CN103305221A - Eu<3+>-doped vanadate fluorescent material, and preparation method and application thereof - Google Patents

Eu<3+>-doped vanadate fluorescent material, and preparation method and application thereof Download PDF

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Publication number
CN103305221A
CN103305221A CN2013102623939A CN201310262393A CN103305221A CN 103305221 A CN103305221 A CN 103305221A CN 2013102623939 A CN2013102623939 A CN 2013102623939A CN 201310262393 A CN201310262393 A CN 201310262393A CN 103305221 A CN103305221 A CN 103305221A
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vanadate
mixes
preparation
compound
luminescent material
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黄彦林
魏东磊
秦琳
陶正旭
关莹
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Suzhou University
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Suzhou University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Abstract

The invention discloses a Eu<3+>-doped vanadate fluorescent material, and a preparation method and the application thereof. Fluorescent powder has the chemical formula of Na3M8-xEuxV3O21, wherein M is one of elements La, Gd and Y; x is greater than or equal to 0.001 and is less than or equal to 0.1. The Eu<3+>-doped vanadate fluorescent material is prepared by a high-temperature solid phase method; and a sample is prepared by the steps of weighing raw materials in proportion; grinding the raw materials and mixing the ground raw materials uniformly; pre-sintering the mixture in an air atmosphere; cooling the pre-sintered mixture naturally; grinding the cooled mixture and mixing the mixture uniformly; calcining the mixture in an air atmosphere; and finally cooling and grinding the calcined mixture. Under the excitation of ultraviolet light, the vanadate red fluorescent powder provided by the invention has the characteristic that the position of the emission peak is near 621 nanometers; the vanadate red fluorescent powder has strong excitation at the wavelength of between 300 and 400 nanometers; the wavelength of the vanadate red fluorescent powder is matched with the emission wavelength of an ultraviolet light-emitting diode (LED) chip; the luminous efficiency is high; and the vanadate red fluorescent powder can be used for preparing white LED lighting devices. The vanadate fluorescent material has a simple preparation process and a low synthesis temperature and facilitates industrial production.

