CN103305216A - Borate red fluorescent powder and preparation method and application thereof - Google Patents

Borate red fluorescent powder and preparation method and application thereof Download PDF

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Publication number
CN103305216A
CN103305216A CN2013102631314A CN201310263131A CN103305216A CN 103305216 A CN103305216 A CN 103305216A CN 2013102631314 A CN2013102631314 A CN 2013102631314A CN 201310263131 A CN201310263131 A CN 201310263131A CN 103305216 A CN103305216 A CN 103305216A
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fluorescent powder
red fluorescent
compound
preparation
borate
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CN103305216B (en
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黄彦林
魏东磊
秦琳
陶正旭
关莹
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Anhui Rongze Technology Co ltd
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Suzhou University
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Abstract

The invention discloses borate red fluorescent powder and a preparation method and application thereof. The fluorescent powder is a borate material activated by rare-earth ions, wherein the chemical formula of the fluorescent powder is K3M1-xEUxB6O12; M is one of elements La, Gd and Y; and x is smaller than or equal to 1.0 and greater than or equal to 0.001. According to the borate red fluorescent powder prepared by a high-temperature solid-phase method, the position of a main emission peak is near 612 nanometers and coincided with an emission wavelength of a near ultraviolet semiconductor chip under excitation of near ultraviolet light. The red fluorescent powder disclosed by the invention is good in optical stability, high in red luminescent intensity, and ideal in color purity. The borate red fluorescent powder disclosed by the invention is low in cost, free of poison, free of pollution, and easy to operate and carry out industrial production.

