method of niobates fluorescent material, comprises the following steps：
By Sr sources, Nb sources and R3+It is sintered and grinds successively after the mixing of source, obtains niobates fluorescent material；
R3+For Tb3+, Sm3+Or Eu3+；
The Sr sources, Nb sources and R3+Source is according to mol ratio Sr：Nb：R3+=(5-x)：4：X is mixed.
Preferably, the Sr sources are SrCO3；
The Nb sources are Nb2O5；The R3+Source is Tb4O7、Sm2O3Or Eu2O3。
Preferably, 0.005≤x≤0.5.
Preferably, the temperature of the sintering is 1100~1300 DEG C；
The time of the sintering is 3~9 hours.
Preferably, the temperature of the sintering is realized by heating up, and the speed of the heating is 200~300 DEG C/h.
The present invention provides a kind of light emitting diode, including niobates fluorescent material described above.
The present invention provides a kind of niobates fluorescent material, has following chemical formula：Sr5-xNb4O15：xR3+, R3+For Tb3+, Sm3+
Or Eu3+.By adjusting proportioning of the different doping with rare-earth ions in matrix, to modulate Sr5-xNb4O15：xR3+Fluorescent material lights
Wavelength.Tb provided by the invention3+/Sm3+/Eu3+Doping niobates fluorescent material can improve the luminescent properties of white light LED luminescent device,
It is wide with colour gamut, low energy consumption, it is pollution-free the advantages that.By adjusting the concentration of each doping with rare-earth ions, the fluorescent material ultraviolet or
Under near ultraviolet excitated, green glow, yellowish-white light and orange light are sent respectively.Fluorescent material preparation method of the present invention is simple, can volume production, cost
It is low, it is pollution-free, the production application requirement of LED field can be met, had wide practical use in illumination, display screen etc..It is real
Test result to show, the red fluorescence powder in the present invention has good heat endurance, and its quantum efficiency is 41.7%.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is Sr of the present invention5-xNb4O15：xTb3+Excitation spectrum and emission spectrum；
Fig. 2 is Sr of the present invention5-xNb4O15：xSm3+Excitation spectrum and emission spectrum；
Fig. 3 is Sr of the present invention5-xNb4O15：xEu3+Excitation spectrum and emission spectrum；
Fig. 4 is the chromaticity coordinate figure of niobates fluorescent material in the embodiment of the present invention 1~16；
Fig. 5 is Sr4.75Nb4O15：0.25Eu3+Orange red fluorescent powder from 30 DEG C to 220 DEG C of room temperature when emission spectrum；
Fig. 6 is the XRD diffracting spectrums of each fluorescent material sample in the embodiment of the present invention 1~16.
Embodiment
The present invention provides a kind of niobates fluorescent material, has following chemical formula：
Sr5-xNb4O15：xR3+,
R3+For Tb3+, Sm3+Or Eu3+；0.005≤x≤0.5.
In the present invention, 0.01≤x≤0.4, specifically, in an embodiment of the present invention, the niobates fluorescent material can
To be below formula：Sr4.995Nb4O15：0.005Tb3+、Sr4.99Nb4O15：0.01Tb3+、Sr4.98Nb4O15：0.02Tb3+、
Sr4.97Nb4O15：0.03Tb3+、Sr4.95Nb4O15：0.05Tb3+、Sr4.99Nb4O15：0.01Sm3+、Sr4.97Nb4O15：0.03Sm3+、
Sr4.96Nb4O15：0.04Sm3+、Sr4.95Nb4O15：0.05Sm3+、Sr4.93Nb4O15：0.07Sm3+、Sr4.90Nb4O15：0.10Eu3+、
Sr4.85Nb4O15：0.15Eu3+、Sr4.80Nb4O15：0.20Eu3+、Sr4.75Nb4O15：0.25Eu3+、Sr4.70Nb4O15：0.30Eu3+Or
Sr4.65Nb4O15：0.35Eu3+。
In the present invention, the excitation wavelength of the niobates fluorescent material is 200~400nm, i.e. niobates in the present invention
Fluorescent material can light under ultraviolet or black light exciting.Under being excited in 200~350nm wave-length coverages, in the present invention
Chemical formula is Sr5-xNb4O15：xTb3+Niobates fluorescent material green light；Under being excited in 200~400nm wave-length coverages, this hair
Bright middle chemical formula is Sr5-xNb4O15：xSm3+Niobates fluorescent material jaundice white light, in 200~400nm wave-length coverages, this hair
Bright middle chemical formula is Sr5-xNb4O15：xEu3+Niobates fluorescent material hair orange light.
