CN105950141A - Preparation method of nitride-boride fluorescent powder material - Google Patents
Preparation method of nitride-boride fluorescent powder material Download PDFInfo
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- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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Abstract
The invention relates to a preparation method of a nitride-boride fluorescent powder material. The preparation method is characterized in that common metal salt or oxide is used as the raw material, a high-temperature solid-phase method is used for preparation, the preparation process of nitride fluorescent powder is simplified, and production cost is lowered. The expression of the nitride-boride fluorescent powder material is AM4-4x(BN2):xD, wherein A is one or more of Li, Na, K, Rb and Cs; M is one or more of Mg, Ca, Sr and Ba, and D is one or more of Mn<2+>, Ce<3+>, Pr<3+>, Nd<3+>, Pm<3+>, Sm<3+>, Sm<2+>, Eu<3+>, Eu<2+>, Tb<3+>, Dy<3+>, Ho<3+>, Er<3+>, Tm<3+>, Yb<3+> and Yb<2+>. The preparation method specifically includes: weighing the raw materials of A, M and D and boric acid according to stoichiometric ratio, adding appropriate amount of acetone into the raw materials, and sufficiently grinding to obtain a mixture; performing heat preservation on the mixture for 1-5 hours in an environment of 400-650 DEG C and under reduction atmosphere; grinding and evenly mixing obtained preliminary-combustion substance, and performing heat preservation on the mixture for 1-8 hours in an environment of 700-900 DEG C to obtain the nitride-boride fluorescent powder material. The preparation method has the advantages that the method using a solid-phase synthesizing method is low in synthesizing temperature, simple in preparation process, low in cost, safe, reliable, short in production cycle and suitable for large-scale industrial production, and the prepared fluorescent powder is excellent in light-emitting efficiency.
Description
Technical field
The present invention relates to a class and be applied to rare earth or the Mn of illumination field2+The preparation side of ion-activated nitrogen boride phosphor material powder
Method.
Background technology
Semiconductor lighting or light emitting diode (LED), due to it, to have energy-efficient, environmental protection, life-span length, luminous efficiency high
Remarkable advantage, thus it is considered forth generation lighting source, obtain countries in the world common concern and accelerated research and development.Realize white at present
Light LED most common method is exactly (such as YAG:Ce, CaAlSiN by blue-light LED chip and gold-tinted and red light fluorescent powder3: Eu2+)
Combine or nearly UV LED chip combines with red, green, blue fluorescent material, realize white by adjusting the light output of different-waveband
Light emission.Thus, the three primary colors fluorescent powder that exploitation is suitable for blue light and near ultraviolet excitation, luminous efficiency is high is that white light LEDs exists
Green illumination obtains right key.
Rare earth or transient metal doped nitride are that a class of discovered in recent years is novel, the white light LEDs luminescent material of excellent performance.
Compared to oxygen-containing fluorescent material such as conventional aluminate and silicate, nitride has following advantages:
(1)N3-Compared to O2-Ion has higher negative charge, and nephelauxetic effect makes material have higher covalency,
Therefore active ions such as Eu2+Or Ce3+Deng the division of 5d excited level bigger, and the center of gravity of 5d energy state also can reduce, profit
In the absorption and the transmitting that realize longer wavelength.
(2) higher covalency makes the Stokes displacement exciting and launching relatively small, is beneficial to improve luminous efficiency.With oxygen
Comparing, nitrogen and metal ion have higher bonding power, and therefore the structure of material is more firm, has more preferable physical and chemical performance.
AM4(BN2)3(A is Li, Na, K, Rb, Cs etc.；M is Mg, Ca, Sr, Ba etc.) it is a kind of novel nitrogen
Compound host material.The near ultraviolet excitated Eu of the reported first such as Wang Yuhua2+The LiSr activated4(BN2)3Red light fluorescent powder.Its report
Preparation method be by Sr3N2, Li3N, BN and EuF3Mix homogeneously in the glove box of exhausted water anoxybiotic, is then charged into BN
Crucible is at N2/H2(95/5) in gaseous mixture, 800 DEG C of sintering obtain final products in 30 minutes.The method preparation process is used
Mostly raw material is all expensive nitride, and the environment synthesized harsher (exhausted water anoxybiotic) thus to be not suitable for industry big
Large-scale production.
