CN101016457A - Green light luminescent powder for plasma radiation screen and preparing method thereof - Google Patents
Green light luminescent powder for plasma radiation screen and preparing method thereof Download PDFInfo
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- CN101016457A CN101016457A CNA2007100032619A CN200710003261A CN101016457A CN 101016457 A CN101016457 A CN 101016457A CN A2007100032619 A CNA2007100032619 A CN A2007100032619A CN 200710003261 A CN200710003261 A CN 200710003261A CN 101016457 A CN101016457 A CN 101016457A
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Abstract
The invention discloses a green light emitting phosphor for plasma radiation screen, which is characterized by the following: setting yttrium-terbium normal borate as base material; adding into III oxygen family element gadolinium and aluminum oxide; making the total chemical gage formula as Y1-x-yGdxTbyB1-zAlzO3; making chemical gage index to vary during X=0.001-0.4, y=0.001-0.2, z=0.01-0.1 range. Besides this invention also provides a plasma radiation screen, which can produce multilayer green light phosphor powder layer. This invention also discloses a preparing method of this product, which possesses high luminosity or better illuminant color coordinate.
Description
[technical field that the present invention belongs to]
The present invention system refers to a kind of fluorescent material of plasma radiation screen especially about a kind of technique of display, and it has higher luminosity and in its radiation spectrum, sub-band λ=580～590nm reduces with λ=610～620nm radiation quantity is relative.
[prior art]
Generally speaking, the plasma radiation screen is on structure, and its composition has comprised the fluorescent material composition of red, green and blue look usually.These composition profiles have formed the vaccum case of plasma radiation screen densification at the internal surface of glass substrate.Being full of noble gas mixtures in plasma radiation screen volume, mainly is xenon (Xe) and krypton (Kr).Under the effect of alternating field (alternative field) (Heng Chang is more rare), in noble gas mixtures, glow gases discharge " being lighted " (exciting).Excite down in the ultra-violet region, at the visible region and the infrared spectral range of electromagnetic spectrum, it has the intensive spectral line of emission.The main Xe spectral line of emission is positioned at intervals such as 147～173nm and 185nm.By these spectral lines, in the Xe discharge process, red, green, blue look luminescent material produces photoluminescence and excites.According to the information content and the horizontal stringer number of plasma radiation screen, the discharge excitation time changes in 0.1～100 microsecond.So, the luminescent material that in plasma panel, uses, its excite with had fall time clear and definite requirement (please refer to Ш e р р Э л e к т р о н н ы e д и с п л e и. М. М и р, с т р .218-250).
Use various fluorescent material in the known plasma flat screen.Detailed consolidated report about these luminescent material parameters is mentioned (please refer to Phosphor Handbook.CRS Press, p.631-635,1999) in academic paper.As the fluorescent material of main green-light radiation, in this academic paper, quoted the orthosilicate Zn that comes from zinc-manganese
2Si0
4The known materials parameter of Mn, the present invention adopts it as analogous material.According to known data, the orthosilicate of zinc-manganese is λ at wavelength
MaxThe green spectral zone radiation of=525nm is different from saturated chromaticity coordinates x≤0.25, y 〉=0.65, and has sufficiently high quantum output η 〉=0.8, and its luminous efficiency is considered to 100% usually.Yet known fluorescent material analogue has defective in essence, and this comprises very slow firing time τ
Excite〉=200 microseconds, and very long τ persistence
e〉=12 milliseconds.In reference (please refer to C.TaMypa и д p.Tech.Res JnstTV Eng Jpa v.18, p.55-65,1999), attempt improving these defectives of known green-light radiation fluorescent material; Yet orthosilicate fluorescent material is along with the increase of manganese concentration, and firing time only shortens half (τ
ExciteAnd slightly reduce to τ time of persistence 〉=100 microseconds),
e＞8 milliseconds.