Description

A kind of Eu 3+Vanadate luminescent material, preparation method and the application of mixing
Technical field
The present invention relates to a kind of fluorescent material, particularly a kind of vanadate luminescent material, preparation method and application thereof of europium doping.
Background technology
Vanadate more and more is subjected to people's attention as inorganic fluorescent material, vanadate matrix can be held the Doped Rare Earth ion well, as rare-earth ion activated material, can obtain the luminous of rare earth ion by transmission ofenergy effectively giving rare earth ion the transmission ofenergy of matrix absorption.It has good chemical stability and thermostability, and also be the fluorescence synthetic materials with high-luminous-efficiency simultaneously, and higher crystallinity and visible light permeability are arranged, be a kind of better luminescent material, therefore have very widely and use.
Vanadate luminescent material mostly is rear-earth-doped material at present, for example: with YVO 4: Eu 3+The vanadate emitting red light powder that activates for the trivalent europium ion that represents is a kind of good fluorescent material, is widely used in high voltage mercury lamp, plasma flat-plate demonstration PDP, cathode-ray tube CRT and medical scintillation material.Along with the development of modern science and technology, the Application Areas of fluorescent material is also more and more, traditional vanadate red fluorescence powder such as YVO 4: Eu 3+Can not meet the needs of.For example, because very low at the launching efficiency of near ultraviolet and blue region, and the easy deliquescence of this system phosphor material powder, cause in the product use affected by environment greatlyyer, chemical stability is relatively poor.Make it in the white light LEDs illumination that develops rapidly now, can not satisfy the demand as the emitting red light powder.Therefore the chemical stability of development of new is good, and the red fluorescence powder that luminous efficiency is high has very important meaning.
Summary of the invention
The purpose of this invention is to provide a kind of good luminous performance, stability is high, and is with low cost, and preparation technology is simple, safety, free of contamination europkium-activated vanadate luminescent material, preparation method and application thereof.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of Eu is provided 3+The vanadate luminescent material that mixes, its chemical formula is Na 3M 8- x Eu x V 3O 21, wherein, M is a kind of among La, Gd, the Y, 0.001≤ x≤ 1.0; Described fluorescent material is with europium ion Eu 3+Be active ions, have effective launching efficiency at the ultraviolet region of 300～400 nanometers.
The described Eu of technical solution of the present invention 3+The vanadate luminescent material that mixes, its preparation method is high temperature solid-state method, comprises the steps:
1, to contain the compound of Na element, contain the compound of M element, contain the compound of Eu element, the compound that contains V element is raw material, presses chemical formula Na 3M 8- x Eu x V 3O 21In the stoichiometric ratio of corresponding element take by weighing each raw material, in the formula, M is a kind of among La, Gd, the Y, 0.001≤ x≤ 1.0; Mix after grinding respectively;
2, with the presintering 1～2 time in air of the raw material that mixes, 300～700 ℃ of sintering temperatures, sintering time is 2～10 hours;
3, the product that obtains is ground and mixes, calcine in air atmosphere, calcining temperature is 700～1200 ℃, and calcination time is 2～18 hours, obtains a kind of Eu 3+The vanadate luminescent material that mixes.
The compound of the Na of containing element of the present invention is a kind of in sodium oxide, sodium hydroxide, yellow soda ash, the SODIUMNITRATE.The compound of the described Eu of containing element is a kind of in europium sesquioxide, europium nitrate, the Europium trichloride.The described compound that contains V element is a kind of in Vanadium Pentoxide in FLAKES, ammonium vanadate, vanadous oxide, the vanadium oxide.
Above-mentioned preparation method's a preferred version is: in the step 2, sintering temperature is 350～650 ℃, and sintering time is 4～8 hours.In the step 3, calcining temperature is 750～1150 ℃, and calcination time is 4～16 hours.
A kind of Eu of the present invention 3+The vanadate luminescent material that mixes cooperates it with an amount of blueness and green emitting phosphor, applies and is packaged in outside the InGaN diode, for the preparation of the White-light LED illumination device.
Compared with prior art, the advantage of technical solution of the present invention is:
1, Eu of the present invention 3+The vanadate red fluorescence powder that activates is near ultraviolet 300～400 nanometers stronger exciting to be arranged, and is fit to the emission wavelength of near ultraviolet InGaN fully.
2, preparation technology is simple, adopts simultaneously that chemical property is stable, cheap compound is raw material, has reduced synthetic cost.
3, with commercial red fluorescence powder Y 2O 2S:Eu 3+Compare, the present invention prepares easy handling, pollution-free, environmental friendliness, especially is fit to serialization production.
Description of drawings
Fig. 1 is the embodiment of the invention 1 prepared Na 3La 7.9Eu 0.1V 3O 21The X-ray powder diffraction collection of illustrative plates of material sample;
Fig. 2 is the embodiment of the invention 1 prepared Na 3La 7.9Eu 0.1V 3O 21The exciting light spectrogram of material sample under monitoring wavelength 621 nanometers;
Fig. 3 is the embodiment of the invention 1 prepared Na 3La 7.9Eu 0.1V 3O 21The luminescent spectrum figure of material sample under 333 nano wave lengths excite;
Fig. 4 is the embodiment of the invention 5 prepared Na 3La 7EuV 3O 21The exciting light spectrogram of material sample under monitoring wavelength 612 nanometers;
