CN100334185C - Rare-earth yttrium-aluminium garnet luminous material and its gas-phase preparing method - Google Patents
Rare-earth yttrium-aluminium garnet luminous material and its gas-phase preparing method Download PDFInfo
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- CN100334185C CN100334185C CNB2005101222541A CN200510122254A CN100334185C CN 100334185 C CN100334185 C CN 100334185C CN B2005101222541 A CNB2005101222541 A CN B2005101222541A CN 200510122254 A CN200510122254 A CN 200510122254A CN 100334185 C CN100334185 C CN 100334185C
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Abstract
The present invention discloses a rare earth yttrium aluminum garnet light emitting material and a gas phase preparing method thereof, which belongs to the technical field of light emitting materials. The light emitting material has a chemical formula of Y<3-m>Al<5-n>RnO<15>: Ce<m>, wherein the R is one or more than one of Ga, In or B; the value range of the atom mole number m in the chemical formula is equal to 0.01 to 0.05, and the value range of the atom mole number n in the chemical formula is equal to 1 to 3. The present invention is characterized in that nanometer imitated thin diasporite colloidal particles in the range of 5 nanometers to 40 nanometers are used as seed crystals and form a stable colloidal sol with salts of each component in the chemical formula; spherical particles are prepared by the gas phase method, and the pure yttrium aluminum garnet phase light emitting material is obtained by high heat treatment. The excitation wavelengths of the light emitting material are between 460 nm and 480 nm, emitting wavelengths change between 531 nm and 560 nm, and the sizes of the particles are between 20 nm to 5 microns. The light emitting material prepared by the method has the advantages of pure phase, uniform size, spherical solid core and stable temperature characteristic of the emitting wavelength of the light emitting material.
Description
[technical field]
The present invention relates to the luminescent material technical field, particularly a kind of sphere and nanometer be the rare-earth yttrium-aluminium garnet luminous material of micron size extremely, and adopts the aluminum oxide seed crystal colloidal sol technology of nanoscale size and the preparation method that the gas phase technology of preparing combines.
[background technology]
(chemical formula is Y to yttrium aluminum garnet
3Al
5O
12, being abbreviated as YAG) and pottery has advantages such as high-temperature oxidation resistant, creep is little, thermal conductivity is low, can be applicable to fire-resistant and insulating material; YAG belongs to tesseral system, does not have birefringence effect, can be applicable to have the crystalline ceramics of excellent optical property, as solid laser material to replace the YAG monocrystalline; Doped with rare-earth elements and transition group ionic YAG are extremely important white light-emitting diodes luminescent materials.
Solid-phase synthesis is the traditional method of the rare earth doped YAG luminescent material of preparation, mass-producing easily, and the main drawback of existence has: the particulate material that (1) adds differs in size, and component is not easy to mix; (2) raw material and burn till product and all need ball milling is usually introduced impurity, for example iron easily in the process; (3) calcining temperature is higher, and product removes principal crystalline phase YAG (Y
3Al
5O
12) outside, there is a small amount of intermediate phase toward contact, for example YAM (YAl
2O
9) and YA (YAlO
3); (5) calcining of comparatively high temps and mechanical milling process energy expenditure height, noise is big.
The wet-chemical coprecipitation method is another method of preparation YAG.The spherical YAG powder that can prepare nanoscale with this method, the deficiency that exists is that each component chemical coprecipitation technique condition (as pH, concentration) is not easy control, and preparation time is long, and operation is many, washing and filtration operation produce waste water, and dry and high temperature burns till and causes particle agglomeration easily.