Summary of the invention
The invention provides a kind of rare earth ion (RE) or Mn2+The AM of doping4(BN2)3(A is Li, Na, K, Rb, Cs etc.；
M is Mg, Ca, Sr, Ba etc.) new method of fluorescent material, it has the advantages such as simple, the cheaper starting materials of preparation method, is suitable for work
Industry large-scale production.
The present invention is achieved through the following technical solutions:
One prepares AM4(BN2)3: the method for D, the wherein A combination of one or more in alkali metal；M is selected from alkaline earth
Metal Be, the combination of one or more in Mg, Ca, Sr, Ba etc.；D is selected from rare earth ion (Ce3+, Pr3+, Nd3+, Sm3+,
Sm2+, Eu3+, Eu2+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+) and Mn2+In one or more combination；It is special
Levying and be, described method comprises the steps:
Step 1: weigh A according to stoichiometric proportion, the raw material of M, D and boric acid, add proper amount of acetone in the feed, fully
Grinding obtains mixture.
Step 2: by obtaining mixture in step 1 in 400-650 DEG C of environment, be incubated 1 hour～5 hours.
Step 3: the mixture regrinding mix homogeneously that will obtain in step 2.
Step 4: the mixture obtained in step 3 is incubated 1 hour in 700-900 DEG C of environment～obtains end product in 8 hours.
According to A in the present invention, step 1, the raw material of M, D can be its oxide, nitrate, carbonate, oxalates etc.,
Preferably nitrate.
According to A in the present invention, step 1, the integral molar quantity adding nitrate anion in the raw material of M, D is greater than or equal to according to change
Formula AM4(BN2)3The molal quantity of calculated N.
According to the introducing form of nitrate anion in the present invention, step 1 except by A, can also be added it outside the nitrate of M, D
It contains the salt such as ammonium nitrate of nitrate anion.
According to the present invention, described alkali metal A be selected from Li, the one or more combination in Na, K, Rb, Cs, preferably Li, Na,
K。
According to the present invention, alkaline-earth metal M is selected from Be, the one or more combination in Mg, Ca, Sr, Ba, preferably Ca, Sr, Ba.
Addition according to the acetone in the present invention, step 1 is volume ratio VAcetone/VRaw material=1-3, preferably VAcetone/VRaw material=1.
Can also substitute such as dehydrated alcohol with other volatile organic solvents according to the acetone added in the present invention, step 1.
Process can carry out the most in air atmosphere according to the ground and mixed in the present invention, step 1.
It is 400-700 DEG C according to the temperature of heat treatment in the present invention, step 2, preferably 600 DEG C；Temperature retention time is 1-5 hour,
It is preferably 3 hours.
It is reducing atmosphere according to the atmosphere of heat treatment in the present invention, step 2, such as CO gas, N2/H2Gaseous mixture, activated carbon
Grain, preferably activated carbon granule.
It is 700-900 DEG C according to the temperature of heat treatment in the present invention, step 4, preferably 800 DEG C；Temperature retention time is that 1-8 is little
Time, preferably 3 hours.
It is reducing atmosphere according to the atmosphere of heat treatment in the present invention, step 4, such as CO gas, N2/H2Gaseous mixture, activated carbon
Grain.
Mol ratio according to the present invention, dopant ion and M is 0.1-30%, preferably 0.5-15%, more preferably 0.5-10%.
Preparation method of the present invention has following features
The present invention uses solid-phase synthesis, and synthesis temperature is low, and preparation technology is simple, low cost, safe and reliable, with short production cycle,
Material luminous efficiency is high, be suitable for large-scale industrial production.
The fluorescent material output at different-waveband can be regulated and controled, it is possible to achieve single-matrix by the kind and concentration adjusting dopant ion
White light emission.
Accompanying drawing explanation
Fig. 1,800 DEG C of synthesis LiSr4(BN2)3: Ce3+The XRD figure of fluorescent material.
Fig. 2,800 DEG C of synthesis LiSr4(BN2)3: Ce3+Exciting and emission spectra of fluorescent material.