Present invention also offers a kind of preparation method of niobates fluorescent material, comprise the following steps：
By Sr sources, Nb sources and R3+It is sintered and grinds successively after the mixing of source, obtains niobates fluorescent material；
R3+For Tb3+, Sm3+Or Eu3+；
The Sr sources, Nb sources and R3+Source is according to mol ratio Sr：Nb：R3+=(5-x)：4：X is mixed.
The present invention is preferably by Sr sources, Nb sources and R3+It is fully ground after the mixing of source, is then transferred in corundum crucible, enters
Row sinters, and takes out sinter after sintering, attrition grinding, obtains niobates fluorescent material.
In the present invention, the Sr sources are SrCO3；The Nb sources are Nb2O5；The R3+Source is Tb4O7、Sm2O3Or Eu2O3。
Grinding no special limitation of the present invention to the raw material, the mixture is fully ground uniformly.Raw material is ground
Mill generally 1 hour, the grinding to the sinter is generally 5 minutes or so.
The temperature of the sintering is preferably 1100~1300 DEG C, more preferably 1250 DEG C；The time of the sintering is 3~9
Hour, more preferably 4~8 hours, most preferably 6 hours, the speed of the heating is preferably 200~300 DEG C/h, more excellent
Elect 250 DEG C/h as.The present invention sintering is preferably carried out under air atmosphere, specifically, can under air atmosphere with
250 DEG C/h of heating rate is heated to 1250 DEG C, is incubated 6 hours, after temperature is down to room temperature, sinter is taken out.
Present invention also offers a kind of light emitting diode, including niobates fluorescent material described above.The present invention luminous two
The miscellaneous part of pole pipe does not have special limitation, the Light emitting diode component commonly used using those skilled in the art.This hair
It is bright there is no special limitation to niobates fluorescent material dosage on a light emitting diode and painting method.
The present invention provides a kind of niobates fluorescent material, has following chemical formula：Sr5-xNb4O15：xR3+, R3+For Tb3+, Sm3+
Or Eu3+.By adjusting proportioning of the different doping with rare-earth ions in matrix, to modulate Sr5-xNb4O15：xR3+Fluorescent material lights
Wavelength.Tb provided by the invention3+/Sm3+/Eu3+Doping niobates fluorescent material can improve the luminescent properties of white light LED luminescent device,
It is wide with colour gamut, low energy consumption, it is pollution-free the advantages that.By adjusting the concentration of each doping with rare-earth ions, the fluorescent material ultraviolet or
Under near ultraviolet excitated, green glow, yellowish-white light and orange light are sent respectively.Fluorescent material preparation method of the present invention is simple, can volume production, cost
It is low, it is pollution-free, the production application requirement of LED field can be met, had wide practical use in illumination, display screen etc..It is real
Test result to show, the red fluorescence powder in the present invention has good heat endurance, and its quantum efficiency is 41.7%.
In order to further illustrate the present invention, with reference to embodiments to a kind of niobates fluorescent material provided by the invention, its
Preparation method and light emitting diode are described in detail, but can not be understood as limiting the scope of the present invention.
Embodiment 1
1.1061g SrCO are accurately weighed respectively3, 0.7974g Nb2O5, 0.0014g Tb4O7, in agate mortar fully
Load corundum Noah's ark after grinding, then be placed in tube furnace, be heated to 1250 DEG C in air atmosphere, be incubated 6 hours, treat its cooling
Taken out after to room temperature, product is ground to fine powder, Sr is made4.995Nb4O15：0.005Tb3+Fluorescent material sample.
Implement 2~5
The SrCO in 1 will be implemented3And Tb4O7Change Weight To table 1 in data, specific chemical formula composition, raw material proportioning and
Corresponding chromaticity coordinate value is as shown in Table 1.
The raw material proportioning of 1 embodiment of the present invention of table 1~5 and corresponding chromaticity coordinate value
Embodiment 1~5 is Sr in the present invention5-xNb4O15：xTb3+Laboratory sample.The excitation and emission spectra of this group of sample
As shown in figure 1, Fig. 1 is Sr of the present invention5-xNb4O15：xTb3+Excitation spectrum and emission spectrum.
(a) is the excitation spectrum under 544nm wavelength monitorings in Fig. 1, and corresponding ion transition is as shown in mark in figure, (b)
450~650nm multimodal spectrum is presented in emission spectrum in the case where 298nm is excited, sample, and specific crest is corresponded in ion transition such as figure
Shown in mark.Peak wavelength is located at 544nm, and in Tb3+During the molar concentration x=0.01 of ion, transmitting light intensity reaches maximum, i.e.,
In example Sr of the present invention5-xNb4O15：xTb3+In, Tb3+Ion optimum doping concentration is 0.01.