These defectives have determined: must develop the green-light radiation fluorescent material that makes new advances.In the middle of this class phosphor material powder, have and a kind ofly (please refer to H.Bechtel et and Phosphors for PDP.Journal of the SID 10/1200 and G.Oversluizen in data, Sde Zwart i dr.Jornal of the SIDV 10/3237-240,2002) put down in writing in.Wherein, as replacing Zn
2SiO
4Mn orthosilicate fluorescent material be that composition is YBO
3The orthoboric acid salt fluorescent material of Tb.According to the above-mentioned data of delivering, excite prototype to originate in f=1000Hz as high frequency discharge of the present invention.It has successfully got rid of the peculiar luminance saturation phenomenon of standard fluorescence powder.With Zn
2SiO
4Mn fluorescent material is standard, is that the fluorescent material of prototype has higher luminosity with yttrium-terbium orthoboric acid salt, at higher frequency f=10
5Luminous intensity can exceed 30～35% of standard under the condition of Hz.Although have some known advantages, measurement of the present invention discloses: also there are a series of defectives in essence in known green-light radiation fluorescent material.Wherein have some must be noted that: under basic Xe ionic radiation long wave λ=147nm and 173nm, orthoboric acid salt fluorescent material absorbs not high.
Not only there is yellow-green colour in the radiation of orthoboric acid salt fluorescent material, and similarly has orange and red sub-band, and this is corresponding to long wave λ=580～590nm and 610～620nm.
In chromaticity coordinates x≤0.34, y≤0.57 o'clock, light-emitting phosphor saturated colour deficiency.In addition, the shortcoming of known single-component phosphor-prototype is: in the plasma panel volume, not high for the stability of geseous discharge effect.
[summary of the invention]
For solving the shortcoming of above-mentioned known technology, main purpose of the present invention is that a kind of green light fluorescent powder that is used for the plasma radiation screen and preparation method thereof is provided, and the green light fluorescent powder of made has higher luminosity.
For solving the shortcoming of above-mentioned known technology, another object of the present invention system provides a kind of green light fluorescent powder that is used for the plasma radiation screen and preparation method thereof, the green light fluorescent powder of made is in its radiation spectrum, sub-band λ=580～590nm is relative with 610～620nm radiation quantity to be reduced, the ratio J between the wavelength simultaneously basic and that replenish
545/ (J
580+ J
610) should increase.
For solving the shortcoming of above-mentioned known technology, another object of the present invention system provides a kind of green light fluorescent powder that is used for the plasma radiation screen and preparation method thereof, the green light fluorescent powder of made can improve the radiation chromaticity coordinates of fullness of shade and orthoboric acid salt green-light radiation fluorescent material, for intensive geseous discharge influence in the plasma radiation screen, it is more stable that the fluorescent material that is proposed should keep equally.
For achieving the above object, the invention provides a kind of green light fluorescent powder that is used for the plasma radiation screen, it is the green light fluorescent powder that is applied to the plasma radiation fluorescent screen, it is to be matrix with yttrium-terbium orthoboric acid salt, it is characterized in that: added the oxide compound of III family element gadolinium and aluminium in this fluorescent material composition, total chemometric equation is: Y
1-x-yGd
xTb
yB
1-zAl
zO
3, x=0.001～0.4 wherein, y=0.001～0.2, z=0.01～0.1.
Wherein, this fluorescent material has triangular lattice, belongs to three-dimensional R3c group.
Wherein, the thin divided powder of this fluorescent material is circular or oval, its tap density ρ 〉=2.5g/cm
3
Wherein, this fluorescent material has absorption band in the zone of 130～150nm and 165-200nm, and main radiation spectral line is positioned at λ=540～550nm, the zone of λ=580～590nm.
Wherein, the short-wave radiation intensity of this fluorescent material is along with the Tb that adds
+ 3Ionic concentration increases and is linear growth, and at this moment, (λ=580～590nm) yield of radiation are inversely proportional to the oxide concentration that joins terbium in the fluorescent material composition long wave; At this moment, in described spectrum sub-band, the radiation belt intensity rate changes simultaneously along with the oxide concentration that joins the aluminium in the composition, J
540: J
580It is 200: 1 to 8: 1.