Fig. 3,800 DEG C of synthesis LiSr4(BN2)3: Ce3+The stereoscan photograph of fluorescent material
Detailed description of the invention
Below in conjunction with example, the present invention is further detailed.But skilled in the art realises that, following embodiment is not right
The restriction of scope, any improvement made on the basis of the present invention and change, all in scope.
The case study on implementation of the present invention is to prepare rare earth or Mn2+Ion-activated AM4(BN2)3The preparation method of fluorescent material, wherein A
For Li, the combination of one or more in Na, K, Rb, Cs, preferably Li, Na and K；M is Be, in Mg, Ca, Sr, Ba etc.
The combination of one or more, preferably Ca, Sr and Ba.In described nitrogen boride fluorescent material, in host material mainly
M atom is replaced, but is not limited to M ion and is replaced.Described nitrogen boride fluorescent material can be excited by black light, should
The luminescence of fluorescent material is adjustable in 400-650nm wave-length coverage, has luminous intensity high, the feature of high color purity.
The method of preparing such fluorescent material is described in detail below.
Step 1: according to AM(1-x)4(BN2): DxStoichiometric proportion weigh following raw material:
Boric acid；
One or more in lithium nitrate, lithium carbonate, sodium nitrate, sodium carbonate, potassium nitrate, potassium carbonate, rubidium nitrate, rubidium carbonate；
One or more in magnesium nitrate, magnesium carbonate, calcium nitrate, calcium carbonate, strontium nitrate, strontium carbonate, barium nitrate, brium carbonate；
Cerous nitrate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, Terbium nitrate (Tb(NO3)3), Dysprosium trinitrate, holmium nitrate, thulium nitrate, nitric acid
Ytterbium, cerous carbonate, praseodymium carbonate, neodymium carbonate, samaric carbonate, europium carbonate, terbium carbonate, dysprosium carbonate, carbonic acid holmium, thulium carbonate, carbonic acid
Ytterbium, cerium oxide, praseodymium oxide, Dineodymium trioxide, Disamarium trioxide, europium oxide, terbia. Diterbium trioxide, dysprosia, holmia, Dithulium trioxide, oxidation
One or more in ytterbium, manganese carbonate, manganese nitrate.
According to volume ratio V in the various raw mixtures weighedRaw material∶VAcetone=1: 1-3 adds acetone, is fully ground mix homogeneously,
Obtain mixture.
Step 2: will obtain mixture in step 1 under reducing atmosphere, in 400-650 DEG C, is incubated 1 hour～5 hours, obtains
Initial burned material.
Step 3: the initial burned material that will obtain in step 2, according to volume ratio VInitial burned material∶VAcetone=1: 0.5-2 adds acetone again
Ground and mixed is uniform.
Step 4: by the burned material that obtains in step 3 under reducing atmosphere, 700-900 DEG C of insulation obtains final for 1 hour～8 hours
Product.
Embodiment
Preparation example is given below in the way of illustrating and noting limit.
Embodiment 1, LiSr4(BN2)3: the preparation of Cel mol%
0.185g Li is weighed according to stoichiometric proportion2CO3、4.190g Sr(NO3)2、0.927g HBO3、0.035g CeO2。
Being put into by the raw material weighed during Achates grinds, do not stop to grind after adding acetone, until acetone vapors away completely, all raw materials mix
Uniformly.Then putting in corundum crucible by mixture, under charcoal heat condition, 650 DEG C sinter 3 hours.The sinter obtained is again
Grinding uniformly, be then placed in corundum crucible, under charcoal heat condition, 800 DEG C sinter 3 hours, obtain LiSr after grinding4(BN2)3: Cel
Mol% fluorescent material.That XRD powder diffraction shows to obtain is pure LiSr4(BN2)3Structure (Fig. 1).
Embodiment 2, LiSr4(BN2)3: the preparation of Ce2mol%
0.185g Li is weighed according to stoichiometric proportion2CO3、4.146g Sr(NO3)2、0.927g HBO3、0.069g CeO2。
Being put into by the raw material weighed during Achates grinds, do not stop to grind after adding acetone, until acetone vapors away completely, all raw materials mix
Uniformly.Then putting in corundum crucible by mixture, under charcoal heat condition, 650 DEG C sinter 3 hours.The sinter obtained is again
Grinding uniformly, be then placed in corundum crucible, under charcoal heat condition, 800 DEG C sinter 3 hours, obtain LiSr after grinding4(BN2)3: Ce2
Mol% fluorescent material.Excitation spectrum and the emission spectrum of fluorescent material is measured, as shown in Figure 2 by fluorescence spectrophotometer.At black light
Exciting down, fluorescent material shows the strongest blue emission.
