CN102942928A - Zirconate-base red phosphor, method for preparing same and application - Google Patents

Zirconate-base red phosphor, method for preparing same and application Download PDF

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CN102942928A
CN102942928A CN2012105028377A CN201210502837A CN102942928A CN 102942928 A CN102942928 A CN 102942928A CN 2012105028377 A CN2012105028377 A CN 2012105028377A CN 201210502837 A CN201210502837 A CN 201210502837A CN 102942928 A CN102942928 A CN 102942928A
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fluorescent powder
europium
red fluorescent
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CN102942928B (en
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黄彦林
秦琳
关莹
陶正旭
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Yangzhou Feng Feng Hi Tech Industry Investment Development Group Co Ltd
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Suzhou University
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Abstract

The invention discloses a zirconate-base red phosphor, a method for preparing the same and an application. The active ion of the phosphor is Eu<3+>, and the chemical formula of the phosphor is MII2RIII1-xEuxZrO5.5, wherein MII is one or a plurality of Sr<2+> and Ba<2+>, RIII is at least one of La<3+>, Ce<3+>, Pr<3+>, Nd<3+>, Sm<3+>, Gd<3+>, Tb<3+>, Dy<3+>, Ho<3+>, Er<3+>, Tm<3+>, Yb<3+>, Lu<3+>, Sc<3+> and Y<3+>, x is the molar percentage coefficient for replacing RIII with Eu<3+>, and x is not more than 1.0 and is not less than 0.0001. The luminescent wavelength of the red phosphor is mainly 613nanometers, strong excitation can be generated around 395nanometers, and the red phosphor is matched with a blue phosphor to be coated and encapsulated outside an InGaN diode, so that white light LED (light-emitting diode) lighting devices are produced. The product has good reproductivity and stable quality, and is suitable for industrial production.

Description

A kind of zirconate base red fluorescent powder, preparation method and application
Technical field
The present invention relates to a kind of fluorescent material as near ultraviolet excitated lower emission red fluorescence, be particularly related to a kind of zirconate base red fluorescent powder and preparation method thereof, it can be applicable to be suitable for use as in the LED fluorescent material that the InGaN tube core of near ultraviolet 350～400nm radiation excites, and belongs to the fluorescent material technical field.
Background technology
The semi-conductor white light-emitting diode is a kind of novel solid-state illumination device that grows up nearly more than ten years.Than traditional incandescent light, luminescent lamp and compact type energy-saving lamp, WLED is called as " the 4th generation lighting source " because having the advantages such as high-level efficiency, little life-span of volume are long, pollution-free, energy-conservation, response is fast.
At present, most of intellecture property in this field is all monopolized by Japan, therefore goes for the intellecture property of oneself, just must develop some novel luminescent materials.One of important channel of white light emission is the body fluorescence conversion technology that utilizes rare earth luminescent material, and 460nm blue light or the 400nm near-ultraviolet light of the emission of InGaN semiconductor element are changed into white light.
Although white light LEDs can both be obtained good result on the individual event index such as luminous efficiency, colour rendering index, colour temperature, chromaticity coordinates at present,, but fail to prepare all gratifying devices of properties.Use fluorescent material and LED combination to realize the technique of white light, emission wavelength that can be by changing fluorescent material, the colourity that fluorescent material thickness is regulated white light LEDs, colour temperature etc., because this mode can obtain very high color developing, colour temperature is to mate arbitrarily within the 2500-10000K scope.Among existing technology, the fluorescent material that is used for white light LEDs lacks the ruddiness composition, and perhaps the luminous efficiency of red fluorescence powder is not high, and perhaps unstable properties causes that the white light LEDs luminous efficiency that encapsulates out is lower or the life-span is shorter.Therefore, the red fluorescence powder of development of new becomes the focus of domestic and international research.
Summary of the invention
The present invention is that red fluorescence powder absorbs weak deficiency near ultraviolet and blue region in the prior art in order to overcome, and provides a kind of degree of crystallinity high, and luminous mass is good, and simple, the free of contamination Eu of preparation technology 3+The zirconate red fluorescence powder, preparation method and the application thereof that activate.
