CN103627392B - A kind of stibnate base red fluorescent powder and its preparation method and application - Google Patents
A kind of stibnate base red fluorescent powder and its preparation method and application Download PDFInfo
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- CN103627392B CN103627392B CN201310585702.6A CN201310585702A CN103627392B CN 103627392 B CN103627392 B CN 103627392B CN 201310585702 A CN201310585702 A CN 201310585702A CN 103627392 B CN103627392 B CN 103627392B
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- stibnate
- fluorescent powder
- ion
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- 239000000843 powder Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims description 78
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 26
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 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 9
- 238000000227 grinding Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052693 Europium Inorganic materials 0.000 claims description 7
- -1 europium ion Chemical class 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910001439 antimony ion Inorganic materials 0.000 claims description 6
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229910000379 antimony sulfate Inorganic materials 0.000 claims description 4
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 claims description 4
- 239000008139 complexing agent Substances 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 4
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- WBJXZTQXFVDYIZ-UHFFFAOYSA-N [Sb].[N+](=O)(O)[O-] Chemical compound [Sb].[N+](=O)(O)[O-] WBJXZTQXFVDYIZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005424 photoluminescence Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 4
- 239000002912 waste gas Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 2
- 229920002994 synthetic fiber Polymers 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 11
- 238000000695 excitation spectrum Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 229910013553 LiNO Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical class [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
Abstract
The invention discloses a kind of stibnate base red fluorescent powder, it is characterized in that: chemical formula is LiLa
2-2xe
u2xsbO
6, wherein x is Eu
3+doping substitutes La
3+mol ratio coefficient, span is 0.001≤x≤0.6.This red fluorescence powder is the fluorescent synthetic materials with high-luminous-efficiency, has higher crystallinity and visible light permeability, its can ultraviolet, near ultraviolet and blue-light excited under, send the ruddiness of predominant wavelength 614 nanometer, red degree is pure; Coordinate with green emitting phosphor, be coated on blue-light LED chip and can prepare novel white light LEDs.The present invention provides the preparation method of described stibnate base red fluorescent powder simultaneously, and the method abundant raw material source is cheap; and preparation technology is simple; easy handling, material without the need to rare gas element or protection of reducing atmosphere, obviously reduces energy consumption and product cost in preparation process.Compared with other sulfide, halogenide, product easily collecting, without waste water and gas discharge, environmentally friendly.
Description
Technical field
The present invention relates to a kind of luminescent material and its preparation method and application, in particular to one at UV-light, near-ultraviolet light under blue-light excited, launch a kind of novel stibnate base red fluorescent powder of red fluorescence, can be applied and be packaged in outside InGaN diode, be applied to and regulate with the various illuminations that are excitaton source of ultraviolet, near ultraviolet and blue light, display and photoluminescence colourity, belong to phosphor technical field.
Background technology
White light LEDs is the green light source got most of the attention 21 century, and have wide market and application prospect, have operating voltage low, current consumption is few, stable performance, and the life-span is long, shock resistance, and vibration resistance is strong, the advantages such as lightweight, volume is little, and cost is low, and luminescence response is fast.Adopt near-ultraviolet light 350 ~ 410 nanometer InGaN tube core to excite three primary colors fluorescent powder to realize white light LEDs and become at present one of focus of this field research and development in the world, be considered to the leading of White-light LED illumination of new generation.
Rare-earth trichromatic luminescent lamp uses red, blue, green three kinds of fluorescent material, the fluorescent material of these three kinds of primary colours is the main raw material(s)s for the production of energy-efficient lamp, this luminescent lamp is compared with ordinary incandescent lamp, reducing power consumption can up to 80%, and the colour temperature close with daylight can be obtained, make illuminated object pure color undistorted, its production process environmentally safe, therefore, exploitation is the redness of new and effective, Heat stability is good, green and blue colour fluorescent powder be the key improving white light LEDs luminous mass.