Fig. 5 is the embodiment of the invention 5 prepared Na 3La 7EuV 3O 21The luminescent spectrum figure of material sample under 333 nano wave lengths excite.
Embodiment
Technical solution of the present invention is further elaborated below in conjunction with drawings and Examples.
Embodiment 1:
Preparation Na 3La 7.9Eu 0.1V 3O 21
According to chemical formula Na 3La 7.9Eu 0.1V 3O 21, take by weighing respectively: yellow soda ash Na 2CO 3: 0.318 gram, lanthanum trioxide La 2O 3: 2.5739 grams, europium sesquioxide Eu 2O 3: 0.0352 gram, ammonium vanadate NH 4VO 3: 0.702 gram, after in agate mortar, grinding and mixing, presintering in the air atmosphere, 500 ℃ of pre-sintering temperatures, sintering time 7 hours is cooled to room temperature, takes out sample; It fully is placed in the retort furnace after the grinding again, calcines under air atmosphere, calcining temperature is 750 ℃, and calcination time is 16 hours, namely obtains powder shaped vanadate red illuminating material.
Referring to accompanying drawing 1, it is the X-ray powder diffraction collection of illustrative plates for preparing sample by the present embodiment technical scheme, and the XRD test result shows, prepared vanadate Na 3La 7.9Eu 0.1V 3O 21Be monophase materials, exist mutually without any other impurity thing, and degree of crystallinity be better.
Referring to accompanying drawing 2, it is the exciting light spectrogram that the prepared sample of present embodiment obtains under the monitoring of 621 nanometers; As can be seen from the figure, the emitting red light of this material excite the source mainly near ultraviolet 333 nanometers, can mate the White-light LED chip of ultraviolet excitation well.
Referring to accompanying drawing 3, it is that the prepared sample of present embodiment excites the luminescent spectrum figure that obtains down at 333 nano wave lengths; Near the emitting red light wave band of luminescence center 621 nanometers that this material is main.
Embodiment 2:
Preparation Na 3Y 7.999Eu 0.001V 3O 21
According to chemical formula Na 3Y 7.999Eu 0.001V 3O 21, take by weighing respectively: sodium oxide Na 2The O:0.2324 gram, Yttrium trinitrate Y (NO 3) 3-6H 2The O:7.6602 gram, europium nitrate Eu (NO 3) 3-6H 2The O:0.0011 gram, Vanadium Pentoxide in FLAKES V 2O 5: 0.6825 gram, after in agate mortar, grinding and mixing, select air atmosphere to carry out presintering, pre-sintering temperature is 350 ℃, sintering time 4 hours is cooled to room temperature then, takes out sample; It is fully ground the back again carry out the presintering second time under air atmosphere, pre-sintering temperature is 500 ℃, and sintering time 6 hours is cooled to room temperature then, takes out sample; It fully is placed in the retort furnace after the grinding again, calcines under air atmosphere, calcining temperature is 850 ℃, and calcination time is 12 hours, namely obtains powder shaped vanadate salt red illuminating material.Its main structure properties, excitation spectrum and luminescent spectrum are similar to embodiment 1.
Embodiment 3:
Preparation Na 3Gd 7.85Eu 0.15V 3O 21
According to chemical formula Na 3Gd 7.85Eu 0.15V 3O 21, take by weighing respectively: sodium hydroxide NaOH:0.2401 gram, Gadolinium trichloride GdCl 3-6H 2O 5.8372 grams, Europium trichloride EuCl 3-6H 2The O:0.0775 gram, vanadous oxide V 2O 3: 0.4496 gram, after in agate mortar, grinding and mixing, select air atmosphere to carry out presintering, pre-sintering temperature is 400 ℃, sintering time 5 hours is cooled to room temperature then, takes out sample; It fully is placed in the retort furnace after the grinding again, calcines under air atmosphere, calcining temperature is 900 ℃, and calcination time is 10 hours, namely obtains powder shaped vanadate red illuminating material.Its main structure properties, excitation spectrum and luminescent spectrum are similar to embodiment 1.
Embodiment 4:
Preparation Na 3Y 7.6Eu 0.4V 3O 21
According to chemical formula Na 3Y 7.6Eu 0.4V 3O 21, take by weighing respectively: SODIUMNITRATE NaNO 3: 0.5099 gram, yttrium oxide Y 2O 3: 1.7166, europium sesquioxide Eu 2O 3: 0.1408 gram, vanadium oxide VO 2: 0.4976 gram, after in agate mortar, grinding and mixing, select air atmosphere to carry out presintering, pre-sintering temperature is 600 ℃, sintering time 6 hours is cooled to room temperature then, takes out sample; It fully is placed in the retort furnace after the grinding again, calcines under air atmosphere, calcining temperature is 1000 ℃, and calcination time is 8 hours, namely obtains powder shaped vanadate red illuminating material.Its main structure properties, excitation spectrum and luminescent spectrum are similar to embodiment 1.
Embodiment 5:
Preparation Na 3La 7EuV 3O 21
According to chemical formula Na 3La 7EuV 3O 21, take by weighing respectively: SODIUMNITRATE NaNO 3: 0.5099 gram, lanthanum nitrate La (NO 3) 3-6H 2The O:6.062 gram, europium sesquioxide Eu 2O 3: 0.352 gram, ammonium vanadate NH 4VO 3: 0.702 gram, after in agate mortar, grinding and mixing, select air atmosphere to carry out presintering, pre-sintering temperature is 650 ℃, sintering time 4 hours is cooled to room temperature then, takes out sample; It fully is placed in the retort furnace after the grinding again, calcines under air atmosphere, calcining temperature is 1150 ℃, and calcination time is 4 hours, namely obtains powder shaped vanadate red illuminating material.
Referring to accompanying drawing 4, it is the exciting light spectrogram that the prepared sample 621 nanometers monitoring of present embodiment obtains down.
Referring to accompanying drawing 5, it is that the prepared sample of present embodiment excites the luminescent spectrum figure that obtains down at 333 nano wave lengths; The main luminescence center of this material is at the emitting red light wave band of 621 nanometers.

