CN1286942C - Vacuum ultraviolet excited green borate luminous material and preparation process thereof - Google Patents

Vacuum ultraviolet excited green borate luminous material and preparation process thereof Download PDF

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CN1286942C
CN1286942C CN 200410025946 CN200410025946A CN1286942C CN 1286942 C CN1286942 C CN 1286942C CN 200410025946 CN200410025946 CN 200410025946 CN 200410025946 A CN200410025946 A CN 200410025946A CN 1286942 C CN1286942 C CN 1286942C
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vacuum ultraviolet
boric acid
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CN1560187A (en
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王育华
张加驰
何玲
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Lanzhou University
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Lanzhou University
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Abstract

The present invention aims at providing a novel preparation method of Y<1-X>Tb<X>BO3 and a green borate luminescent material (Y<1-w-x-y-z>Gd<w>Sc<x>Tb<y>Ce<z>)BO3 excited by vacuum ultraviolet light, wherein the w is at most 0.5, the x is at most 0.1, the y is at most 0.26, the z is at most 0.1. Compared with the existing Y<1-X>Tb<X>BO3, the material (Y<1-w-x-y-z>Gd<w>Sc<x>Tb<y>Ce<z>)BO3 has better luminescence property under the excitation of ultraviolet light or vacuum ultraviolet light. The preparation method of the present invention comprises the following steps: adding each soluble salt of rare earth element and raw materials for providing boron, such as boracic acid, boric acid ester, etc., to water or solution of water and ethanol; adding or not adding a hydrolyst to a reaction system; causing the raw materials to react at 250 to 300 DEG C for several hours; centrifugating, washing, separating and drying the product. In this way, the target product is obtained. The method has the advantages of low reaction temperature, simple technology, controllable granule size and topography of the obtained product, without needing treating the obtained product by grinding, etc., and particularly uniform spherical products can be obtained.