With trivalent europium ion Eu
3+the red fluorescence powder excited, due to notable features such as the good stability of its compound, luminous intensity are high, high color purities, has been widely used in each luminescence display field.At present, the LED red fluorescence powder researched and developed mainly contains Eu
3+the compounds such as the vanadic acid alkali excited, phosphate base, boric acid alkali, oxyfluoride base.But they ultraviolet, blue-light excited under, luminous efficiency is low, and stability is poor, or synthesis technique is complicated, cost is higher, can't meet actual requirement, thus limits its application in the led.Simultaneously, yellow both domestic and external and green emitting phosphor are very ripe in package application, and the luminous efficiency of red fluorescence powder and stability can not be compared with other powder far away, thus develop one and can obtain high color rendering index (CRI), efficient stable, long service life, low price, and the focus of research both at home and abroad at present just can have been become by the red fluorescence powder that UV-light, nearly purple light or blue-light LED chip efficiently excite.Stibnate is a kind of traditional phosphor host, and it has high stable performance, low raw-material cost and the advantage such as preparation technology is simple.Therefore, stibnate fluorescent material is one of fluorescent material of excellent property.Therefore, use stibnate is base starting material, develop the focus that a kind of novel stibnate base red fluorescent powder becomes research both at home and abroad, but the report of metaantimmonic acid lanthanum lithium salts red fluorescence powder has not seen reported.
Summary of the invention
The present invention seeks to: low in ultraviolet, blue-light excited lower luminous efficiency for overcoming existing red fluorescence powder, poor stability, and the deficiency that synthesis technique is complicated, cost is higher, and provide that a kind of degree of crystallinity is high, luminous mass good, preparation condition safety, preparation technology are simple, cost is low, the stibnate base red fluorescent powder of safety non-pollution, it to the red-emitting of blue-light excited lower energy efficient stable, promotes the widespread use of phosphor in ultraviolet, near ultraviolet with this.
Technical scheme of the present invention is: a kind of stibnate base red fluorescent powder, is characterized in that: chemical formula is LiLa
2-2xe
u2xsbO
6, wherein x is Eu
3+doping substitutes La
3+mol ratio coefficient, span is 0.001≤x≤0.6.
Further, red fluorescence powder described in the present invention ultraviolet, near ultraviolet and blue-light excited under, send the ruddiness of predominant wavelength in 614 nanometers.
The present invention provides the preparation method of above-mentioned stibnate base red fluorescent powder simultaneously, and this preparation method's process is simple, easy handling, and raw material without the need to rare gas element or protection of reducing atmosphere, obviously reduces energy consumption and product cost in preparation process.Compared with other sulfide, halogenide, product easily collecting, without waste water and gas discharge, environmentally friendly.It adopts high temperature solid-state method, comprises the following steps:
1) by chemical formula LiLa
2-2xeu
2xsbO
6in the nonstoichiometric molar ratio of each element take following raw material: the compound containing lithium ion, the compound containing lanthanum ion, the compound containing europium ion and the compound containing antimony ion, grinding makes it mix, and wherein, x is Eu
3+doping substitutes La
3+mol ratio coefficient, 0.001≤x≤0.6;
2) by said mixture presintering 1-2 time in air atmosphere, calcining temperature is 300 ~ 900 DEG C, and calcination time is once 2 ~ 10 hours;
3) by step 2) the mixture naturally cooling that obtains after calcining, grind and mix, calcining in air atmosphere, calcining temperature is 900 ~ 1300 DEG C, and calcination time is 5 ~ 16 hours, namely obtains described stibnate base red fluorescent powder.
Further, described in the present invention containing the one that the compound of lithium ion is in Lithium Oxide 98min, Quilonum Retard, lithium hydroxide, lithium nitrate, Lithium Sulphate; The described compound containing lanthanum ion is the one in lanthanum trioxide, lanthanum nitrate, lanthanum sulfat; Described contains europium ion Eu
3+compound be one in europium sesquioxide, europium nitrate, europium sulfate; Described contains antimony ion Sb
3+compound comprise one in antimonous oxide, nitric acid antimony, antimony trisulfate.
Further, step 2 described in the present invention) described in calcining temperature be 350 ~ 850 DEG C, calcination time is 5 ~ 9 hours; Calcining temperature described in step 3) is 950 ~ 1250 DEG C, and calcination time is 5 ~ 10 hours.