Claims (9)

1. Eu 3+The vanadate luminescent material that mixes, it is characterized in that: its chemical formula is Na 3M 8- x Eu x V 3O 21, wherein, M is a kind of among La, Gd, the Y, 0.001≤ x≤ 1.0; Described fluorescent material is with europium ion Eu 3+Be active ions, have effective launching efficiency at the ultraviolet region of 300～400 nanometers.
2. a kind of Eu according to claim 1 3+The preparation method of the vanadate luminescent material that mixes is characterized in that adopting high temperature solid-state method, comprises the steps:
(1) to contain the compound of Na element, contain the compound of M element, contain the compound of Eu element, the compound that contains V element is raw material, presses chemical formula Na 3M 8- x Eu x V 3O 21In the stoichiometric ratio of corresponding element take by weighing each raw material, in the formula, M is a kind of among La, Gd, the Y, 0.001≤ x≤ 1.0; Mix after grinding respectively;
(2) with the presintering 1～2 time in air of the raw material that mixes, 300～700 ℃ of sintering temperatures, sintering time is 2～10 hours;
(3) product that obtains is ground and mixes, calcine in air atmosphere, calcining temperature is 700～1200 ℃, and calcination time is 2～18 hours, obtains a kind of Eu 3+The vanadate luminescent material that mixes.
3. a kind of Eu according to claim 2 3+The preparation method of the vanadate luminescent material that mixes is characterized in that: the compound of the described Na of containing element is a kind of in sodium oxide, sodium hydroxide, yellow soda ash, the SODIUMNITRATE.
4. a kind of Eu according to claim 2 3+The preparation method of the vanadate luminescent material that mixes is characterized in that: the compound of the described Eu of containing element is a kind of in europium sesquioxide, europium nitrate, the Europium trichloride.
5. a kind of Eu according to claim 2 3+The preparation method of the vanadate luminescent material that mixes is characterized in that: the compound of the described M of containing element is a kind of in the oxide compound, muriate, nitrate of M.
6. a kind of Eu according to claim 2 3+The preparation method of the vanadate luminescent material that mixes is characterized in that: the described compound that contains V element is a kind of in Vanadium Pentoxide in FLAKES, ammonium vanadate, vanadous oxide, the vanadium oxide.
7. a kind of Eu according to claim 2 3+The preparation method of the vanadate luminescent material that mixes, it is characterized in that: in the step (2), sintering temperature is 350～650 ℃, and sintering time is 4～8 hours.
8. a kind of Eu according to claim 2 3+The preparation method of the vanadate luminescent material that mixes, it is characterized in that: in the step (3), calcining temperature is 750～1150 ℃, and calcination time is 4～16 hours.
9. by the described a kind of Eu of claim 1 3+The application of the vanadate luminescent material that mixes is characterized in that: it is cooperated an amount of blueness and green emitting phosphor, apply and be packaged in outside the InGaN diode, preparation White-light LED illumination device.
CN2013102623939A 2013-06-27 2013-06-27 Eu<3+>-doped vanadate fluorescent material, and preparation method and application thereof Pending CN103305221A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104673314A (en) * 2015-01-28 2015-06-03 江苏师范大学 Vanadate-based down-conversion luminescent material and preparation method thereof
CN104910914A (en) * 2015-05-08 2015-09-16 江苏师范大学 Lanthanum boron vanadate-based red fluorescent material and preparation method thereof
CN105355712A (en) * 2015-10-29 2016-02-24 严梅霞 Silicon-based solar cell and preparation method thereof
CN108148582A (en) * 2018-01-11 2018-06-12 山东师范大学 A kind of fluorescent powder and preparation method and application based on barium metaborate
CN109988574A (en) * 2019-04-16 2019-07-09 龙岩学院 One kind vanadate phosphor containing strontium and preparation method thereof
CN112447961A (en) * 2020-12-12 2021-03-05 安徽嘉誉伟丰机电科技有限公司 Preparation method of high-specific-capacity lithium battery positive electrode material