Wherein, this radiation ion Tb
+ 3Main can tape lifetime τ
eReduce according to equation τ
e=b-k[Tb]
0.5, and be positioned at 6～3.5 milliseconds interval, for optimum concn [Tb]=0.1 atomic fraction, life value τ
e=5 milliseconds.
Wherein, the optimum concn ratio of the oxide compound of this gadolinium (Gd) and aluminium (Al) is [Gd
2O
3]: [Al
2O
3]=100: 1～10: 1, it is along with the oxide concentration of the terbium that adds in the fluorescent material composition increases and increases simultaneously.
Wherein, this phosphor powder mean diameter exceeds 1.5～4 times than the main spectrum maximum value of about λ=540nm, and simultaneously, the variance that is evenly distributed of this phosphor powder changes in interval 2≤σ≤5.
Wherein, this fluorescent material has following composition: Y
0.62Gd
0.3Tb
0.08B
0.96Al
0.04O
3
For achieving the above object, the invention provides a kind of plasma radiation screen, it has aforesaid green light fluorescent powder, it is characterized in that: can be made into multiwalled green light fluorescent powder layer, and its reflection efficiency is positioned at interval 30%＜R＜60%, and the unit volume quality of above-mentioned green light fluorescent powder is 1.5～2.5mg/cm in the plasma radiation screen
2
For achieving the above object, the invention provides a kind of making method that is used for the green light fluorescent powder of plasma radiation screen, it comprises the following steps: to mix with boric acid and sintering by the oxide compound of yttrium, gadolinium and terbium; In strainer, mix continually and wash; And carry out the calcination of two stages again.
Wherein, in this oxide compound by yttrium, gadolinium and terbium mix with boric acid and the agglomerating step in use the precursor compound of the liquid substance of the nitrate come from yttrium, gadolinium, terbium as described element, and in containing the boric acid alcohol aqueous solution of some amount, interact, temperature is T=50～100 ℃.
Wherein, carry out in the step of two stages calcination at this, when temperature T=600～750 ℃, the time is 1～2 hour, and when temperature is T=1150～1250 ℃, the time is 1～3 hour.
Wherein, the total chemometric equation of the composition of this green light fluorescent powder is: Y
1-x-yGd
xTb
yB
1-zAl
zO
3, and this stoichiometry index changes in following interval: x=0.001～0.4, y=0.001～0.2, z=0.01～0.1.
[embodiment]
At first, the objective of the invention is to eliminate the above-mentioned shortcoming that is used for the green light fluorescent powder of plasma radiation screen.In order to reach this target, the green light fluorescent powder system that is used for the plasma radiation screen of the present invention is a matrix with yttrium-terbium orthoboric acid salt, it is characterized in that: added the oxide compound of III family element gadolinium and aluminium in this fluorescent material composition, total chemometric equation is: Y
1-x-yGd
xTb
yB
1-zAl
zO
3, wherein, this stoichiometry index changes in following interval: x=0.001～0.4, y=0.001～0.2, z=0.01～0.1.At this moment, fluorescent material has the trilateral crystal structure, belongs to three-dimensional R3c group.Wherein the parameter ratio is c/a 〉=3.4 between the lattice.When adding gadolinium (Gd) in mentioned component, ratio is reduced to c/a ≈ 3.3, because the single thin divided powder of fluorescent material has circle or elliptical shape, its tap density ρ 〉=2.5g/cm
3
Below the brief physical-chemical essence of setting forth orthoboric acid salt green-light radiation fluorescent material proposed by the invention.According to the research of being carried out, the present invention determines: although substantially add the gadolinium particle on yttrium borate fluorescent powder basis, the crystal structure of compound is also keeping trilateral, is equivalent to be subordinate to three-dimensional R3c group.As known technology, one YBO
3, GdBO
3And TbBO
3Compound is formed can have various crystal structures.Yet the adding gadolinium ion proposed by the invention and the interval of terbium ion make the single phase property of the novel green light fluorescent powder of known inorganic matrix to keep.Because gadolinium ion Gd
+ 3With terbium ion Tb
+ 3The total amount that adds can be ∑ TR
+ 3=∑ Gd+Tb=0.5 atomic fraction.The structure isomrorphis that is reached is unconspicuous, and this finds first for us.The present invention simultaneously is also noted that the isomrorphis that is reached has caused the one-way of the product that obtains.Similarly, the one-way of orthosilicate yttrium-gadolinium-terbium fluorescent material proposed by the invention improves 4～5% with quantum output.In steady state along with on a parameter and changing, its luminosity improves 15～25% simultaneously.