The present invention also provides the another kind of preparation method of above-mentioned stibnate base red fluorescent powder simultaneously, and this preparation method's process is simple, easy handling, and raw material without the need to rare gas element or protection of reducing atmosphere, obviously reduces energy consumption and product cost in preparation process.Compared with other sulfide, halogenide, product easily collecting, without waste water and gas discharge, environmentally friendly.It adopts chemical solution method, comprises the following steps:
1) by chemical formula LiLa
2-2xeu
2xsbO
6in the nonstoichiometric molar ratio of each element take following raw material: the compound containing lithium ion, the compound containing lanthanum ion, the compound containing europium ion and the compound containing antimony ion, wherein x is Eu
3+doping substitutes La
3+mol ratio coefficient, span is 0.001≤x≤0.6; The raw material taken to be dissolved in respectively in nitric acid and with deionized water dilution, then to add complexing agent respectively by 0.5 ~ 2.0wt% of reactant quality in each raw material, obtain the mixed solution of each raw material; Described complexing agent is the one in citric acid, oxalic acid;
2) mixed solution of each raw material is slowly mixed, in temperature be under the condition of 50 ~ 100 DEG C stir 1 ~ 2 hour, leave standstill, dry after obtain fluffy presoma;
3) by presoma presintering 1-2 time in air atmosphere, calcining temperature is 200 ~ 600 DEG C, and one time calcination time is 1 ~ 8 hour;
4), after product naturally cooling step 3) obtained, grinding also mixes again, and calcine in air atmosphere, calcining temperature is 600 ~ 900 DEG C, and calcination time is 8 ~ 16 hours, obtains a kind of stibnate base red fluorescent powder.
Further, the compound containing lithium ion described in the present invention is the one in Lithium Oxide 98min, Quilonum Retard, lithium hydroxide, lithium nitrate, Lithium Sulphate; The described compound containing lanthanum ion is the one in lanthanum trioxide, lanthanum nitrate, lanthanum sulfat; Described contains europium ion Eu
3+compound be one in europium sesquioxide, europium nitrate, europium sulfate; Described contains antimony ion Sb
3+compound comprise one in antimonous oxide, nitric acid antimony, antimony trisulfate.
Further, the calcining temperature described in the present invention described in step 3) is 200 ~ 400 DEG C, and calcination time is 3 ~ 7 hours; Calcining temperature in described step 4) is 600 ~ 850 DEG C, and calcination time is 10 ~ 15 hours.
The present invention also provides the application of above-mentioned stibnate base red fluorescent powder, it is characterized in that this red fluorescence powder to be applied to regulate with the various illuminations that are excitaton source of ultraviolet, near ultraviolet and blue light, display and photoluminescence colourity.
Advantage of the present invention is:
1, the stibnate base red fluorescent powder that prepared by the present invention is the fluorescent synthetic materials with high-luminous-efficiency, and has higher crystallinity and visible light permeability.
2, stibnate base red fluorescent powder of the present invention can ultraviolet, near ultraviolet and blue-light excited under, send the ruddiness of predominant wavelength in 614 nanometers, red degree is pure, coordinates with green emitting phosphor, is coated on blue-light LED chip and can prepares novel white light LEDs.
3, the preparation method of stibnate base red fluorescent powder provided by the invention, the method abundant raw material source, cheap; and preparation technology is simple; easy handling, material without the need to rare gas element or protection of reducing atmosphere, obviously reduces energy consumption and product cost in preparation process.Compared with other sulfide, halogenide, product easily collecting, without waste water and gas discharge, environmentally friendly.