Description

A kind of borate base red fluorescent powder, preparation method and application
Technical field
The present invention relates to a kind ofly under near ultraviolet excitation, launch a kind of borate base fluorescent powder of red fluorescence, can apply and be packaged in outside the InGaN diode, preparation White-light LED illumination device belongs to the fluorescent material technical field.
Background technology
The plurality of advantages such as that white light LEDs (Light Emitting Diode) has is nontoxic, energy-efficient, the life-span long, shock resistance and safety are decided.Can be widely used on the various lighting installations, be a kind of environmental protection, energy-conservation green illumination light source, therefore is generally considered the new light sources that substitutes traditional lighting.
At present, realize that White-light LED illumination mainly contains 3 kinds of approach, the first approach is to be combined to form white light by red, green and blue look led chip; The second approach is to use quantum effect to realize Single chip white light; The third is to add that with the chip of sending out UV-light or blue light fluorescent material realizes white light.The third method be cost minimum, simple, simultaneously also be the most ripe method, this fluorescent material mainly is the YAG yttrium aluminum garnet, its chemical formula is Y 3Al 5O 12: Ce 3+, the white light LEDs that this fluorescent material is made has very high luminous efficiency, but owing to the few colour rendering index that makes of ruddiness comparison of ingredients in the emmission spectrum is on the low side, colour temperature is higher.This has just reduced the application of white light LEDs at low colour temperature, warm white lighting field.At present, LED mainly is Y with commercial red fluorescence powder 2O 2S:Eu 3+, this red fluorescence powder is sulfide, and the preparation method is complicated, and luminous efficiency is low.Therefore develop a kind of stable performance, low price, can have been become by the red fluorescence powder that UV-light, purple light or blue-light LED chip efficiently excite at present the focus of research both at home and abroad.
Summary of the invention
The object of the present invention is to provide that a kind of luminous efficiency is high, stable chemical nature, and the simple borate base red fluorescent powder of preparation method, preparation method and application thereof.
The present invention is achieved through the following technical solutions: a kind of borate base red fluorescent powder is provided, and its chemical formula is K 3M 1-xEu xB 6O 12, wherein, the M element is a kind of among La, Gd, the Y, xBe Eu 3+The molecular fraction of mixing, 0.001≤ x≤ 1.0; Described fluorescent material is launched the red fluorescence that wavelength is 590~720 nanometers under near ultraviolet excitation.
Borate base red fluorescent powder of the present invention, its preparation method comprises the steps: for adopting high temperature solid-state method
1, with contain the K element compound, contain the compound of M element, contain the Eu element compound, contain the B element compound be raw material, press chemical formula K 3M 1-xEu xB 6O 12The stoichiometric ratio of middle corresponding element takes by weighing each raw material, and in the formula, the M element is a kind of among La, Gd, the Y, 0.001≤ x≤ 1.0; Mix after grinding respectively, obtain mixing raw material;
2, with the presintering 1~2 time in air of the mixing raw material that obtains, sintering temperature is 300~650 ℃, and sintering time is 2~10 hours;
3, the product after the presintering is ground and mixes, calcine in air atmosphere, calcining temperature is 700~1200 ℃, and calcination time is 2~18 hours, obtains a kind of borate base red fluorescent powder.
The compound of the K of containing element of the present invention is a kind of in potassium hydroxide, salt of wormwood, the saltpetre; The compound that contains the M element is a kind of in oxide compound, the nitric acid thing, and the M element is a kind of among La, Gd, the Y; The compound that contains the Eu element is a kind of in europium sesquioxide, the europium nitrate; The compound that contains the B element is a kind of in boron oxide, the boric acid.
A kind of preferred version of above-mentioned preparation method is: the described sintering temperature of step 2 is 350~600 ℃, and sintering time is 3~8 hours; The described calcining temperature of step 3 is 750~1100 ℃, and calcination time is 3~15 hours.
A kind of borate base red fluorescent powder provided by the invention can cooperate an amount of blueness and green emitting phosphor, applies and is packaged in outside the 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 provided by the invention 3+The borate base red fluorescent powder that activates sends the ruddiness that main peak is 612 nanometers under the exciting of 350~400 nanometer light, red degree is pure, cooperates with green emitting phosphor, is coated on the blue-light LED chip to prepare novel white light LEDs.
2, can cooperate with ultraviolet or near ultraviolet LED chip, prepare white light LEDs as red fluorescence powder; Also can cooperate with blue light, purple light, ultraviolet leds, or mix the fluorescent material of other type, the preparation multi-color LED.
3, the borate base red fluorescent powder of the present invention's preparation is compared with other sulfide, halogenide, and its base starting material source is abundant, cheap, and preparation technology is simple, and is without the waste water and gas discharging, environmentally friendly.Have good thermostability, color developing and granularity are conducive to realize the high-power LED of preparation.
Description of drawings
Fig. 1 is the embodiment of the invention 1 prepared K 3Y 0.95Eu 0.05B 6O 12The X-ray powder diffraction collection of illustrative plates of material sample;
Fig. 2 is the embodiment of the invention 1 prepared K 3Y 0.95Eu 0.05B 6O 12The exciting light spectrogram of material sample under monitoring wavelength 612 nanometers;