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US3565816A (en) * 1967-04-28 1971-02-23 Int Standard Electric Corp Fluorescent polycrystalline materials
CN102399558A (en) * 2011-11-24 2012-04-04 苏州大学 Vanadate red phosphor, preparation method and application
CN103275720A (en) * 2013-05-14 2013-09-04 苏州大学 Sodium lanthanum vanadate-based luminous material as well as preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3565816A (en) * 1967-04-28 1971-02-23 Int Standard Electric Corp Fluorescent polycrystalline materials
CN102399558A (en) * 2011-11-24 2012-04-04 苏州大学 Vanadate red phosphor, preparation method and application
CN103275720A (en) * 2013-05-14 2013-09-04 苏州大学 Sodium lanthanum vanadate-based luminous material as well as preparation method and application thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104673314A (en) * 2015-01-28 2015-06-03 江苏师范大学 Vanadate-based down-conversion luminescent material and preparation method thereof
CN104910914A (en) * 2015-05-08 2015-09-16 江苏师范大学 Lanthanum boron vanadate-based red fluorescent material and preparation method thereof
CN105355712A (en) * 2015-10-29 2016-02-24 严梅霞 Silicon-based solar cell and preparation method thereof
CN108148582A (en) * 2018-01-11 2018-06-12 山东师范大学 A kind of fluorescent powder and preparation method and application based on barium metaborate
CN108148582B (en) * 2018-01-11 2021-04-02 山东师范大学 Fluorescent powder based on barium metaborate, preparation method and application
CN109988574A (en) * 2019-04-16 2019-07-09 龙岩学院 One kind vanadate phosphor containing strontium and preparation method thereof
CN112447961A (en) * 2020-12-12 2021-03-05 安徽嘉誉伟丰机电科技有限公司 Preparation method of high-specific-capacity lithium battery positive electrode material
CN112447961B (en) * 2020-12-12 2021-11-09 安徽嘉誉伟丰机电科技股份有限公司 Preparation method of high-specific-capacity lithium battery positive electrode material

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Application publication date: 20130918