Description

A kind of preparation method of vacuum ultraviolet-excited green light emitting borate material
Technical field
The present invention relates to a kind of vacuum ultraviolet-excited green light emitting borate material Y 1-XTb XBO 3The preparation method of (0.0≤x≤0.26), and open to Y 1-XTb XBO 3Improvement has obtained a kind of advanced luminescent material, and its general formula is: (Y 1-w-x-y-zGd wSc xTb yCe z) BO 3(0.0≤w≤0.5,0.0≤x≤0.1,0.0≤y≤0.26,0.0≤z≤0.1).
Background technology
Plasma display (PDP) is a kind of emerging display device, compare with CRT monitor, LCD display commonly used, so numerous advantages such as the PDP indicating meter has that the visual angle is wide, big area, in light weight, good contrast, response are fast, undistorted, vibration and shock resistant are PDP indicating meter great prospect.The two big key components that PDP shows are circuit and luminescent material, and perfect day by day along with circuit layout, luminescent material select the technology that becomes PDP demonstration most critical for use.The three primary colours of using in PDP at present are: (Y, Gd) BO 3: Eu, green Zn 2SiO 4: Mn, blue BaMgAl 10O 17: Eu.Green luminescent material wherein is with Mn 2+As activator.But because Mn 2+Spin forbidden ( 4T 1→ 6A 1) emission, cause its time of persistence longer, make picture when conversion, produce hysteresis.Increase Mn 2+Doping content can shorten time of persistence, but can reduce the luminous intensity of luminescent material, therefore studying a kind of new green luminescent material becomes a kind of exigence.As activator, Tb 3+Have feature green (543nm) emission, and its spin coupling makes it to have short time of persistence to the shielding of spin forbidden, overcome lag-effect.Selecting for use of luminescent material matrix, RE(rare earth) borate, especially Y, the borate of elements such as Gd have good vacuum ultraviolet (VUV) absorption characteristic, good luminescent properties and highly stable physics-chem characteristic and cause that people pay close attention to greatly.In addition, at present because the PDP three-color light-emitting material adopts different matrix, thereby their physicochemical property have than big-difference, and this makes the fluorescent screen painting process of luminescent material complicated more, has also influenced the display effect of PDP.If can unite the matrix of three-color light-emitting material, just can improve the display effect of PDP better, simplify production technique, (Y, Gd) BO 3: Eu is present widely used red illuminating material, so exploitation YBO 3: Tb is as new green luminescent material and improve its luminescent properties and will have very important significance.
The synthetic method relevant with this luminescent material has high temperature solid-state method (M.Ren, J.H.Lin, Y.Dong, L.Q.Yang, and M.Z.Su, Chem.Mater., 11.1576 (1999).F.J.Avella, O.J.Sovers, andC.S.Wiggins, J.Electrochem.Soc., 114.613 (1967)), sol-gel method (Zhanggui Wei, Lingdong Sun, Chunsheng Liao, J.Phys.Chem.B.106.10610-10617 (2002)), flux method (Yong Yune Shin, Jean Chae, Tae Hwan Cho, et al.IDW-96, p.81) and ultrasonic heat solution (D.Boyer, G.b.Chadeyron, R.Mahiou, C.Caperaa and J.C.Cousseins, J.Mater.Chem..9.211-214 (1999).D.S.Kim and R.Y.Lee, J.Mater.Sci., 35,4777-4782 (2000)) etc.Wherein the raw material of high temperature solid-state method can not thorough mixing, needs mechanical mill and B when raw material mixes 2O 3Want excessive 5%-20% with B in the compensatory reaction process 2O 3Volatilization loss, this method temperature of reaction height (more than 1100 ℃), the grain size distribution inequality of generation, out-of-shape, sintering is serious, this all has considerable influence to the luminescent properties of product.Sol-gel method also must could obtain single-phasely heat-treating more than 900 ℃, and its essence also is solid state reaction, can have all deficiencies of solid-phase synthesis equally.Flux method in reaction process, need to add fusing assistant and behind 1100 ℃ of sintering, could obtain single-phase, so easy introducing impurity.The ultrasonic heat solution needs special equipment, thereby is difficult to widespread use.
Hydrothermal method is a kind of emerging method of Recent study inorganic materials synthetic, the hydro-thermal synthetic technology can make the reaction raw materials thorough mixing, reduces temperature of reaction, shortens the reaction times, and can control the pattern and the granularity of product by controlling reaction conditions, make it to have preferable luminescent properties.
The present invention has synthesized a kind of vacuum ultraviolet-excited green light emitting borate material Y with hydrothermal method 1-XTb XBO 3(0.0≤x≤0.26) is simultaneously for improving its luminescent properties, to Y 1-XTb XBO 3Improvement has obtained a kind of advanced luminescent material, and its general formula is: (Y 1-w-x-y-zGd wSc xTb yCe z) BO 3(0.0≤w≤0.5,0.0≤x≤0.1,0.0≤y≤0.26,0.0≤z≤0.1).
Summary of the invention
The purpose of this invention is to provide a kind of preparation green luminescent material Y 1-XTb XBO 3The novel method of (0.0≤x≤0.26), this method temperature of reaction is low, and technology is simple, and can control the pattern granularity of product by the control reaction conditions, can obtain uniform sheet or spherical product, and products therefrom need not to carry out milled processed again.
The present invention also provides a kind of new vacuum ultraviolet-excited green light emitting borate material (Y 1-w-x-y-zGd wSc xTb yCe z) BO 3(0.0≤w≤0.5,0.0≤x≤0.1,0.0≤y≤0.26,0.0≤z≤0.1), it is than existing Y 1-XTb XBO 3Luminescent material has better luminescent properties.
Method of the present invention is that the nitrate of yttrium, terbium and boric acid are dissolved in the distilled water, then mixing solutions being moved into has in the small-sized stainless steel cauldron of teflon lined, react at 250 ℃～300 ℃, reaction is centrifugal with product after finishing, washing, separate, oven dry can obtain purpose product Y 1-XTb XBO 3(0.0≤x≤0.26).
Improvement as the inventive method, also the nitrate and the boric acid fat of yttrium, terbium can be added in entry and the alcoholic acid mixing solutions, the hydrolyst that in system, adds acid or alkali again, react at 250 ℃～300 ℃, reaction is centrifugal with product again after finishing, washing, separate, oven dry can obtain purpose product Y 1-XTb XBO 3(0.0≤x≤0.26).Studies show that, the used boric acid fat of the present invention with boric acid three formicesters or boric acid tri butyl ester for well; And water and ethanol volume ratio should be in 1: 1～1: 3 in the used solvent; The hydrolyst that is added in reaction system can be nitric acid, boric acid or ammoniacal liquor.It is spherical adopting this product pattern that obtains of improving one's methods.
The general formula of advanced luminescent material of the present invention is: (Y 1-w-x-y-zGd wSc xTb yCe z) BO 3(0.0≤w≤0.5,0.0≤x≤0.1,0.0≤y≤0.26,0.0≤z≤0.1).Owing to added sensitizing agents such as scandium, cerium and gadolinium in the material, the luminescent properties of material is further improved.The preparation method of this advanced luminescent material is identical with preceding method basically.
The present invention compared with prior art has following advantage:
1, preparation technology is simple, is easy to grasp, and production cost is low, the products therefrom good dispersity, and no agglomeration also need not to carry out milled processed again;
2, temperature of reaction is low, and the products therefrom pattern is controlled, both can obtain granularity and be fit to, and the platy particle that is evenly distributed also can obtain uniform spherical particle by the adjustment to technology;