For arriving above purpose, the technical solution used in the present invention provides a kind of zirconate base red fluorescent powder, and its active ions are trivalent europium ion Eu 3+The chemical formula of described fluorescent material is M II 2R III 1-xEu xZrO 5.5, wherein, M IIBe alkaline-earth metal strontium ion Sr 2+, barium ion Ba 2+In one or more, R IIIBe lanthanum ion La 3+, cerium ion Ce 3+, praseodymium ion Pr 3+, neodymium ion Nd 3+, samarium ion Sm 3+, europium ion Eu 3+, gadolinium ion Gd 3+, terbium ion Tb 3+, dysprosium ion Dy 3+, holmium ion Ho 3+, erbium ion Er 3+, ytterbium ion Yb 3+, lutetium ion Lu 3+, and scandium ion Sc and ruthenium ion Y 3+In at least a, xBe Eu 3+Replace R IIIThe molar percentage coefficient, 0.0001≤x≤1.0.
A kind of preparation method of aforesaid zirconate base red fluorescent powder comprises the steps:
(1) to contain alkaline-earth metal ions M II, rare earth ion R III, europium ion Eu 3+, zirconium ion Zr 4+Compound be raw material, press chemical formula M II 2R III 1-xEu xZrO 5.5In the mol ratio of each element take by weighing raw material, grind and mix, obtain mixture; In the described chemical formula, M IIBe alkaline-earth metal strontium ion Sr 2+, barium ion Ba 2+In a kind of or their arbitrary combination, R IIIBe lanthanum ion La 3+, cerium ion Ce 3+, praseodymium ion Pr 3+, neodymium ion Nd 3+, samarium ion Sm 3+, europium ion Eu 3+, gadolinium ion Gd 3+, terbium ion Tb 3+, dysprosium ion Dy 3+, holmium ion Ho 3+, erbium ion Er 3+, ytterbium ion Yb 3+, lutetium ion Lu 3+And scandium ion Sc 3+With ruthenium ion Y 3+In at least a, xBe Eu 3+Replace R IIIThe molar percentage coefficient, 0.0001≤x≤1.0;
(2) with the presintering 1～2 time under air atmosphere of the mixture that obtains, sintering temperature is 200～1200 ℃, and sintering time once is 1～20 hour;
(3) behind the naturally cooling, grind and mix, the mixture that obtains is calcined in air atmosphere, calcining temperature is 1200～1500 ℃, and calcination time is 1～20 hour, obtains a kind of zirconate base red fluorescent powder.
The alkaline-earth metal ions M that contains of the present invention IICompound be M IIOxide compound, M IIOxyhydroxide, M IICarbonate, M IINitrate, M IIOxalate and M IIVitriol in a kind of, or their arbitrary combination.
The described rare-earth element R that contains IIICompound be R IIIOxide compound, nitrate, and R IIIRare earth organic complex in a kind of, or their arbitrary combination.
The described europium ion Eu that contains 3+Compound be a kind of in europium sesquioxide, the europium nitrate, or their arbitrary combination.
The described zirconium ion Zr that contains 4+Compound be a kind of in zirconium dioxide, the zirconium tetrachloride, or their arbitrary combination.
The preferred scheme that the present invention prepares described zirconate base red fluorescent powder is: mixture in air atmosphere presintering once, sintering temperature is 200～1200 ℃, sintering time is 1～20 hour; Calcining temperature is 1200～1500 ℃, and calcination time is 1～20 hour.
The excitation wavelength of fluorescent material of the present invention is the near ultraviolet region of 350～400nm, is matched with the radiation wavelength of near ultraviolet InGaN chip, cooperates an amount of blue colour fluorescent powder, applies and is packaged in outside the InGaN diode, preparation 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 zirconate base red fluorescent powder that activates can send main peak at the ruddiness of 613nm under the exciting of 350～460nm 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 purple light or ultraviolet leds chip, prepare white light LEDs as red fluorescence powder; Also can cooperate with blue light, purple light, ultraviolet leds, perhaps mix the fluorescent material of other type, the preparation multi-color LED.
3, with other sulfide Y 2O 2S:Eu 3+, halogenide etc. compares for the red fluorescence powder of substrate material, the preparation process of substrate material of the present invention is simple, the product easily collecting is without waste water and gas discharging, environmental friendliness.