The sol-gel method of metal alkoxide also is used for preparing the YAG:Ce luminescent material, and complex procedures, technical qualification are not easy control, and alkoxide raw material cost height is not suitable for scale production.Employing urea is that the polymer sol combustion synthesis method of fuel obtains research.Adopt the sol-gel method of the inorganic salt of not introducing hetero-ion can greatly reduce aspect the material preparation cost, the peptisation that patent ZL03117872.3 and ZL03117871.5 disclose with the pseudo-boehmite nano particle has prepared luminescent material and discloses a kind of colloidal state working method.The nitrate of human yttrium, cerium and aluminium such as Chung-Hsin Lua mixes with urea and polyvinyl alcohol, becomes gel in 2 hours 250 ℃ of heating, at 800-1100 ℃ of burning Synthetic 2 to 6 hour, obtains luminescent powder again.Subject matter be particle easily amorphous and and reunite, combustion processes discharges water vapor and a large amount of obnoxious flavour (Cerium-ion-doped yttrium aluminum garnet nanophosphorsprepared through sol-gel pyrolysis for luminescent lighting, Applied Physics letters, 2002,80 (19): 3609-3610).
Adopt the spraying-pyrolytic technique of soluble salt (being generally the nitrate of each component) solution developed in the luminescent material technology of preparing. each composition of spraying-pyrolytic process raw material is at ion, molecular level uniform mixing, be a kind of gas phase synthetic technology that forms liquid-droplet aerosol with air or ultrasonic wave in essence, moisture is rapid evaporation in atomization process, can significantly overcome the deficiency in the washing and filtering operation of the component uniformity of existing solid-phase synthesis and liquid phase synthesizing method.Simultaneously, the subject matter that existing spraying-pyrolysis exists is, be entirely drop that the solution of salt ion is atomized when the moisture rapid evaporation and dry gel particle when follow-up burning till, particle is damaged easily or be hollow shape, is not easy to form sphere.
[summary of the invention]
Purpose of the present invention is intended to overcome the deficiencies in the prior art, and discloses a kind of vapor phase production technology that contains nanometer seed crystal micelle of rare-earth yttrium-aluminium garnet luminous material.The outstanding feature of this method is to adopt cheap nanoscale pseudo-boehmite as seed crystal, through peptization, form even colloidal sol with each component at molecular scale and nanoscale level, prepare the YAG luminescent material that not need ball milling with the gas phase two-step approach that atomizes-burn till again.
The present invention discloses a kind of rare-earth yttrium-aluminium garnet luminous material for achieving the above object, it is characterized in that: its substrate material is the spheroplast of the nanometer of aluminate to the micron size; Its chemical formula is Y
3-mAl
5-nR
nO
12: Ce
mWherein R is one or more among Ga, In or the B; It is m=0.01～0.05 that atomic molar in the chemical formula is counted span, n=1～3.
The invention also discloses the preparation method of this luminescent material, it is characterized in that may further comprise the steps:
1) alumina gel preparation: the pseudo-boehmite of the nanoscale that adopts pseudo-boehmite to coordinate to be divided into percent by weight 98-99% is as the nanometer seed crystal, with pseudo-boehmite: water=5～15%: 95～85% (weight percents), and adjust acidity to pH=2-6;
2) adulterated alumina gel preparation:, stir with adding corresponding chlorinated thing or nitrate in the above-mentioned alumina gel;
3) doping colloidal atomizing: at 150 ℃～250 ℃ of compressed air temperature, dry air amount 100～300m
3/ h under streams 1～2L/h, obtains dried particle;
4) burn till, at reducing atmosphere, reach 1200 ℃～1400 ℃ of firing temperatures, carry out high temperature in time 2-5 hour and burn till, obtaining body colour is the pure YAG phase of xanchromatic product.
The present invention is by adjusting solid content, acidity and the dispersing mode of material solution, control preembedded pseudo-boehmite seed crystal size; Change by the atomizing droplet parameter, obtain spherical solid light-emitting particles material controlled from the nanometer to the submicron-scale; Because particle is little, firing temperature is reduced.The excitation wavelength of the luminescent material of this law preparation is between 460 nanometer to 480 nanometers, and emission wavelength changes between the 560nm nanometer in 531 nanometers, and granular size is between 20nm to 5 micron.Luminescent material of the present invention does not need ball milling, pollutes for a short time, and energy consumption is low, and size evenly, and is spherical in shape solid, and the temperature profile of the emission wavelength of luminescent material is stable, can be used for the large-scale production of white light-emitting diodes luminescent material.