Fig. 3 is the embodiment of the invention 1 prepared K 3Y 0.95Eu 0.05B 6O 12The luminescent spectrum figure of material sample under 396 nano wave lengths excite;
Fig. 4 is the embodiment of the invention 5 prepared K 3La 0.75Eu 0.25B 6O 12The exciting light spectrogram of material sample under monitoring wavelength 612 nanometers;
Fig. 5 is the embodiment of the invention 5 prepared K 3La 0.75Eu 0.25B 6O 12The luminescent spectrum figure of material sample under 396 nano wave lengths excite.
Embodiment
Technical solution of the present invention is further elaborated below in conjunction with drawings and Examples.
Embodiment 1:
Preparation K 3Y 0.95Eu 0.05B 6O 12
According to chemical formula K 3Y 0.95Eu 0.05B 6O 12, take by weighing respectively: salt of wormwood K 2CO 3: 1.38191 grams, yttrium oxide Y 2O 3: 0.7151 gram, europium sesquioxide Eu 2O 3: 0.0587 gram, boric acid H 3BO 3: 2.4732 grams, after in agate mortar, grinding and mixing, in air atmosphere, carry out presintering, pre-sintering temperature is 500 ℃, 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 15 hours, namely obtains powder shaped boric acid alkali 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 borate K 3Y 0.95Eu 0.05B 6O 12Be monophase materials, without any other impurity phase existence, and degree of crystallinity is better.
Referring to accompanying drawing 2, it is the lower exciting light spectrogram that obtains of the prepared sample 612 nanometers monitoring of the present embodiment; As can be seen from the figure, the emitting red light of this material excite the source mainly near ultraviolet 396 nanometers, can mate well the White-light LED chip of near ultraviolet excitation.
Referring to accompanying drawing 3, it is that the prepared sample of the present embodiment excites the lower luminescent spectrum figure that obtains at 396 nano wave lengths; The main luminescence center of this material is at the emitting red light wave band of 612 nanometers.
Embodiment 2:
Preparation K 3Gd 0.9Eu 0.1B 6O 12
According to chemical formula K 3Gd 0.9Eu 0.1B 6O 12, take by weighing respectively: saltpetre KNO 3: 2.022 grams, gadolinium sesquioxide Gd 2O 3: 1.0875 grams, europium nitrate Eu (NO 3) 3-6H 2The O:0.1487 gram, boron oxide B 2O 3: 1.3924 grams, after in agate mortar, grinding and mixing, select air atmosphere to carry out presintering, pre-sintering temperature is 350 ℃, sintering time 8 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 900 ℃, and calcination time is 12 hours, namely obtains the powder shaped borate red luminescent material.Its main structure properties, excitation spectrum and luminescent spectrum are similar to embodiment 1.
Embodiment 3:
Preparation K 3La 0.999Eu 0.001B 6O 12
According to chemical formula K 3La 0.999Eu 0.001B 6O 12, take by weighing respectively potassium hydroxide KOH:1.122 gram, lanthanum trioxide La 2O 3: 1.0849 grams, europium nitrate Eu (NO 3) 3-6H 2The O:0.0015 gram, boron oxide B 2O 3: 1.3924 grams, after in agate mortar, grinding and mixing, select air atmosphere to carry out presintering, pre-sintering temperature is 600 ℃, then sintering time 3 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 850 ℃, and calcination time is 16 hours, namely obtains the powder shaped borate red luminescent material.Its main structure properties, excitation spectrum and luminescent spectrum are similar to embodiment 1.
Embodiment 4:
Preparation K 3Gd 0.8Eu 0.2B 6O 12
According to chemical formula K 3Gd 0.8Eu 0.2B 6O 12, take by weighing respectively: salt of wormwood K 2CO 3: 1.3819 grams, Gadolinium trinitrate Gd (NO 3) 3-6H 2The O:2.407 gram, europium nitrate Eu (NO 3) 3-6H 2The O:1.7842 gram, boron oxide B 2O 3: 1.3924 grams, after in agate mortar, grinding and mixing, select air atmosphere to carry out presintering, pre-sintering temperature is 400 ℃, then sintering time 8 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 950 ℃, and calcination time is 10 hours, namely obtains the powder shaped borate red luminescent material.Its main structure properties, excitation spectrum and luminescent spectrum are similar to embodiment 1.
Embodiment 5:
Preparation K 3La 0.75Eu 0.25B 6O 12
According to chemical formula K 3La 0.75Eu 0.25B 6O 12, take by weighing respectively: saltpetre KNO 3: 2.022 grams, lanthanum nitrate La (NO 3) 3-6H 2The O:2.165 gram, europium nitrate Eu (NO 3) 3-6H 2The O:0.7434 gram, boric acid H 3BO 3: 2.4732 grams, after in agate mortar, grinding and mixing, select air atmosphere to carry out presintering, pre-sintering temperature is 450 ℃, 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 1000 ℃, and calcination time is 15 hours, namely obtains the powder shaped borate red luminescent material.
Referring to accompanying drawing 4, it is the lower exciting light spectrogram that obtains of the prepared sample 612 nanometers monitoring of the present embodiment; As can be seen from the figure, the emitting red light of this material excite the source mainly near ultraviolet 396 nanometers, can mate well the White-light LED chip of near ultraviolet excitation.
Referring to accompanying drawing 5, it is that the prepared sample of the present embodiment excites the lower luminescent spectrum figure that obtains at 396 nano wave lengths; The main luminescence center of this material is at the emitting red light wave band of 612 nanometers.
Embodiment 6:
Preparation K 3Y 0.6Eu 0.4B 6O 12
According to chemical formula Na 2Y 0.6Eu 0.4PO 4F 2, take by weighing respectively salt of wormwood K 2CO 3: 1.3819 grams, yttrium oxide Y 2O 3: 0.4517 gram, europium sesquioxide Eu 2O 3: 0.4692 gram, boron oxide B 2O 3: 1.3924 grams, after in agate mortar, grinding and mixing, select air atmosphere to carry out presintering, pre-sintering temperature is 500 ℃, sintering time 5 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 1100 ℃, and calcination time is 13 hours, namely obtains the powder shaped borate red luminescent material.Its main structure properties, excitation spectrum and luminescent spectrum are similar to embodiment 1.