Description of drawings
Fig. 1 is the Ba that the embodiment of the invention provides 2Gd 0.8Eu 0.2ZrO 5.5The X-ray powder diffraction collection of illustrative plates of sample specimens and the comparison of standard card PDF#47-0389;
Fig. 2 is the Ba that the embodiment of the invention provides 2Gd 0.8Eu 0.2ZrO 5.5Sample specimens is monitored exciting light spectrogram that red utilizing emitted light 613 nm obtain and is excited the lower luminescent spectrum figure that obtains at 395nm.
Fig. 3 is the Ba that the embodiment of the invention provides 2Gd 0.8Eu 0.2ZrO 5.5The decay of luminescence curve of sample specimens.
Fig. 4 is the Ba that the embodiment of the invention provides 2EuZrO 5.5The X-ray powder diffraction collection of illustrative plates of sample specimens and the comparison of standard card PDF#53-1007;
Fig. 5 is the Ba that the embodiment of the invention provides 2EuZrO 5.5Sample specimens is monitored exciting light spectrogram that red utilizing emitted light 613 nm obtain and is excited the lower luminescent spectrum figure that obtains at 395nm and 310nm.
Fig. 6 is the Ba that the embodiment of the invention provides 2Gd 0.8Eu 0.2ZrO 5.5The decay of luminescence curve of sample specimens;
Fig. 7 is the Ba that the embodiment of the invention provides 2Dy 0.8Eu 0.2ZrO 5.5The X-ray powder diffraction collection of illustrative plates of sample specimens and the comparison of standard card PDF#50-1646;
Fig. 8 is the BaSrY that the embodiment of the invention provides 0.8Eu 0.2ZrO 5.5The X-ray powder diffraction collection of illustrative plates of sample specimens and the comparison of standard card PDF#51-0255;
Fig. 9 is the BaSrY that the embodiment of the invention provides 0.8Eu 0.2ZrO 5.5Sample specimens is monitored exciting light spectrogram that red utilizing emitted light 611 nm obtain and is excited the lower luminescent spectrum figure that obtains at 395nm.
Figure 10 is the BaSrY that the embodiment of the invention provides 0.8Eu 0.2ZrO 5.5The decay of luminescence curve of sample specimens.
Figure 11 is the Sr that the embodiment of the invention provides 2La 0.8Eu 0.2ZrO 5.5Sample specimens is monitored exciting light spectrogram that red utilizing emitted light 594 nm obtain and is excited the lower luminescent spectrum figure that obtains at 395nm.
Figure 12 is the BaSrY that the embodiment of the invention provides 0.8Eu 0.2ZrO 5.5The decay of luminescence curve of sample specimens.
Embodiment
Below in conjunction with drawings and Examples technical solution of the present invention is further described.
Embodiment 1
According to chemical formula Ba 2Gd 0.8Eu 0.2ZrO 5.5In the stoichiometric ratio of each element, take by weighing respectively barium carbonate BaCO 3: 1.9735 grams, gadolinium sesquioxide Gd 2O 3: 0.725 gram, europium sesquioxide Eu 2O 3: 0.176 gram, zirconium white ZrO 2: 0.6161 gram, after grinding in agate mortar and mixing, among air atmosphere, 1350 ℃ of lower twice sintering, sintering time are 24 hours, cooling causes room temperature, takes out sample.Again even the abundant mixed grinding of compound, among air atmosphere, 1450 ℃ of lower sintering, sintering time is 24 hours, is cooled to room temperature, namely obtains the red fluorescence powder of powder shaped doping with rare-earth ions europium.
Referring to accompanying drawing 1, the X-ray powder diffraction collection of illustrative plates and the standard card PDF#47-0389 that prepare sample by the present embodiment technical scheme compare, the demonstration of XRD test result, and prepared material is monophase materials.
Referring to accompanying drawing 2, from closely finding out prepare the excitation spectrum that sample specimens monitoring utilizing emitted light 613 nm obtain by the technology of the present invention, luminous excites the source mainly in the scope of 390nm and 400nm, can mate well the light that the near ultraviolet diode chip for backlight unit sends.
Referring to accompanying drawing 2, it is to excite the lower luminescent spectrum that obtains by the material sample that the present embodiment technical scheme prepares at near-ultraviolet light 395nm, can find out that this material is main luminous at red spectral band, and luminescence center is positioned at about 615nm.And obtaining colourity is x=0.661 y=0.339.
Referring to accompanying drawing 3, it is to excite down the extinction curve figure that 615nm is luminous at 355nm by the material sample that the present embodiment technical scheme prepares.The luminous life-span is about 547 microseconds, is the characteristic decay of trivalent europium ion, does not have the existence of twilight sunset.