3, the activator (Tb of products therefrom of the present invention 3+) quenching concentration be 22%, and the sample of solid state reaction gained has only 12%, illustrates that the luminescence center of products therefrom of the present invention is more than the luminescence center of solid state reaction, thus luminescent properties is better than solid state reaction gained sample.
4, reactant of the present invention is to mix on atom or molecular level, therefore can make activator (Tb 3+) be evenly distributed in the lattice dot matrix.
5, initial feed of the present invention accurately takes by weighing by stoichiometric ratio, and H in the solid state reaction 3BO 3Must be excessive 5%～20%, so defective increases, this can influence the luminescent properties of luminescent material.
6, when adopting advanced luminescent material of the present invention, its luminescent properties will be better than the luminescent material of existing other technology preparation.
Description of drawings
Accompanying drawing 1 is an X-ray diffractogram, and wherein: a is the X-ray diffractogram of the inventive method gained sheet product, and b is for adopting the X-ray diffractogram of high temperature solid state reaction products therefrom.
The NMR figure that accompanying drawing 2 is the feedstock production products therefrom for the present invention with the nitrate and the boric acid of yttrium, terbium.
Accompanying drawing 3 is the sem photograph of feedstock production products therefrom for the present invention with the nitrate and the boric acid of yttrium, terbium.
Accompanying drawing 4 is the sem photograph of feedstock production products therefrom for the present invention with the nitrate and the boric acid fat of yttrium, terbium.
Accompanying drawing 5 is for adopting the sem photograph of high temperature solid state reaction products therefrom.
Accompanying drawing 6 is Y 1-XTb XBO 3Luminous intensity and Tb 3+The relation curve of doping content, wherein: a is for adopting the sample of the present invention's preparation, and b is for adopting the prepared sample of high temperature solid state reaction.
Accompanying drawing 7 compares for emmission spectrum, and a is the emmission spectrum of the sheet sample of employing the present invention preparation, and b is the emmission spectrum of the prepared sample of employing high temperature solid state reaction.
Embodiment
Below provide relevant embodiment of the present invention and Comparative Examples.
Embodiment one
Initial feed: Yttrium trinitrate, Terbium trinitrate, boric acid.
By stoichiometric ratio Y 1-xTb xBO 3(0≤x≤0.26) is each component of weighing accurately.With the raw material dissolved in distilled water, mixing solutions is transferred in the small-sized stainless steel cauldron of teflon lined, add distilled water, in reaction under 260 ℃ of temperature after 6 hours, product is centrifugal, washing, separate, oven dry can obtain sheet purpose product Y 1-xTb xBO 3(0≤x≤0.26), its luminous strength ratio is high by 10% with the luminescent material of high temperature solid-state method preparation.
Embodiment two
Initial feed: Yttrium trinitrate, Terbium trinitrate, boric acid tri butyl ester; Solvent: distilled water: ethanol=1: 2 (volume ratio); Hydrolyst: ammoniacal liquor.
By stoichiometric ratio Y 1-xTb xBO 3(0≤x≤0.26) is each component of weighing accurately, joins then in water and the alcohol mixeding liquid, and water and alcoholic acid volume ratio are 1: 2.System is mixed the back and add hydrolyst in solution, disperseing the back to move in ultrasonic wave reaction system has in the small-sized stainless steel cauldron of teflon lined, 260 ℃ of insulations 6 hours, after reaction finishes, furnace cooling is to room temperature, use dehydrated alcohol and distilled water wash respectively, filter at last and, promptly obtain spherical purpose product Y 100 ℃ of dryings 1-xTb xBO 3(0≤x≤0.26).
Embodiment three
Initial feed: the nitrate of yttrium, gadolinium, terbium, scandium and cerium and boric acid tri butyl ester; Solvent: distilled water: ethanol=1: 2 (volume ratio); Hydrolyst: ammoniacal liquor.、
By stoichiometric ratio (Y 1-w-x-y-zGd wSc xTb yCe z) BO 3(0.0≤w≤0.5,0.0≤x≤0.1,0.0≤y≤0.26,0.0≤z≤0.1) is each component of weighing accurately, joins in water and the alcoholic acid mixed solution, and water and alcoholic acid volume ratio are 1: 2.System is mixed the back and add hydrolyst in solution, disperseing the back to move in ultrasonic wave reaction system has in the small-sized stainless steel cauldron of teflon lined, 260 ℃ of insulations 6 hours, after reaction finishes, furnace cooling is to room temperature, use dehydrated alcohol and distilled water wash respectively, filter at last and, promptly obtain spherical purpose product (Y 100 ℃ of dryings 1-w-x-y-zGd wSc xTb yCe z) BO 3(0.0≤w≤0.5,0.0≤x≤0.1,0.0≤y≤0.26,0.0≤z≤0.1), this product excites down at 147nm, has higher luminous efficiency, after the thermal treatment sometimes luminous intensity the phenomenon of obvious increase is arranged.
Comparative Examples
Initial feed: yttrium oxide, terbium sesquioxide, boric acid.
As with contrast of the present invention, adopt the high temperature solid-state method of prior art to prepare corresponding product Y 1-xTb xBO 3(0≤x≤0.12).Its technology is: take by weighing each component by stoichiometric ratio, its mesoboric acid excessive 5% is to replenish volatilization loss, and the raw material ground and mixed is even, is incubated 2.5 hours down prior to 500 ℃, is incubated 2 hours down in 1100 ℃ again, obtains product Y 1-xTb xBO 3(0≤x≤0.12).
Aforesaid embodiment is used X-ray powder diffractometer (XRD respectively; Model D/max-2400, RigakuCo.Ltd.Japan) working sample thing phase; With scanning electron microscope (SEM; Model JSM-5600LV, JapanElectron Optics Laboratory Co.Ltd.Japan) sample is carried out the grain morphology analysis; With infrared absorption spectrum (IR; Model Nexus 670, Nicolet Instrument Corporation.America) and nuclear magnetic resonance spectrum (NMR; Model Varian Infinity Plus 400 Inc.American) is used for the coordination mode of study sample boron.Sample adopts spectrophotofluorometer (Model RF-540, Shimadzu Corporation.Japan) to measure exciting with emmission spectrum of UV wave band; The characteristics of luminescence under vacuum ultraviolet-excited is to record and proofread and correct with sodium salicylate (Sodium Benzoate) with ARCModel VM-502 type vacuum monochromator.
Accompanying drawing 1 is the XRD figure spectrum with the sample of embodiment one preparation, and analysis revealed: the sample of the inventive method preparation is single-phase, and belongs to hexagonal system.
Accompanying drawing 2 is with hydrothermal method synthetic YBO 3: the NMR spectrogram of Tb sample.In NMR analyzed, commonly used to this parameter of coupling constant eqQ, for the plane triangle structure of boron oxygen three-fold coordination, its eqQ was approximately 5.39Mc/see, by Δ V x=25 (eqQ) 2/ 192v0 (v0 is the frequency that operating instrument is selected for use) is Δ V as can be seen xBe worth greatlyyer, its resonance absorbing peak is in downfield on spectrogram.And for the boron oxygen four-coordination tetrahedral structure of symmetrical configuration, its eqQ is approximately 0.0504Mc/sec, and its resonance absorbing peak will be positioned near the 0ppm of upfield.Strong peak by 0ppm place in upfield among the figure shows: hydrothermal reaction at low temperature synthetic YBO 3: mainly contain the tetrahedron group of boron oxygen four-coordination among the Tb, this is consistent with analytical results to its IR spectrogram.
Accompanying drawing 3 is that the Tb doping with embodiment one gained is 22%YBO 3: the stereoscan photograph of Tb.As seen from the figure, its size of particles is 5-7um, the distribution homogeneous, is laminar.
Accompanying drawing 4 is with embodiment two gained YBO 3: the sem photograph of Tb.As seen from the figure, the product particle is spherical (5um) that is evenly distributed.