Embodiment 3, LiSr4(BN2)3: the preparation of Ce 0.5mol%, Tb2mol%
0.185g Li is weighed according to stoichiometric proportion2CO3、4.169g Sr(NO3)2、0.927g HBO3、0.017g CeO2、
0.083g Tb(NO3)3·4(H2O).The raw material weighed is put into during Achates grinds, do not stop after adding acetone to grind, until third
Ketone vapors away completely, all raw material mix homogeneously.Then mixture is put in corundum crucible, 650 DEG C of burnings under charcoal heat condition
Tie 3 hours.The sinter obtained re-grinds uniformly, is then placed in corundum crucible, 800 DEG C of sintering 3 under charcoal heat condition
Hour, obtain LiSr after grinding4(BN2)3: Ce2mol% fluorescent material.Excitation spectrum and the transmitting of fluorescent material is measured by fluorescence spectrophotometer
Spectrum, as shown in Figure 2.Under the exciting of black light, fluorescent material shows the strongest blue emission.
Embodiment 4, NaSr4(BN2)3: the preparation of Cel mol%
0.264g Na is weighed according to stoichiometric proportion2CO3、4.190g Sr(NO3)2、0.927g HBO3、0.035g CeO2。
Being put into by the raw material weighed during Achates grinds, do not stop to grind after adding acetone, until acetone vapors away completely, all raw materials mix
Uniformly.Then putting in corundum crucible by mixture, under charcoal heat condition, 650 DEG C sinter 3 hours.The sinter obtained is again
Grinding uniformly, be then placed in corundum crucible, under charcoal heat condition, 800 DEG C sinter 3 hours, obtain LiSr after grinding4(BN2)3: Cel
Mol% fluorescent material.That XRD powder diffraction shows to obtain is pure LiSr4(BN2)3Structure (Fig. 1).
Embodiment 5, LiCa4(BN2)3: the preparation of Cel mol%
0.185g Li is weighed according to stoichiometric proportion2CO3、4.675g Ca(NO3)2·4(H2O)、0.927g HBO3、0.035
g CeO2.The raw material weighed is put into during Achates grinds, do not stop after adding acetone to grind, until acetone vapors away completely, all
Raw material mix homogeneously.Then putting in corundum crucible by mixture, under charcoal heat condition, 650 DEG C sinter 3 hours.The burning obtained
Knot thing re-grinds uniformly, is then placed in corundum crucible, and under charcoal heat condition, 800 DEG C sinter 3 hours, obtain after grinding
LiSr4(BN2)3: Cel mol% fluorescent material.
Embodiment 6, NaCa4(BN2)3: the preparation of Cel mol%
0.264g Na is weighed according to stoichiometric proportion2CO3、4.675g Ca(NO3)2·4(H2O)、0.927g HBO3、0.035
g CeO2.The raw material weighed is put into during Achates grinds, do not stop after adding acetone to grind, until acetone vapors away completely, all
Raw material mix homogeneously.Then putting in corundum crucible by mixture, under charcoal heat condition, 650 DEG C sinter 3 hours.The burning obtained
Knot thing re-grinds uniformly, is then placed in corundum crucible, and under charcoal heat condition, 800 DEG C sinter 3 hours, obtain after grinding
LiSr4(BN2)3: Cel mol% fluorescent material.
Embodiment 7, LiSr4(BN2)3: the preparation of Cel mol%
0.185g Li is weighed according to stoichiometric proportion2CO3、4.190g Sr(NO3)2、0.927g HBO3、0.035g CeO2。
Being put into by the raw material weighed during Achates grinds, do not stop to grind after adding acetone, until acetone vapors away completely, all raw materials mix
Uniformly.Then putting in corundum crucible by mixture, under charcoal heat condition, 650 DEG C sinter 3 hours.The sinter obtained is again
Grinding uniformly, be then placed in corundum crucible, under charcoal heat condition, 750 DEG C sinter 3 hours, obtain LiSr after grinding4(BN2)3: Cel
Mol% fluorescent material.