[description of drawings]
The XRD figure of the YAG luminescent material of Fig. 1 the present invention preparation;
The excitation spectrum of the YAG luminescent material of Fig. 2 the present invention preparation;
The emitting fluorescence spectrogram of the YAG luminescent material of Fig. 3 the present invention preparation.
[embodiment]
Following example is unrestricted the present invention in order further to illustrate technological process feature of the present invention.Rare-earth yttrium-aluminium garnet luminous material its gas-phase preparation method of the present invention can be prepared by following steps:
1. alumina gel: adopt the pseudo-boehmite of a kind of size of nanometer seed crystal at the 5-40 nanoscale, purity is 98-99% (percent by weight), uses dissolved in distilled water, and solid-to-liquid ratio is pseudo-boehmite: water=5-15%: 95-85%.With percentage concentration is that 30% hydrochloric acid soln or salpeter solution are adjusted acidity to the pH=2-6 scope, obtains the colloid of different micelle sizes after homogenizing is disperseed.
2. doped aluminium colloid: according to chemical formula is Y
3-mAl
5-nR
nO
12: Ce
m, wherein atomic molar is counted m=0.01～0.05, n=1～3, R=Ga, In, B.(purity is 99.99-99.999% (percent by weight) to add the muriate of corresponding component or nitrate in the alumina gel successively, adopt the mode of mechanical stirring or ultrasonic agitation carry out uniform dopingization, after homogenizing is disperseed, obtain the alumina gel of different doping compositions.
3. the atomizing of colloidal droplets: on apparatus for gas-phase synthesis, add 150 ℃-250 ℃ of hot air temperatures, dry air amount 100-300m after the control compression
3/ h, streams 1-2L/h obtains the particle of different sizes and composition.
4. burn till: 1200 ℃-1600 ℃ of controlled temperature in weakly reducing atmosphere thermal treatment 2-5 hour, without ball milling, can obtain the light-emitting particles material.Reducing atmosphere can adopt N
2+ H
2, a kind of in decomposed ammonia body or the coal gas.
Example 1
Press pseudo-boehmite: water=5: 95 (percent by weight), pseudo-boehmite is dissolved in the deionized water, be that 30% salpeter solution is adjusted acidity to pH=2 with percentage concentration, behind ultra-sonic dispersion, obtain stable colloid, about 5 nanometers of seed crystal; By chemical formula is Y
3-mAl
5-nR
nO
12: Ce
m, wherein atomic molar is counted m=0.02, n=1, and R=Ga, B adds simultaneously, and the atomic molar number respectively is 0.5.Add Yttrium trinitrate, cerous nitrate, gallium nitrate and boric acid, carry out mechanical stirring, form doping colloidal sol, colloidal sol left standstill 24 hours; Atomization parameter is set is: 250 ℃ of temperature ins, dry air amount 100m
3/ h, streams 2L/h, atomized particle; Feeding flow in horizontal pipe furnace is the N of 2L/h
2+ H
2Mixed gas, after burning till 2 hours under 1200 ℃, obtaining body colour is the pure YAG phase of xanchromatic product, the particle median size is 20 nanometers, and is spherical in shape solid.
Accompanying drawing 1 shows the XRD figure spectrum of the product of this example 1 preparation, shows that product is single pure YAG crystalline phase; Accompanying drawing 2 and Fig. 3 are that (the monitoring emmission spectrum is λ for the excitation spectrum of YAG luminescent material of preparation
Ex=533nm) and emitting fluorescence (excitation spectrum is λ
Ex=460nm) spectrogram, X-coordinate is wavelength (unit is nm) in the spectrogram, ordinate zou is luminous intensity (unit for arbitrarily, i.e. a.u.).