Implement 6~10
The Tb in 1 will be implemented4O7Replace with Sm2O3, SrCO3And Sm2O3Data in Change Weight To table 2, remaining operation are same
Embodiment 1.Specific chemical formula composition, raw material proportioning and corresponding chromaticity coordinate value are as shown in table 2.
The raw material proportioning of 2 embodiment of the present invention of table 6~10 and corresponding chromaticity coordinate value
Embodiment 6~10 is Sr in the present invention5-xNb4O15：xSm3+Laboratory sample.This group of sample excites and launches light
Spectrum is as shown in Fig. 2 Fig. 2 is Sr of the present invention5-xNb4O15：xSm3+Excitation spectrum and emission spectrum.
In Fig. 2, (a) figure is the excitation spectrum under 598 wavelength monitorings, and (b) figure is the transmitting light in the case where 407nm is excited
500~700nm multimodal spectrum is presented in spectrum, sample, and specific crest corresponds to ion transition as shown in mark in figure.Peak wavelength is located at
598nm, and in Sm3+During the molar concentration x=0.03 of ion, transmitting light intensity reaches maximum, i.e., in example Sr of the present invention5- xNb4O15：xSm3+In, Sm3+Ion optimum doping concentration is 0.03.
Implement 11~16
The Tb in 1 will be implemented4O7Replace with Eu2O3, SrCO3And Eu2O3Data in Change Weight To table 3, remaining operation are same
Embodiment 1.Specific chemical formula composition, raw material proportioning and corresponding chromaticity coordinate value are as shown in table 3.
Raw material proportioning and corresponding chromaticity coordinate value in the embodiment of the present invention 11~16 of table 3
Embodiment 11~16 is Sr in the present invention5-xNb4O15：xEu3+Laboratory sample.This group of sample excites and launches light
Spectrum is as shown in figure 3, Fig. 3 is Sr of the present invention5-xNb4O15：xEu3+Excitation spectrum and emission spectrum.
(a) is the excitation spectrum under 612nm wavelength monitorings in Fig. 3；(b) it is the emission spectrum in the case where 393nm is excited, sample
550~700nm multimodal spectrum is presented in product, and specific crest corresponds to ion transition as shown in mark in figure.Peak wavelength is located at
612nm, and in Eu3+During the molar concentration x=0.25 of ion, transmitting light intensity reaches maximum, i.e., in example Sr of the present invention5- xNb4O15：xEu3+In, Eu3+Ion optimum doping concentration is 0.25.
The present invention is mapped the chromaticity coordinate value of each sample in embodiment 1~16, as shown in figure 4, Fig. 4 is the present invention
The chromaticity coordinate figure of niobates fluorescent material in embodiment 1~16.
A curves are Sr in the present invention in Fig. 45-xNb4O15：xTb3In different Tb3+The chromaticity coordinate of fluorescent material under doping concentration
Value set, it is green glow to show the light-emitting phosphor color region.Optimal luminescent concentration samples Sr5-xNb4O15：0.01Tb3+Corresponding diagram
A ' samples in 6, its corresponding glow color is in green.
B curves are Sr in the present invention in Fig. 45-xNb4O15：0.03Sm3+In different Sm3+The colourity of fluorescent material under doping concentration
Set of coordinate values, it is yellowish-white light to show the light-emitting phosphor color region.Optimal luminescent concentration samples Sr5-xNb4O15：0.03Sm3+
B ' samples in corresponding diagram 6, its corresponding glow color is in yellow-white.
C curve is Sr in the present invention in Fig. 45-xNb4O15：0.03Eu3+In different Eu3+The colourity of fluorescent material under doping concentration
Set of coordinate values, show the light-emitting phosphor color region from orange light to feux rouges.Optimal luminescent concentration samples Sr5-xNb4O15：
0.25Eu3+C ' samples in corresponding diagram 6, its corresponding glow color is in orange red.
The present invention is to Sr4.75Nb4O15：0.25Eu3+Fluorescent material has carried out heat stability testing, as a result as shown in figure 5, Fig. 5
For Sr4.75Nb4O15：0.25Eu3+Orange red fluorescent powder from 30 DEG C to 220 DEG C of room temperature when emission spectrum.Excitation wavelength is
393nm, from emission spectrum, transmitting peak position keeps constant, and launches peak intensity and raise and reduce with temperature, 140 DEG C of hair
Penetrate 78% when spectral intensity is 30 DEG C, intensity is down to 62% at 180 DEG C.During higher than 180 DEG C, transmitting peak intensity continues slightly drop
It is low, it is seen that Sr4.75Nb4O15：0.25Eu3+Fluorescent material has good heat endurance, and its quantum efficiency is 41.7%, can be used as latent
Near ultraviolet excitated orange red fluorescent powder.