Claims (7)
1. an AM4(BN2)3: the preparation method of D fluorescent material, the wherein A combination of one or more in alkali metal；M selects
From alkaline-earth metal Be, the combination of one or more in Mg, Ca, Sr, Ba etc.: D selected from rare earth ion (Ce3+, Pr3+, Nd3+,
Sm3+, Sm2+, Eu3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+) and Mn2+In one or more combination；Its
Being characterised by, described method comprises the steps:
(1) A is weighed according to stoichiometric proportion, the raw material of M, B and boric acid, add proper amount of acetone in the feed, be fully ground
To mixture.
(2) by step 1 obtaining mixture in 400-650 DEG C of environment, it is incubated 1 hour～5 hours.
(3) the mixture regrinding mix homogeneously that will obtain in step 2.
(4) mixture obtained in step 3 it is incubated 1 hour in 700-900 DEG C of environment～obtains end product in 8 hours.
2. according to claim 1, it is characterised in that the component of fluorescent material is AM4-4x(BN2)3:Dx(x=1-30mol%).
3. according to claim 1 and 2, it is characterised in that the raw material of A, M, D can be its oxide, nitrate, carbonate,
Oxalates etc..
4., according to claim 1 and 3, it is characterised in that A in step 1, the raw material of M, D adds the integral molar quantity of nitrate anion
It is greater than or equal to according to chemical formula AM4(BN2)3The molal quantity of calculated N.
5., according to claim 4, in step 1, the introducing form of nitrate anion is except by A, adding outside the nitrate of M, D
Other contains the salt such as ammonium nitrate of nitrate anion.
6., according to claim 1, in step 2, the temperature of heat treatment is 400-700 DEG C；The atmosphere of heat treatment is reducing atmosphere, such as CO
Gas, N2/H2Gaseous mixture, activated carbon granule etc.；Temperature retention time is 1-5 hour.
7., according to claim 1, in step 4, the temperature of heat treatment is 700-900 DEG C；The atmosphere of heat treatment is reducing atmosphere, such as CO
Gas, N2/H2Gaseous mixture, activated carbon granule etc.；Temperature retention time is 1-8 hour.
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Citations (4)
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|---|---|---|---|---|
| CN1424254A (en) * | 2003-01-03 | 2003-06-18 | 浙江大学 | Preparation of boron nitride nano tube |
| CN101962540A (en) * | 2009-09-29 | 2011-02-02 | 鹤壁佳多科工贸有限责任公司 | Method for preparing europium-excited strontium fluoroborate ultraviolet fluorescent powder |
| CN102337124A (en) * | 2011-07-20 | 2012-02-01 | 厦门大学 | Rare-earth doped red-light fluorescent powder and preparation method thereof |
| WO2016055140A1 (en) * | 2014-10-09 | 2016-04-14 | Merck Patent Gmbh | Phosphors |
-
2016
- 2016-05-13 CN CN201610330393.1A patent/CN105950141B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424254A (en) * | 2003-01-03 | 2003-06-18 | 浙江大学 | Preparation of boron nitride nano tube |
| CN101962540A (en) * | 2009-09-29 | 2011-02-02 | 鹤壁佳多科工贸有限责任公司 | Method for preparing europium-excited strontium fluoroborate ultraviolet fluorescent powder |
| CN102337124A (en) * | 2011-07-20 | 2012-02-01 | 厦门大学 | Rare-earth doped red-light fluorescent powder and preparation method thereof |
| WO2016055140A1 (en) * | 2014-10-09 | 2016-04-14 | Merck Patent Gmbh | Phosphors |
Non-Patent Citations (3)
| Title |
|---|
| A. O. CHAUHAN等: "Synthesis and PL study of UV emitting phosphor LiSr4(BO3)3:Pb2+", 《INTERNATIONAL JOURNAL OF LUMINESCENCE AND APPLICATIONS》 * |
| QIANG LONG等: "Synthesis and luminescence properties of a novel red-emitting LiSr4(BN2)3:Eu2+ phosphor", 《DALTON TRANS.》 * |
| 江东亮等: "《无机非金属材料手册 上》", 31 July 2009 * |
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