4, the stibnate base red fluorescent powder that prepared by the present invention has good color developing and granularity, is conducive to realizing the high-power LED of preparation.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described:
Fig. 1 is the LiLa prepared by the embodiment of the present invention 1 technical scheme
1.9eu
0.1sbO
6x-ray powder diffraction pattern;
Fig. 2 is the LiLa prepared by the embodiment of the present invention 1 technical scheme
1.9eu
0.1sbO
6sEM figure;
Fig. 3 is the LiLa prepared by the embodiment of the present invention 1 technical scheme
1.9eu
0.1sbO
6the ultraviolet obtained under the light detection of 614 nanometers is to the exciting light spectrogram of blue region;
Fig. 4 is the LiLa prepared by the embodiment of the present invention 1 technical scheme
1.9eu
0.1sbO
6luminescent spectrum figure under the optical excitation of 395 nanometers;
Fig. 5 is the LiLa prepared by the embodiment of the present invention 2 technical scheme
1.8eu
0.2sbO
6luminescent spectrum figure under the optical excitation of 395 nanometers;
Fig. 6 is the LiLaEuSbO prepared by the embodiment of the present invention 7 technical scheme
6sEM figure.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further described.
Embodiment 1:
Preparation LiLa
1.9eu
0.1sbO
6
According to chemical formula LiLa
1.9eu
0.1sbO
6in the nonstoichiometric molar ratio of each element, take Quilonum Retard Li respectively
2cO
3: 0.2463 gram, lanthanum trioxide La
2o
3: 2.0635 grams, europium sesquioxide Eu
2o
3: 0.1174 gram, antimonous oxide Sb
2o
3: 0.9718 gram, to grind in agate mortar and after mixing, select air atmosphere first time calcining, temperature is 350 DEG C, and calcination time 5 hours, is then cooled to room temperature, takes out sample; By the raw material of first time calcining, fully mixed grinding is even again, and again calcine in air atmosphere, temperature 850 DEG C, calcination time 9 hours, is then chilled to room temperature, takes out sample; Be placed on air calcination in retort furnace after finally it again fully being ground, calcining temperature is 1250 DEG C, and calcination time is 10 hours, namely obtains powder shaped stibnate red illuminating material.
See accompanying drawing 1, it is the X-ray powder diffraction pattern that the present embodiment technical scheme prepares sample, and XRD test result shows, prepared material LiLa
1.9eu
0.1sbO
6for monophase materials, the impurity thing without any other exists mutually.
Are the SEM figure of the material sample prepared by embodiment of the present invention technical scheme see accompanying drawing 2, this material crystalline is functional, uniform particle sizes, and median size is at 5.0 microns.
See accompanying drawing 3, as can be seen from material sample monitoring utilizing emitted light 614 nanometer prepared by the technology of the present invention is obtained in the exciting light spectrogram of ultraviolet blue region, the emitting red light of this material excite the main ultraviolet between 200 ~ 500 nanometers in source to blue region, ultraviolet can be mated well and excite to blue-light LED chip.
See accompanying drawing 4, it is stibnate LiLa
1.9eu
0.1sbO
6excite the luminescent spectrum figure obtained in fluorescent material with near-ultraviolet light 395 nanometer, the main center emission wavelength of this material is the emitting red light wave band of 614 nanometers, calculates simultaneously, learn that its coordinate is x=0.630, y=0.355, also just in time drop on red area through CIE.
Embodiment 2:
Preparation LiLa
1.8eu
0.2sbO
6
According to chemical formula LiLa
1.8eu
0.2sbO
6, take Quilonum Retard Li respectively
2cO
3: 0.2463 gram, lanthanum trioxide La
2o
3: 1.9549 grams, europium sulfate Eu
2(SO
4)
3h
2o:0.3948 gram, antimonous oxide Sb
2o
3: 0.9718 gram, to grind in agate mortar and after mixing, select air atmosphere first time calcining, temperature is 425 DEG C, and calcination time 6 hours, is then cooled to room temperature, takes out sample; By the raw material of first time calcining, fully mixed grinding is even again, and again calcine in air atmosphere, temperature 700 DEG C, calcination time 7 hours, is then chilled to room temperature, takes out sample; Be placed on air calcination in retort furnace after finally it again fully being ground, calcining temperature is 950 DEG C, and calcination time is 5 hours, namely obtains powder shaped stibnate red illuminating material.Its main structure properties, excitation spectrum are similar to embodiment 1.