By observing, we notice: fluorescent material proposed by the invention also has different characteristics, i.e. the crystal habit of phosphor powder uniqueness-oval crystalline particle.If having usually, the composition of traditional orthoboric acid salt splits broken shape; The characteristics of the superiority that composition had so proposed by the invention are: phosphor powder is oval-shaped.Above-mentioned advantage is extremely important, because these advantages have determined phosphor powder to have higher tap density.Do not having under the situation of tangible powder-tight, the tap density that fluorescent material has surpasses 2.5g/cm
3Moreover, this parameter can also reach ρ ≈ 3.6g/cm
3, approach tightness γ ≈ 70%, for the conventional fluorescent powder, this is inaccessiable.All physics-chemical parameters of fluorescent material proposed by the invention according to the standard method of X ray phase analysis and granulated material pile up quality really Rob Roy determine.So unidirectional achievement more is better than using the luminous borate of terbium-gadpolinium alloy.This is the essential advantage of green-light radiation fluorescent material proposed by the invention.Phosphor material powder tap density value of the present invention is quite big, and does not have analogous analogue.
With yttrium-gadolinium-terbium borate be matrix fluorescent material proposed by the invention these advantages with the comparison of other luminescent material in embodied.This phosphor material powder has main absorption band in the zone of 130～150nm and 165～200nm; And has main luminous zone in the zone of λ=540～550nm, λ=580～590nm as multipotency band radiation spectral line.At this moment the short-wave radiation intensity of λ=540～550nm is along with the Tb that adds in the fluorescent material composition
+ 3Concentration increases simultaneously from the increase of [Tb]=0.01～0.1 atomic fraction; At this moment, the long-wave radiation intensity of λ=580～590nm is inverse ratio with the terbium ion concentration that joins in the composition; At this moment, in the pointed spectrum sub-band of the present invention, the ratio J of radiation belt intensity
540: J
580Change in 200: 1～8: 1 intervals, and along with the oxide concentration that joins the aluminium in the fluorescent material anion lattice composition increases and increases.
In the present invention is devoted to the process of research work, find, in composition, add Gd
+ 3The time, the optical energy of fluorescent material matrix absorption band increases 1.3～1.4 times in the zone of 130～150nm.In orthoboric acid salt lattice, a part of Gd
+ 3Replace Y
+ 3In the zone of λ=544nm, the main green-light radiation band of fluorescent material increases simultaneously.The radiation characteristics of fluorescent material of the present invention are: along with adding [Tb
+ 3], mainly energy band strength linear growth meets equation J
540=a[Tb
+ 3]+const (constant).Simultaneously, along with Tb
+ 3The increase of concentration, the radiation quantity intensity that λ=540nm can be with increases, and relative λ=580nm can be with yield of radiation to reduce.At this moment work as aluminium ion concentration [Al in the anion lattice
+ 3] be 8: 1 o'clock can take up beginning ratio, when the aluminium ion concentration that adds in the anion lattice increased, this initial ratio can be brought up to 200: 1.Side by side, the regularity of finding this ratio belongs to simple straight-line law J
540/ J
580=c[Al
+ 3]+const.This regularity depends on a very important characteristic: it is characterized in that fluorescent material radiating colourity.The fluorescent material radiation has obtained more green tones, and becomes more saturated, it is characterized in that chromaticity coordinates x=0.31 and y=0.61.These chromaticity coordinatess are with narrow-band radiated (the Δ λ that mainly can be with
540≤ 10nm) equally, can substantially increase the color scale of plasma panel screen picture, especially when fluorescent screen has been subjected to the intensive external disturbance.