Embodiment 2
According to chemical formula Ba 2EuZrO 5.5In the stoichiometric ratio of each element, take by weighing respectively barium carbonate BaCO 3: 1.9735 grams, europium sesquioxide Eu 2O 3: 0.88 gram, zirconium white ZrO 2: 0.6161 gram, after grinding in agate mortar and mixing, among air atmosphere, 1525 ℃ of lower sintering, sintering time are 6 hours, cooling causes room temperature, takes out sample, namely obtains the red fluorescence powder of powder shaped doping with rare-earth ions europium.Main structure properties, excitation spectrum, luminescent spectrum and decay of luminescence curve are similar to embodiment 1.
Referring to accompanying drawing 4, the X-ray powder diffraction collection of illustrative plates and the standard card PDF#53-1007 that prepare sample by the present embodiment technical scheme compare, the demonstration of XRD test result, and prepared material is monophase materials.
Referring to accompanying drawing 5, it is the Ba that the present embodiment provides 2EuZrO 5.5Sample specimens is monitored exciting light spectrogram that red utilizing emitted light 613 nm obtain and is excited the lower luminescent spectrum figure that obtains at 395nm and 310nm.From closely finding out prepare the excitation spectrum that sample specimens monitoring utilizing emitted light 613 nm obtain by the technology of the present invention, luminous excites the source mainly in the scope of 390nm to 410nm, can mate well the light that the near ultraviolet diode chip for backlight unit sends.It can also be seen that, this material is main luminous at red spectral band, and luminescence center is positioned at about 615nm.And obtaining colourity is x=0.637 y=0.362.
Referring to accompanying drawing 6, it is to excite down the extinction curve figure that 615nm is luminous at 355nm by the material sample that the present embodiment technical scheme prepares.The luminous life-span is about 1345 microseconds, is the characteristic decay of trivalent europium ion, does not have the existence of twilight sunset.
Embodiment 3
According to chemical formula Ba 2Dy 0.8Eu 0.2ZrO 5.5In the stoichiometric ratio of each element, take by weighing respectively barium carbonate BaCO 3: 1.9735 grams, dysprosium oxide Dy 2O 3: 0.746 gram, europium sesquioxide Eu 2O 3: 0.176 gram, zirconium white ZrO 2: 0.6161 gram, after grinding in agate mortar and mixing, among air atmosphere, 1200 ℃ of lower sintering, sintering time are 20 hours, cooling causes room temperature, takes out sample.Again even the abundant mixed grinding of compound, among air atmosphere, 1300 ℃ of lower sintering, sintering time is 15 hours, is cooled to room temperature, namely obtains the red fluorescence powder of powder shaped doping with rare-earth ions europium.Main structure properties, excitation spectrum, luminescent spectrum and decay of luminescence curve are similar to embodiment 1.
Referring to accompanying drawing 7, it is the Ba that the present embodiment provides 2Dy 0.8Eu 0.2ZrO 5.5The X-ray powder diffraction collection of illustrative plates of sample specimens and the comparison of standard card PDF#50-1646; The demonstration of XRD test result, prepared material is monophase materials.
Embodiment 4
According to chemical formula Ba 2Sm 0.8Eu 0.2ZrO 5.5In the stoichiometric ratio of each element, take by weighing respectively barium carbonate BaCO 3: 1.9735 grams, Samarium trioxide Sm 2O 3: 0.6974 gram, europium sesquioxide Eu 2O 3: 0.176 gram, zirconium white ZrO 2: 0.6161 gram, after grinding in agate mortar and mixing, among air atmosphere, 1350 ℃ of lower twice sintering, sintering time are 72 hours, cooling causes room temperature, takes out sample.Again even the abundant mixed grinding of compound, among air atmosphere, 1450 ℃ of lower sintering, sintering time is 24 hours, is cooled to room temperature, namely obtains the red fluorescence powder of powder shaped doping with rare-earth ions europium.Main structure properties, excitation spectrum, luminescent spectrum and decay of luminescence curve are similar to embodiment 1.