Claims (4)

1, a kind of preparation method of vacuum ultraviolet-excited green light emitting borate material, it is characterized in that the nitrate and the boric acid ester of yttrium, terbium are added in entry and the alcoholic acid mixed solution, water and alcoholic acid volume ratio are 1: 1～1: 3, system is mixed the back and add hydrolyst in solution, react at 250 ℃～300 ℃, reaction is centrifugal with product again after finishing, washing, separate, oven dry can obtain the purpose product.
2, preparation method according to claim 1 is characterized in that described boric acid ester is trimethyl borate or tributyl borate.
3, preparation method according to claim 1 and 2, the hydrolyst that it is characterized in that in the system being added is nitric acid or boric acid.
4, preparation method according to claim 1 and 2, the hydrolyst that it is characterized in that in the system being added is an ammoniacal liquor.
CN 200410025946 2004-02-25 2004-02-25 Vacuum ultraviolet excited green borate luminous material and preparation process thereof Expired - Fee Related CN1286942C (en)

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JP5593394B2 (en) 2009-12-04 2014-09-24 オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド Borate luminescent material and method for producing the same
CN103184050B (en) * 2013-03-12 2014-11-05 西北大学 Preparation method for rare-earth-doped borate nanosheet or nanoflower fluorescent powder
JP7033540B2 (en) * 2016-10-28 2022-03-10 大電株式会社 Ultraviolet light emitting phosphor, light emitting element, and light emitting device
CN110016342A (en) * 2019-03-21 2019-07-16 中国科学院青海盐湖研究所 Thin film phosphor and preparation method thereof
CN110484756B (en) * 2019-09-24 2020-11-06 江西沪昌电缆有限公司 Preparation method of aluminum-based high-conductivity wire

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