These advantages have guaranteed plasma radiation screen high quality images.And in the screen that uses orthoboric acid salt fluorescent material proposed by the invention, reached corresponding requirement.It is characterized in that: radiation ion Tb
+ 3Main can tape lifetime τ
eReduce according to equation τ
e=b-k[Tb]
0.5, and be positioned at 6～3.5 milliseconds interval.For optimum concn [Tb]=0.1 atomic fraction, life value τ
e=5 milliseconds.
The life-span of green light fluorescent powder of the present invention exciting of pulse Xe-lamp by excitation wavelength lambda=147nm on the device of specialty determined.In essence, when main excited ion concentration value was low, its life value substantially was lower than the life value of orthosilicate fluorescent material analogue, and adds up to τ
e=6 milliseconds.The hurried reduction of the firing time of fluorescent material is τ
Excite=60 microseconds.For optimum concentration value [Tb]=0.1 atomic fraction, life value reduces to τ
e=4.5 milliseconds.Tb
+ 3Main excited state
5D
4-
7F
5Life value τ
e(persistence) increases along with exciting agent concentration, and meets equation τ
e c=τ
e 0-k[Tb]
0.5Wherein, τ
e 0Expression is (≈ 0.0001 atomic fraction) Tb when concentration value is low
+ 3Life value, k is a constant.With respect to particular case, orthoboric acid salt fluorescent material is k=3.Like this, as concentration [Tb
+ 3] growth of tenfold was from 0.01～0.1 o'clock, we find life value τ
eBe changed to τ
∈=6～4.5 milliseconds.Along with the shortening of firing time, reduce persistence simultaneously; At this moment, when the plasma radiation screen excites, just can improve frame (frame) f frequently
Frame=150～200Hz.Simultaneously, the brightness of flat screen laboratory sample increases 2～3.5 times.And, the peculiar saturated phenomenon of standard fluorescence powder does not appear.
Then can increase transmission of Information speed when in theory, discharge excited operating frequency improves in the plasma radiation screen.If for coming from Zn
2SiO
4The standard fluorescence powder of Mn, the sharpness of traditional plasma radiation screen is being that 625 row are best along diagonal lines; So, adopt orthoboric acid salt fluorescent material the sharpness of plasma panel can be brought up to 1000 lines along the level direction, and substantially improved the Q factor of image.The advantage of orthosilicate fluorescent material proposed by the invention has determined these difference beyond all doubtly.The optimum concn of the III family element oxide that in the fluorescent material composition, adds, such as the ratio of gadolinium (Gd) and aluminium (Al) is positioned at [Gd
2O
3]/[A1
2O
3]=100: 1～10: 1, it increases simultaneously along with the increase of the oxide concentration of the main exciting agent terbium that adds in the fluorescent material composition.In being devoted to working process of the present invention, notice orthosilicate matrix YBO
3The unit cell parameter value change at a/c=3.3～3.4.That is to say that parameter value has reduced.The minimizing of fluorescent material identical element lattice capacity is accompanied by the growth of inner crystal field gradient usually, and this has caused internal excitation ion Tb
+ 3The increase of radiative transition quantity.Above phenomenon has caused the increase of luminosity integral exponential in the steady excited state.Yet the remarkable minimizing of orthoboric acid salt lattice parameter can be accompanied by the crystal structure reorganization of fluorescent material matrix, and to the structure cell transition of hanging down symmetrical monocline type.The low symmetry of lattice crystal field has caused Tb
+ 3The substance of radiation spectral line quantity increases in the spectrum, and their intensity reduces simultaneously, and this is extremely not conform with hope.In order in time to prevent this phenomenon, in the present invention, propose in anion lattice, to add the oxide compound Al of aluminium
2O
3Be substituted in the oxide compound of boron in the matrix.Add Al
2O
3Can in time prevent the minimizing of parameter equally, and YBO
3The lattice reorganization of Tb fluorescent material exciting agent boron.The Al that in anion lattice, adds
2O