Embodiment 5
According to chemical formula Ba 2Y 0.8Eu 0.2ZrO 6In the stoichiometric ratio of each element, take by weighing respectively barium carbonate BaCO 3: 1.9735 grams, yttrium oxide Y 2O 3: 0.4516 gram, europium sesquioxide Eu 2O 3: 0.176 gram, zirconium white ZrO 2: 0.6161 gram, after grinding in agate mortar and mixing, among air atmosphere, 1400 ℃ of lower twice sintering, sintering time are 45 hours, cooling causes room temperature, takes out sample.Again even the abundant mixed grinding of compound, among air atmosphere, 1500 ℃ of lower sintering, sintering time is 12 hours, is cooled to room temperature, namely obtains the red fluorescence powder of powder shaped doping with rare-earth ions europium.Main structure properties, excitation spectrum, luminescent spectrum and decay of luminescence curve are similar to embodiment 1.
Embodiment 6
According to chemical formula BaSrY 0.8Eu 0.2ZrO 5.5In the stoichiometric ratio of each element, take by weighing respectively barium carbonate BaCO 3: 0.9868 gram, cesium carbonate SrCO 3: 0.7382 gram, yttrium oxide Y 2O 3: 0.4516 gram, europium sesquioxide Eu 2O 3: 0.176 gram, zirconium white ZrO 2: 0.6161 gram, after in agate mortar, grinding and mixing, among air atmosphere, 1500 ℃ of lower sintering 4 hours, cooling causes room temperature, takes out sample, namely obtains the red fluorescence powder of powder shaped doping with rare-earth ions europium.Main structure properties, excitation spectrum, luminescent spectrum and decay of luminescence curve are similar to embodiment 1.
Referring to accompanying drawing 8, it is X-ray powder diffraction collection of illustrative plates and the standard card PDF#51-0255 comparison for preparing sample by the present embodiment technical scheme, the demonstration of XRD test result, and prepared material is monophase materials.
Referring to accompanying drawing 9, it is the BaSrY that the present embodiment provides 0.8Eu 0.2ZrO 5.5Sample specimens is monitored exciting light spectrogram that red utilizing emitted light 611 nm obtain and is excited the lower luminescent spectrum figure that obtains at 395nm.From closely finding out prepare the excitation spectrum that sample specimens monitoring utilizing emitted light 611 nm obtain by the technology of the present invention, luminous excites the source mainly in the scope of 390nm to 400nm, can mate well the light that the near ultraviolet diode chip for backlight unit sends.Material product by the preparation of the present embodiment technical scheme excite the lower luminescent spectrum that obtains to find out at near-ultraviolet light 395nm, and this material is main luminous at red spectral band, and luminescence center is positioned at about 615nm.And obtaining colourity is x=0.617 y=0.354.
Referring to accompanying drawing 10, it is to excite down the extinction curve figure that 611nm is luminous at 266nm by the material sample that the present embodiment technical scheme prepares.The luminous life-span is about 996 microseconds, is the characteristic decay of trivalent europium ion, and the result shows the existence that does not have twilight sunset.
Embodiment 7
According to chemical formula Sr 2La 0.8Eu 0.2ZrO 5.5In the stoichiometric ratio of each element, take by weighing respectively cesium carbonate SrCO 3: 1.4763 grams, lanthanum trioxide La 2O 3: 0.6516 gram, europium sesquioxide Eu 2O 3: 0.176 gram, zirconium white ZrO 2: 0.6161 gram, after in agate mortar, grinding and mixing, among air atmosphere, 1500 ℃ of lower sintering 4 hours, cooling causes room temperature, takes out sample, namely obtains the red fluorescence powder of powder shaped doping with rare-earth ions europium.Main structure properties, excitation spectrum, luminescent spectrum and decay of luminescence curve are similar to embodiment 1.
Referring to accompanying drawing 11, from closely finding out prepare the excitation spectrum that sample specimens monitoring utilizing emitted light 594 nm obtain by the technology of the present invention, luminous excites the source mainly in the scope of 390nm to 400nm, can mate well the light that the near ultraviolet diode chip for backlight unit sends.
Referring to accompanying drawing 11, it is the Sr that the present embodiment provides 2La 0.8Eu 0.2ZrO 5.5Sample specimens is monitored exciting light spectrogram that red utilizing emitted light 594 nm obtain and is excited the lower luminescent spectrum figure that obtains at 395nm; Excite the lower luminescent spectrum that obtains to find out by sample at near-ultraviolet light 395nm, this material is main luminous at red spectral band, and luminescence center is positioned at about 615nm.And obtaining colourity is x=0.624 y=0.324.