See accompanying drawing 5, it is stibnate LiLa
1.8eu
0.2sbO
6excite the luminescent spectrum figure obtained in fluorescent material with near-ultraviolet light 395 nanometer, the main center emission wavelength of this material is the emitting red light wave band of 614 nanometers, calculates simultaneously, learn that its coordinate is x=0.659, y=0.341, also just in time drop on red area through CIE.
Embodiment 3:
Preparation LiLa
1.6eu
0.4sbO
6
According to chemical formula LiLa
1.6eu
0.4sbO
6, take Quilonum Retard Li respectively
2cO
3: 0.2469 gram, lanthanum trioxide La
2o
3: 1.7377 grams, europium nitrate Eu (NO
3)
36H
2o:1.1896 gram, antimonous oxide Sb
2o
3: 0.9718 gram, to grind in agate mortar and after mixing, select air atmosphere first time calcining, temperature is 375 DEG C, and calcination time 6 hours, is then cooled to room temperature, takes out sample; By the raw material of first time calcining, fully mixed grinding is even again, and again calcine in air atmosphere, temperature 500 DEG C, calcination time 8 hours, is then chilled to room temperature, takes out sample; Be placed on air calcination in retort furnace after finally it again fully being ground, calcining temperature is 1125 DEG C, and calcination time is 9 hours, namely obtains powder shaped stibnate red illuminating material.Its main structure properties, excitation spectrum are similar to embodiment 1 with luminescent spectrum.
Embodiment 4:
Preparation LiLa
1.4eu
0.6sbO
6
According to chemical formula LiLa
1.4eu
0.6sbO
6, take Lithium Oxide 98min Li respectively
2o:0.0498 gram, lanthanum nitrate La (NO
3)
3: 2.0207 grams, europium sesquioxide Eu
2o
3: 0.352 gram, antimonous oxide Sb
2o
3: 0.4859 gram, to grind in agate mortar and after mixing, select air atmosphere first time calcining, temperature is 450 DEG C, and calcination time 7 hours, is then cooled to room temperature, takes out sample; By the raw material of first time calcining, fully mixed grinding is even again, and again calcine in air atmosphere, temperature 550 DEG C, calcination time 8 hours, is then chilled to room temperature, takes out sample; Be placed on air calcination in retort furnace after finally it again fully being ground, calcining temperature is 1150 DEG C, and calcination time is 8 hours, namely obtains powder shaped stibnate red illuminating material.Its main structure properties, excitation spectrum are similar to embodiment 1 with luminescent spectrum.
Embodiment 5:
Preparation LiLa
1.2eu
0.8sbO
6
According to chemical formula LiLa
1.2eu
0.8sbO
6, take lithium nitrate LiNO respectively
3: 0.4597 gram, lanthanum trioxide La
2o
3: 1.3033 grams, europium sesquioxide Eu
2o
3: 0.9387 gram, antimonous oxide Sb
2o
3: 0.9718 gram, to grind in agate mortar and after mixing, select air atmosphere first time calcining, temperature is 475 DEG C, and calcination time 6 hours, is then cooled to room temperature, takes out sample; By the raw material of first time calcining, fully mixed grinding is even again, and again calcine in air atmosphere, temperature 750 DEG C, calcination time 9 hours, is then chilled to room temperature, takes out sample; Be placed on air calcination in retort furnace after finally it again fully being ground, calcining temperature is 1200 DEG C, and calcination time is 10 hours, namely obtains powder shaped stibnate red illuminating material.Its main structure properties, excitation spectrum are similar to embodiment 1 with luminescent spectrum.
Embodiment 6:
Preparation LiLa
1.998eu
0.002sbO
6
According to chemical formula LiLa
1.998eu
0.002sbO
6, take lithium hydroxide LiOH:0.1596 gram respectively, lanthanum trioxide La
2o
3: 2.1699 grams, europium sesquioxide Eu
2o
3: 0.0024 gram, antimonous oxide Sb
2o
3: 0.9718 gram, to grind in agate mortar and after mixing, select air atmosphere first time calcining, temperature is 300 DEG C, and calcination time 9 hours, is then cooled to room temperature, takes out sample; By the raw material of first time calcining, fully mixed grinding is even again, and again calcine in air atmosphere, temperature 800 DEG C, calcination time 8 hours, is then chilled to room temperature, takes out sample; Be placed on air calcination in retort furnace after finally it again fully being ground, calcining temperature is 1220 DEG C, and calcination time is 7 hours, namely obtains powder shaped stibnate red illuminating material.Its main structure properties, excitation spectrum are similar to embodiment 1 with luminescent spectrum.