3Concentration should not surpass the Tb that adds in the positively charged ion lattice
+ 3Concentration.Just as described above, at optimum concn [Tb
+ 3During]=0.1 atomic fraction, aluminium (Al) composition that is substituted in boron in the anion lattice (B) is 0.05 atomic fraction.At this moment fluorescent material parent lattice parameter is similar to standard value for orthoboric acid salt crystal structure.As being showed, what circular luminescenjt powder replacement was traditional splits broken and the not good powder of form.This class powder utilization method for printing screen forms in the operation at screen surface layer sintering and produces.
This essential advantage of phosphor powder proposed by the invention is characterised in that: the phosphor powder mean diameter is than main spectrum maximum value (about λ=540nm) exceed 1.5～4 times.Simultaneously, the variance that is evenly distributed of phosphor powder changes in interval 2≤σ≤5.Following explanation will be pointed out the distribution variance of the main radiation spectral line of fluorescent material value and the detection of powder size.Compare with the radiation wavelength of known fluorescent material, some is accompanied by light diffusion and reduces from 1.5～4 times increase.Because the diameter of the phosphor powder of radiation wavelength λ=540nm has proportionality, therefore the reflection coefficient from the powder thin layer adds up to 40～60%, and this can make fluorescent coating volumetrical radiation output become difficult.Correspondingly, whole luminosity reduces.The polydispersity of phosphor powder increases between σ=2～5, and can improve the radiation output from fluorescent coating.Therefore can obtain proof, when the phosphor powder distribution variance increases to σ=5, the corresponding minimizing 25～30% of continuous coated reflection coefficient.Thereby, when phosphor powder layer thickness is insufficient, in fluorescent coating, can form very trickle hole.Luminescent material of the present invention and the essential advantage that comes from its formed screen surface layer fluorescent coating just do not have hole, it is characterized in that: be better than double-deck multilayer and realize.The two sides all scribbles the fluorescent material of individual layer before and after traditional plasma radiation screen inside, and its pack density is 1.5～2.5mg/cm
2If use fluorescent material of the present invention, then the coating of fluorescent material no longer is limited to individual layer, can be multi-layer coatedly, and its pack density can be increased to 6～12mg/cm
2So can use the radiation power of the inner plasma discharge of plasma radiation screen to greatest extent.
In addition, the present invention also provides a kind of plasma radiation screen, it has aforesaid green light fluorescent powder, it is characterized in that: can be made into multiwalled green light fluorescent powder layer, and its reflection efficiency is positioned at interval 30%＜R＜60%, and the unit volume quality of above-mentioned green light fluorescent powder is 1.5～2.5mg/cm in the plasma radiation screen
2Wherein, the detailed content of this green light fluorescent powder please refer to above-mentioned explanation.
In addition, refer to the fluorescent material of some new green-light radiation in patent of quoting in front of having delivered or the article, but do not point out to come from (Y, Gd, Tb) BO
3The making method of orthosilicate phosphorescent substance.The traditional fabrication method system of green light fluorescent powder is based upon on the basis of standard ceramic technology (please refer to H.Bechtel et and Phosphors for PDP.Journal of the SID 10/1200).According to this method, with the oxide compound Y of necessary stoichiometric
2O
3, Gd
2O
3, Tb
4O
7Same boric acid (H
3BO
3) be mixed together.After this, sintered material when temperature surpasses T=1350 ℃.Known ceramic process is causing the synthetic composition impure phenomenon that occurred of material aspect the optical tech attribute, and it is characterized in that: the powder size of big dispersity is greater than 9～10 microns, and the powder that comes from this size can not form the best radiation coating that is fit to self brightness.