The XRD diffracting spectrums of each fluorescent material sample are as shown in fig. 6, Fig. 6 is implemented for the present invention in the embodiment of the present invention 1~16
The XRD diffracting spectrums of each fluorescent material sample in example 1~16.Shown through XRD test results, it is each glimmering in the embodiment of the present invention 1~16
The diffracting spectrum and Sr of light powder sample and pure matrix sample5Nb4O15Standard card substantially conforms to, and shows to work as embodiment rare earth ion
It is incorporated into matrix Sr5Nb4O15When, the parent lattice structure does not change, that is, the sample synthesized is single-phase, therefore the experiment
Fluorescent material of the present invention can be successfully made in preparation method.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of niobates fluorescent material, there is following chemical formula：
Sr5-xNb4O15：xR3+,
R3+For Tb3+, Sm3+Or Eu3+；0.005≤x≤0.5.
2. niobates fluorescent material according to claim 1, it is characterised in that 0.01≤x≤0.4.
3. niobates fluorescent material according to claim 1, it is characterised in that the excitation wavelength of the niobates fluorescent material is
200~400nm.
4. a kind of preparation method of niobates fluorescent material, comprises the following steps：
By Sr sources, Nb sources and R3+It is sintered and grinds successively after the mixing of source, obtains niobates fluorescent material；
R3+For Tb3+, Sm3+Or Eu3+；
The Sr sources, Nb sources and R3+Source is according to mol ratio Sr：Nb：R3+=(5-x)：4：X is mixed.
5. preparation method according to claim 4, it is characterised in that the Sr sources are SrCO3；
The Nb sources are Nb2O5；The R3+Source is Tb4O7、Sm2O3Or Eu2O3。
6. preparation method according to claim 4, it is characterised in that 0.005≤x≤0.5.
7. preparation method according to claim 4, it is characterised in that the temperature of the sintering is 1100~1300 DEG C；
The time of the sintering is 3~9 hours.
8. preparation method according to claim 4, it is characterised in that the temperature of the sintering is realized by heating up, described
The speed of heating is 200~300 DEG C/h.
A kind of 9. light emitting diode, it is characterised in that including the niobates fluorescent material described in claims 1 to 3 any one or
Niobates fluorescent material made from preparation method described in claim 4~8 any one.
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Cited By (3)
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| CN108531174A (en) * | 2018-04-27 | 2018-09-14 | 常州工程职业技术学院 | A kind of Eu3+Niobate red illuminating material of doping and preparation method thereof |
| CN108893112A (en) * | 2018-08-09 | 2018-11-27 | 中山大学 | A kind of red fluorescence powder and preparation method thereof that the trivalent europium ion applied to WLED device adulterates |
| CN114574203A (en) * | 2022-03-25 | 2022-06-03 | 成都理工大学 | Blue light excitated Pr3+、Eu3+Doped color-adjustable nano fluorescent powder and preparation method thereof |
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| CN104560040A (en) * | 2015-01-23 | 2015-04-29 | 南京工业大学 | Niobate fluorescent powder for near ultraviolet white light LED and preparation method thereof |
| CN105524615A (en) * | 2015-12-14 | 2016-04-27 | 常熟理工学院 | Niobate red phosphor for white-light LEDs and preparation method thereof |
| CN106833642A (en) * | 2017-01-05 | 2017-06-13 | 中山大学 | A kind of polyion activation single-matrix white fluorescent material being applied in WLED devices and preparation method thereof |
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| CN102433118A (en) * | 2011-11-24 | 2012-05-02 | 苏州大学 | Niobate red fluorescent powder as well as preparation method and application thereof |
| CN104560040A (en) * | 2015-01-23 | 2015-04-29 | 南京工业大学 | Niobate fluorescent powder for near ultraviolet white light LED and preparation method thereof |
| CN105524615A (en) * | 2015-12-14 | 2016-04-27 | 常熟理工学院 | Niobate red phosphor for white-light LEDs and preparation method thereof |
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| CN108531174A (en) * | 2018-04-27 | 2018-09-14 | 常州工程职业技术学院 | A kind of Eu3+Niobate red illuminating material of doping and preparation method thereof |
| CN108893112A (en) * | 2018-08-09 | 2018-11-27 | 中山大学 | A kind of red fluorescence powder and preparation method thereof that the trivalent europium ion applied to WLED device adulterates |
| CN114574203A (en) * | 2022-03-25 | 2022-06-03 | 成都理工大学 | Blue light excitated Pr3+、Eu3+Doped color-adjustable nano fluorescent powder and preparation method thereof |
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