Embodiment 7:
Preparation LiLaEuSbO
6
According to chemical formula LiLaEuSbO
6, take Lithium Sulphate Li respectively
2sO
4: 0.3665 gram, lanthanum sulfat La
2(SO
4)
3: 0.7833 gram, europium sesquioxide Eu
2o
3: 1.1734 grams, antimony trisulfate Sb
2(SO
4)
3: 1.7724 grams, then the citric acid of 0.5wt% taking above medicine total mass.The Li first will taken
2sO
4stir with appropriate deionized water, nitric acid dissolve, to dissolving completely, adding appropriate citric acid, being heated to 50 DEG C afterwards and carrying out stir process; The La will taken again
2(SO
4)
3, Eu
2o
3and Sb
2o
3process in the same way, namely first stir with appropriate deionized water, nitric acid dissolve, adding appropriate citric acid completely to dissolving, being heated to 50 DEG C afterwards and carrying out stir process; Finally above-mentioned four kinds of solution mixing, then add a certain amount of citric acid heated and stirred wherein, and add appropriate amount of deionized water and nitric acid several times, continue stirring 2 hours, leave standstill, dry, obtain fluffy presoma.Calcining temperature is 200 DEG C for the first time, calcination time 3 hours; Second time calcining temperature is 400 DEG C, calcination time 7 hours; Third firing temperature is 850 DEG C, calcination time 15 hours, namely obtains powder shaped stibnate red illuminating material.Its main structure properties, excitation spectrum are similar to embodiment 1 with luminescent spectrum.
Are the SEM figure of the material sample prepared by embodiment of the present invention technical scheme see accompanying drawing 6, this material crystalline is functional, uniform particle sizes, and median size is at 5.0 microns.
Embodiment 8:
Preparation LiLa
0.8eu
1.2sbO
6
According to chemical formula LiLa
0.8eu
1.2sbO
6, take lithium nitrate LiNO respectively
3: 0.2299 gram, lanthanum nitrate La (NO
3)
3: 1.1547 grams, europium sesquioxide Eu
2o
3: 0.704 gram, antimonous oxide Sb
2o
3: 1.026 grams, then the citric acid of 0.5wt% taking above medicine total mass.The LiNO first will taken
3stir with appropriate deionized water, nitric acid dissolve, adding appropriate citric acid completely to dissolving, being heated to 50 DEG C afterwards and carrying out stir process; La (the NO will taken again
3)
3, Eu
2o
3and Sb
2o
3process in the same way, namely first stir with appropriate deionized water, nitric acid dissolve, adding appropriate citric acid completely to dissolving, being heated to 50 DEG C afterwards and carrying out stir process; Finally above-mentioned two kinds of solution mixing, then add a certain amount of citric acid heated and stirred wherein, and add appropriate amount of deionized water and nitric acid several times, continue stirring 2 hours, leave standstill, dry, obtain fluffy presoma.Calcining temperature is 300 DEG C for the first time, calcination time 5 hours; Second time calcining temperature is 350 DEG C, calcination time 6 hours; Third firing temperature is 800 DEG C, calcination time 10 hours, namely obtains powder shaped stibnate red illuminating material.Its main structure properties, excitation spectrum are similar to embodiment 1 with luminescent spectrum.Its main structure properties, excitation spectrum are similar to embodiment 1 with luminescent spectrum.
Certain above-described embodiment is just exemplifying of illustrating that technical conceive of the present invention and feature do and non exhaustive, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All modifications done according to the spirit of main technical schemes of the present invention, all should be encompassed within protection scope of the present invention.