Claims (6)

1. borate base red fluorescent powder, it is characterized in that: its chemical formula is K 3M 1-xEu xB 6O 12, wherein, the M element is a kind of among La, Gd, the Y, xBe Eu 3+The molecular fraction of mixing, 0.001≤ x≤ 1.0; Described fluorescent material is launched the red fluorescence that wavelength is 590~720 nanometers under near ultraviolet excitation.
2. the preparation method of borate base red fluorescent powder as claimed in claim 1 is characterized in that adopting high temperature solid-state method, comprises the steps:
(1) with contain the K element compound, contain the compound of M element, contain the Eu element compound, contain the B element compound be raw material, press chemical formula K 3M 1-xEu xB 6O 12The stoichiometric ratio of middle corresponding element takes by weighing each raw material, and in the formula, the M element is a kind of among La, Gd, the Y, 0.001≤ x≤ 1.0; Mix after grinding respectively, obtain mixing raw material;
(2) with the presintering 1~2 time in air of the mixing raw material that obtains, sintering temperature is 300~650 ℃, and sintering time is 2~10 hours;
(3) product after the presintering is ground and mixes, calcine in air atmosphere, calcining temperature is 700~1200 ℃, and calcination time is 2~18 hours, obtains a kind of borate base red fluorescent powder.
3. the preparation method of a kind of borate base red fluorescent powder according to claim 2 is characterized in that: the compound of the described K of containing element is a kind of in potassium hydroxide, salt of wormwood, the saltpetre; The compound that contains the M element is a kind of in oxide compound, the nitric acid thing, and the M element is a kind of among La, Gd, the Y; The compound that contains the Eu element is a kind of in europium sesquioxide, the europium nitrate; The compound that contains the B element is a kind of in boron oxide, the boric acid.
4. the preparation method of a kind of borate base red fluorescent powder according to claim 2, it is characterized in that: the described sintering temperature of step (2) is 350~600 ℃, and sintering time is 3~8 hours.
5. the preparation method of a kind of borate base red fluorescent powder according to claim 2, it is characterized in that: the described calcining temperature of step (3) is 750~1100 ℃, and calcination time is 3~15 hours.
6. by the application of a kind of borate base red fluorescent powder claimed in claim 1, it is characterized in that: cooperate an amount of blueness and green emitting phosphor, apply and be packaged in outside the diode, for the preparation of the White-light LED illumination device.
CN201310263131.4A 2013-06-27 2013-06-27 Borate red fluorescent powder and preparation method and application thereof Expired - Fee Related CN103305216B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105885836A (en) * 2014-12-17 2016-08-24 温州大学 Multi-wavelength emission Eu3+ uni-doped borate luminescent material and preparing method thereof
CN106544029A (en) * 2016-11-05 2017-03-29 桂林理工大学 fluorine-containing phosphate red fluorescent powder and preparation method thereof
CN107858146A (en) * 2017-09-30 2018-03-30 西安建筑科技大学 A kind of Eu3+Ion doping borate(K6Ba4B8O19)The synthetic method of base red fluorescent powder
WO2018098690A1 (en) * 2016-11-30 2018-06-07 深圳市耀铭豪智能科技有限公司 Led illuminating device and preparation method therefor
CN108822836A (en) * 2018-06-08 2018-11-16 南通纺织丝绸产业技术研究院 A kind of Eu2+And Eu3+The fluorescent powder of europium ion mixing activation, preparation method and application

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JP2004123764A (en) * 2002-08-07 2004-04-22 Nec Lighting Ltd Red light-emitting phosphor and light-emitting element using the same

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JP2004123764A (en) * 2002-08-07 2004-04-22 Nec Lighting Ltd Red light-emitting phosphor and light-emitting element using the same

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105885836A (en) * 2014-12-17 2016-08-24 温州大学 Multi-wavelength emission Eu3+ uni-doped borate luminescent material and preparing method thereof
CN106544029A (en) * 2016-11-05 2017-03-29 桂林理工大学 fluorine-containing phosphate red fluorescent powder and preparation method thereof
WO2018098690A1 (en) * 2016-11-30 2018-06-07 深圳市耀铭豪智能科技有限公司 Led illuminating device and preparation method therefor
KR20190032490A (en) 2016-11-30 2019-03-27 선전 와이엠에이치 인텔리전트 테크놀러지 컴퍼니 리미티드 Led illuminating device and preparation method therefor
US10920135B2 (en) 2016-11-30 2021-02-16 Shenzhen Ymh Intelligent Technology Co., Ltd. Preparation method of an LED illuminating device
CN107858146A (en) * 2017-09-30 2018-03-30 西安建筑科技大学 A kind of Eu3+Ion doping borate(K6Ba4B8O19)The synthetic method of base red fluorescent powder
CN108822836A (en) * 2018-06-08 2018-11-16 南通纺织丝绸产业技术研究院 A kind of Eu2+And Eu3+The fluorescent powder of europium ion mixing activation, preparation method and application

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