Therefore, the present invention discloses a kind of making method that is used for the green light fluorescent powder of plasma radiation screen.Please refer to Fig. 1, it illustrates the schematic flow sheet of making method that the present invention is used for the green light fluorescent powder of plasma radiation screen.As shown in the figure, the making method that is used for the green light fluorescent powder of plasma radiation screen of the present invention comprises the following steps: to mix with boric acid and sintering (step 1) by the oxide compound of yttrium, gadolinium and terbium; In strainer, mix continually and wash (step 2); And carry out two stages calcination (step 3) again.
In step 1, the oxide compound by yttrium, gadolinium and terbium mixes with boric acid and sintering; Wherein, use the precursor compound of the liquid substance of the nitrate come from yttrium, gadolinium, terbium as described element in step 1, and interact in containing the boric acid alcohol aqueous solution of some amount, temperature is T=50～100 ℃.
In step 3, carry out the calcination of two stages again; Wherein, when temperature T=600～750 ℃, the time is 1～2 hour in step 3, and when temperature is T=1150～1250 ℃, the time is 1～3 hour.
Wherein, the total chemometric equation of the composition of this green light fluorescent powder is: Y
1-x-yGd
xTb
yB
1-zAl
zO
3, and this stoichiometry index changes in following interval: x=0.001～0.4, y=0.001～0.2, z=0.01～0.1.
Below will explain the essence practice of the making method of a kind of green light fluorescent powder that is used for the plasma radiation screen of the present invention.At first, the oxide compound by yttrium and terbium mixes with boric acid and sintering.It is characterized in that: material is synthetic by the interactional approach of the liquid substance that comes from inorganic salt.Wherein, preferentially adopt the ethanol aqueous solution of the nitrate of yttrium, gadolinium, terbium and aluminium.The concentration that it contains necessary amount is 5～12% boric acid.When interactional temperature was T=50～100 ℃, the throw out that will carefully loose in the clock time at 5～60 minutes was separated from mixture.Carrying out following two stages hot-work then handles.Temperature T=600～750 ℃, the time is 1～2 hour; Temperature is 1150～1250 ℃, and the time is 1～3 hour.
The concrete food ingredient example that is used to make green light fluorescent powder of the present invention is as follows:
0.58M Y(NO
3)
3·6H
2O 0.32M Gd(NO
3)
3·6H
2O
0.1M Tb(NO
3)
3·6H
2O 0.05M Al(NO
3)
3·9H
2O
And above-mentioned substance is heated to T=90 ℃.With the mixture degasification of salt 25 minutes.After this mixture is poured into second reactive tank.Wherein pack into 1 liter 12% boric acid solution.Start agitator, rotating speed is ω=60 time/minute, and the throw out mixture begins deposition.Subsequently, in suction filter, wash nitrate ion.Washing was carried out 17～20 minutes.After this, the product of being produced is dried in thermostat container to powder, T=120 ℃, the time is 3 hours.Then powder is put into crucible, heat-treat in the High Temperature Furnaces Heating Apparatus of SiC in the following manner: T=700 ℃, the calcination time length is 1 hour.After this, rate of rise in temperature is υ
T=10 °/minute, and reach 1225 ℃.Hot-work continues 2 hours.The crucible that batching is housed is cooled to 100 ℃.Product is cleaned with the mixture (1: 1) of hydrochloric acid and acetic acid, and in the time of T=120 °, dried 1 hour.Coat SiO on the phosphor powder surface
2Thin layer (about 20nm).