Claims (5)
1. a stibnate base red fluorescent powder, is characterized in that: this fluorescent material adopts following chemical solution method to obtain, and the method comprises the following steps:
1) by chemical formula LiLa
2-2xeu
2xsbO
6in the nonstoichiometric molar ratio of each element take following raw material: the compound containing lithium ion, the compound containing lanthanum ion, the compound containing europium ion and the compound containing antimony ion, wherein x is Eu
3+doping substitutes La
3+mol ratio coefficient, span is 0.001≤x≤0.6; The raw material taken to be dissolved in respectively in nitric acid and with deionized water dilution, then to add complexing agent respectively by 0.5 ~ 2.0wt% of reactant quality in each raw material, obtain the mixed solution of each raw material; Described complexing agent is the one in citric acid, oxalic acid;
2) mixed solution of each raw material is slowly mixed, in temperature be under the condition of 50 ~ 100 DEG C stir 1 ~ 2 hour, leave standstill, dry after obtain fluffy presoma;
3) by presoma presintering 1-2 time in air atmosphere, calcining temperature is 200 ~ 600 DEG C, and one time calcination time is 1 ~ 8 hour;
4) by step 3) after the product naturally cooling that obtains, grinding also mixes again, and calcine in air atmosphere, calcining temperature is 600 ~ 900 DEG C, and calcination time is 8 ~ 16 hours, obtains a kind of stibnate base red fluorescent powder.
2. a kind of stibnate base red fluorescent powder according to claim 1, is characterized in that: described red fluorescence powder ultraviolet, near ultraviolet and blue-light excited under, send the ruddiness of predominant wavelength in 614 nanometers.
3. a kind of stibnate base red fluorescent powder according to claim 1, is characterized in that: the described compound containing lithium ion is the one in Lithium Oxide 98min, Quilonum Retard, lithium hydroxide, lithium nitrate, Lithium Sulphate; The described compound containing lanthanum ion is the one in lanthanum trioxide, lanthanum nitrate, lanthanum sulfat; Described contains europium ion Eu
3+compound be one in europium sesquioxide, europium nitrate, europium sulfate; Described contains antimony ion Sb
3+compound comprise one in antimonous oxide, nitric acid antimony, antimony trisulfate.
4. a kind of stibnate base red fluorescent powder according to claim 1, is characterized in that: described step 3) described in calcining temperature be 200 ~ 400 DEG C, calcination time is 3 ~ 7 hours; Described step 4) in calcining temperature be 600 ~ 850 DEG C, calcination time is 10 ~ 15 hours.
5. the application of a kind of stibnate base red fluorescent powder as described in Claims 1 to 4 any one, is characterized in that this red fluorescence powder to be applied to and regulates with the various illuminations that are excitaton source of ultraviolet, near ultraviolet and blue light, display and photoluminescence colourity.
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| CN104789221B (en) * | 2015-04-28 | 2016-11-30 | 江苏师范大学 | Erbium-ytterbium co-doped antimonate up-conversion luminescent material and preparation method and application thereof |
| CN104910908B (en) * | 2015-05-08 | 2016-09-07 | 江苏师范大学 | Red fluorescent material for white light LED and preparation method thereof |
| CN105419798B (en) * | 2015-12-23 | 2017-08-25 | 江苏师范大学 | A kind of preparation method and application of orange red antimonate luminescent materials |
| CN109825296B (en) * | 2019-03-05 | 2021-03-02 | 常州工程职业技术学院 | Europium ion Eu3+Activated fluorine antimonate orange red fluorescent powder and preparation method thereof |
| CN112251226B (en) * | 2020-09-23 | 2021-12-21 | 华南理工大学 | Near-infrared luminescent material, preparation method thereof and conversion type LED (light-emitting diode) luminescent device |
| CN113583672B (en) * | 2021-07-21 | 2023-04-14 | 厦门理工学院 | Eu 3+ Doped composite antimonate red fluorescent powder and preparation method and application thereof |
| CN113717723B (en) * | 2021-10-08 | 2023-07-25 | 常州工程职业技术学院 | Eu (Eu) 3+ Doped bismuthate red fluorescent powder and preparation method and application thereof |
| CN115477946B (en) * | 2022-09-30 | 2023-05-23 | 云南大学 | Green fluorescent material for non-contact temperature sensor and preparation method thereof |
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