Example 2
Press pseudo-boehmite: water=10: 90 (percent by weight), pseudo-boehmite is dissolved in the deionized water, be that 30% hydrochloric acid soln is adjusted acidity to pH=4 with percentage concentration, after mechanical dispersion, obtain stable colloid, about 20 nanometers of seed crystal; Press Y
3-mAl
5-nB
nO
12: Ce
m, m=0.05, n=3 adds Yttrium trinitrate, cerous nitrate, magnesium nitrate and boric acid, carries out mechanical stirring, forms doping colloidal sol, and colloidal sol left standstill 24 hours; Atomization parameter is set is: 1500 ℃ of temperature ins, dry air amount 200m
3/ h, streams 1L/h, atomized particle; In elevator furnace, obtain weakly reducing atmosphere with activated carbon,, after burning till 3 hours under 1300 ℃, obtaining body colour is the pure YAG phase of xanchromatic product, the particle median size is 1 micron, and is spherical in shape solid.The XRD figure spectrum of luminescent material excites with emmission spectrum and sees curve 2 corresponding among accompanying drawing 2 and Fig. 3 respectively with example 1.
Example 3
Press pseudo-boehmite: water=15: 85 (percent by weight), pseudo-boehmite is dissolved in the deionized water, be that 30% hydrochloric acid soln is adjusted acidity to pH=6 with percentage concentration, after mechanical dispersion, obtain stable colloid, about 40 nanometers of seed crystal; Press Y
3-mAl
5-nB
nO
12: Ce
m, m=0.01, n=1 adds Yttrium trinitrate, cerous nitrate and boric acid, carries out ultra-sonic dispersion, forms doping colloidal sol, and colloidal sol left standstill 24 hours; Atomization parameter is set is: 110 ℃ of temperature ins, dry air amount 300m
3/ h, streams 1.5L/h, atomized particle; Separate stove with ammonia and obtain weakly reducing atmosphere, after burning till 5 hours under 1600 ℃, obtaining body colour is the pure YAG phase of xanchromatic product, and the particle median size is 5 microns, and is spherical in shape solid.The XRD figure spectrum of luminescent material excites with emmission spectrum and sees curve 3 corresponding among accompanying drawing 2 and Fig. 3 respectively with example 1.
Claims (5)
1. its gas-phase preparation method of a rare-earth yttrium-aluminium garnet luminous material is characterized in that may further comprise the steps:
1) alumina gel preparation: adopt purity be the pseudo-boehmite of nanoscale of percent by weight 98-99% as the nanometer seed crystal, with pseudo-boehmite: water is percent by weight 5～15%: 95～85%, and adjust acidity to pH=2-6;
2) adulterated alumina gel preparation:, stir with adding corresponding chlorinated thing or nitrate in the above-mentioned alumina gel;
3) doping colloidal atomizing: at 150 ℃～250 ℃ of compressed air temperature, dry air amount 100～300m
3/ h under streams 1～2L/h, obtains dried particle;
4) burn till,, reach 1200 ℃～1600 ℃ of firing temperatures, carry out high temperature in time 2-5 hour and burn till at reducing atmosphere; Obtaining substrate material is aluminate, and its chemical formula is Y
3-mAl
5-nR
nO
12: Ce
m, wherein R is one or more among Ga, In or the B, and it is m=0.01～0.05 that the atomic molar in the chemical formula is counted span, and n=1～3 body colours are the pure YAG phase of xanchromatic product.
2. according to the described preparation method of claim 1, the size that it is characterized in that nanometer seed crystal in the step 1) is in the 5-40 nanometer range.
3. according to the described preparation method of claim 1, it is characterized in that adjusting in the step 1) acidity percentage concentration and be 30% hydrochloric acid soln or salpeter solution.
4. according to the described preparation method of claim 1, it is characterized in that step 2) in adopt the mode of mechanical stirring or ultrasonic agitation carry out uniform dopingization.
5. according to the described preparation method of claim 1, it is characterized in that the reducing atmosphere that burns till in the step 4) can adopt N
2+ H
2, a kind of in decomposed ammonia body or the coal gas.
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| CN104178158A (en) * | 2013-05-23 | 2014-12-03 | 海洋王照明科技股份有限公司 | Europium- dysprosium- co-doped rare earth boron indate luminescent film, preparing method thereof and electroluminescent device |
| CN111883788A (en) * | 2020-06-24 | 2020-11-03 | 华南理工大学 | Preparation method of cerium oxide-based medium-low temperature solid oxide fuel cell key material |
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