Referring to accompanying drawing 12, it is to excite down the extinction curve figure that 611nm is luminous at 355nm by the material sample that the present embodiment technical scheme prepares.The luminous life-span is about 1038 microseconds, is the characteristic decay of trivalent europium ion, and the result shows the existence that does not have twilight sunset.
Embodiment 8
According to chemical formula Sr 2Gd 0.8Eu 0.2ZrO 5.5In the stoichiometric ratio of each element, take by weighing respectively cesium carbonate SrCO 3: 1.4763 grams, gadolinium sesquioxide Gd 2O 3: 0.725 gram, europium sesquioxide Eu 2O 3: 0.176 gram, zirconium white ZrO 2: 0.6161 gram, after in agate mortar, grinding and mixing, among air atmosphere, 1500 ℃ of lower sintering 4 hours, cooling causes room temperature, takes out sample, namely obtains the red fluorescence powder of powder shaped doping with rare-earth ions europium.Main structure properties, excitation spectrum, luminescent spectrum and decay of luminescence curve are similar to embodiment 1.
Embodiment 9
According to chemical formula Sr 2Y 0.8Eu 0.2ZrO 6In the stoichiometric ratio of each element, take by weighing respectively cesium carbonate SrCO 3: 1.4763 grams, yttrium oxide Y 2O 3: 0.4516 gram, europium sesquioxide Eu 2O 3: 0.176 gram, zirconium white ZrO 2: 0.6161 gram, after in agate mortar, grinding and mixing, among air atmosphere, 1450 ℃ of lower sintering 4 hours, cooling causes room temperature, takes out sample, namely obtains the red fluorescence powder of powder shaped doping with rare-earth ions europium.Main structure properties, excitation spectrum, luminescent spectrum and decay of luminescence curve are similar to embodiment 1.
Embodiment 10
According to chemical formula Ba 2La 0.8Eu 0.2ZrO 5.5In the stoichiometric ratio of each element, take by weighing respectively barium carbonate BaCO 3: 1.9735 grams, lanthanum trioxide La 2O 3: 0.6516 gram, europium sesquioxide Eu 2O 3: 0.176 gram, zirconium white ZrO 2: 0.6161 gram, after in agate mortar, grinding and mixing, among air atmosphere, 1350 ℃ of lower three sintering, sintering time is 72 hours, cooling causes room temperature, takes out sample.Again even the abundant mixed grinding of compound, among air atmosphere, 1550 ℃ of lower sintering, sintering time is 12 hours, is cooled to room temperature, namely obtains the red fluorescence powder of powder shaped doping with rare-earth ions europium.Main structure properties, excitation spectrum, luminescent spectrum and decay of luminescence curve are similar to embodiment 1.
Embodiment 11
According to chemical formula Sr 2Gd 0.8Eu 0.2ZrO 5.5In the stoichiometric ratio of each element, take by weighing respectively cesium carbonate SrCO 3: 1.4763 grams, gadolinium sesquioxide Gd 2O 3: 0.725 gram, europium sesquioxide Eu 2O 3: 0.176 gram, zirconium tetrachloride ZrCl 4: 0.9261 gram, after in agate mortar, grinding and mixing, among air atmosphere, 1500 ℃ of lower sintering 4 hours, cooling causes room temperature, takes out sample, namely obtains the red fluorescence powder of powder shaped doping with rare-earth ions europium.Main structure properties, excitation spectrum, luminescent spectrum and decay of luminescence curve are similar to embodiment 1.

Claims (9)

1. zirconate base red fluorescent powder, the active ions that it is characterized in that it are trivalent europium ion Eu 3+The chemical formula of described fluorescent material is M II 2R III 1-xEu xZrO 5.5, wherein, M IIBe alkaline-earth metal strontium ion Sr 2+, barium ion Ba 2+In one or more, R IIIBe lanthanum ion La 3+, cerium ion Ce 3+, praseodymium ion Pr 3+, neodymium ion Nd 3+, samarium ion Sm 3+, europium ion Eu 3+, gadolinium ion Gd 3+, terbium ion Tb 3+, dysprosium ion Dy 3+, holmium ion Ho 3+, erbium ion Er 3+, ytterbium ion Yb 3+, lutetium ion Lu 3+, and scandium ion Sc and ruthenium ion Y 3+In at least a, xBe Eu 3+Replace R IIIThe molar percentage coefficient, 0.0001≤x≤1.0.
2. a preparation method who requires described zirconate base red fluorescent powder such as right 1 is characterized in that comprising the steps:
(1) to contain alkaline-earth metal ions M II, rare earth ion R III, europium ion Eu 3+, zirconium ion Zr 4+Compound be raw material, press chemical formula M II 2R III 1-xEu xZrO 5.5In the mol ratio of each element take by weighing raw material, grind and mix, obtain mixture; In the described chemical formula, M IIBe alkaline-earth metal strontium ion Sr 2+, barium ion Ba 2+In a kind of or their arbitrary combination, R IIIBe lanthanum ion La 3+, cerium ion Ce 3+, praseodymium ion Pr 3+, neodymium ion Nd 3+, samarium ion Sm 3+, europium ion Eu 3+, gadolinium ion Gd 3+, terbium ion Tb 3+, dysprosium ion Dy 3+, holmium ion Ho 3+, erbium ion Er 3+, ytterbium ion Yb 3+, lutetium ion Lu 3+And scandium ion Sc 3+With ruthenium ion Y 3+In at least a, xBe Eu 3+Replace R IIIThe molar percentage coefficient, 0.0001≤x≤1.0;
(2) with the presintering 1～2 time under air atmosphere of the mixture that obtains, sintering temperature is 200～1200 ℃, and sintering time once is 1～20 hour;
(3) behind the naturally cooling, grind and mix, the mixture that obtains is calcined in air atmosphere, calcining temperature is 1200～1500 ℃, and calcination time is 1～20 hour, obtains a kind of zirconate base red fluorescent powder.
3. the preparation method of a kind of zirconate base red fluorescent powder according to claim 2 is characterized in that: the described alkaline-earth metal ions M that contains IICompound be M IIOxide compound, M IIOxyhydroxide, M IICarbonate, M IINitrate, M IIOxalate and M IIVitriol in a kind of, or their arbitrary combination.
4. the preparation method of a kind of zirconate base red fluorescent powder according to claim 2 is characterized in that: contain rare-earth element R IIICompound be R IIIOxide compound, nitrate, and R IIIRare earth organic complex in a kind of, or their arbitrary combination.
5. the preparation method of a kind of zirconate base red fluorescent powder according to claim 2 is characterized in that: the described europium ion Eu that contains 3+Compound be a kind of in europium sesquioxide, the europium nitrate, or their arbitrary combination.
6. the preparation method of a kind of zirconate base red fluorescent powder according to claim 2 is characterized in that: the described zirconium ion Zr that contains 4+Compound be a kind of in zirconium dioxide, the zirconium tetrachloride, or their arbitrary combination.
7. the preparation method of a kind of zirconate base red fluorescent powder according to claim 2 is characterized in that: mixture in air atmosphere presintering once, sintering temperature is 200～1200 ℃, sintering time is 1～20 hour.
8. the preparation method of a kind of zirconate base red fluorescent powder according to claim 2, it is characterized in that: calcining temperature is 1200～1500 ℃, calcination time is 1～20 hour.
9. a kind of zirconate base red fluorescent powder as claimed in claim 1, it is characterized in that: the excitation wavelength of using described fluorescent material is the near ultraviolet region of 350～400nm, be matched with the radiation wavelength of near ultraviolet InGaN chip, cooperate an amount of blue colour fluorescent powder, apply and be packaged in outside the InGaN diode, preparation White-light LED illumination device.
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CN104178147A (en) * 2013-05-22 2014-12-03 海洋王照明科技股份有限公司 Praseodymium and holmium co-doped zirconium dioxide up-conversion luminescent material, and preparation method and application thereof
CN104974755A (en) * 2014-12-25 2015-10-14 陕西科技大学 Green rare-earth fluorescent powder for LED (Light Emitting Diode) and preparation method of fluorescent powder
CN113387565A (en) * 2020-03-13 2021-09-14 包头稀土研究院 Fluorescent glass and preparation method and application thereof
CN113387565B (en) * 2020-03-13 2022-04-05 包头稀土研究院 Fluorescent glass and preparation method and application thereof
WO2022134002A1 (en) * 2020-12-25 2022-06-30 苏州君诺新材科技有限公司 Dual-doped ultra-wide spectrum fluorescent powder and method for preparation thereof and device

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