In professional optical tech parameter photon instrument, the material of having produced is measured.Instrument comprises the Xe-lamp of two band optical filterings, and the differentiation wavelength is λ=147 and 173nm.In the vacuum space of having filled green-light radiation fluorescent material laboratory sample, the Xe-lamp is settled.The dispersity of phosphor powder determines that in the instrument of SCS-2001 model data provides by computer.The phosphor powder mean diameter is d
50=0.98 micron, distribution variance is σ=4.8 units, and the powder diameter of most of fluorescent material is no more than d
90=1.8 microns.By using monatomic alcohol mixt to form similar double-deck phosphor powder layer.Zn coexists
2SiO
4The phosphor powder layer of making on the Mn standard fluorescence powder basis is compared, and with regard to the radiation screen, its luminosity is brought up to L=120%.
With regard to the high-quality technology of producing fluorescent material, this is not unique advantage of the preparation method that proposed.Similarly, the high chemical stability of fluorescent material also is a big advantage.It is embodied in, and to stir the back hydrogen ion concentration constant phosphor powder being inserted in the steamer water.Even after the fluorescent material suspension liquid was boiled, the variation of pH value was no more than Δ pH=0.2 unit.
In table 1, list the concrete composition of the fluorescent material of making by above method.Wherein, corresponding with various mixture materials is optical tech parameter and dispersity.The impurity of introducing except scope, the parameter value of all the components is listed in table 1.By comparing, it has high luminosity or better illuminant colour coordinate.
Table 1 is listed the parameter of the green-light radiation fluorescent material that is applied to plasma panel.
Table 1
| № | Fluorescent material is formed | Relative luminosity % | The illuminant colour coordinate | Powder mean diameter d 50 | |
| x | y | ||||
| 1.1 | Y 0,58Gd 0,32Tb 0,1B 0,95Al 0,05O 3 | 119 | 0.312 | 0.601 | 0.98 |
| 1.2 | Y 0,78Gd 0,12Tb 0,1B 0,99Al 0,01O 3 | 104 | 0.318 | 0.612 | 1.84 |
| 1.3 | Y 0,58Gd 0,12Tb 0,2B 0,9Al 0,1O 3 | 106 | 0.310 | 0.602 | 1.05 |
| 1.4 | Y 0,899Gd 0,001Tb 0,1B 0,9Al 0,1O 3 | 102 | 0.34 | 0.578 | 1.12 |
| 1.5 | Y 0,58Gd 0,4Tb 0,02B 0,94Al 0,06O 3 | 107 | 0.28 | 0.584 | 1.96 |
| 1.6 | Y 0,68Gd 0,22Tb 0,1B 0,95Al 0,05O 3 | 116 | 0.310 | 0.606 | 1.0 |
| 1.7 | Y 0,88Gd 0,02Tb 0,1B 0,99Al 0,01O 3 | 119 | 0.311 | 0.608 | 1.76 |
| 1.8 | Y 0,58Gd 0,33Tb 0,06B 0,995Al 0,005O 3 | 101 | 0.276 | 0.575 | 1.1 |
| 1.9 | Y 0,98Gd 0,01Tb 0,01B 0,99Al 0,01O 3 | 95 | 0.273 | 0.571 | 1.92 |
| 2.0 | Y 0,998Gd 0,001Tb 0,01B 0,99Al 0,01O 3 | 92 | 0.270 | 0.569 | 1.5 |
| Master body | YBO 3The Tb master body | 100 | 0.274 | 0.576 | 3～6 |
In sum, with regard to green light fluorescent powder that is used for the plasma radiation screen of the present invention and preparation method thereof, this fluorescent material is the green-light radiation fluorescent material with higher luminosity, and sub-band λ=580～590nm reduces with λ=610～620nm radiation quantity is relative in its radiation spectrum, the ratio J between the wavelength simultaneously basic and that replenish
545/ (J
580+ J
610) should increase, in addition, can improve the radiation chromaticity coordinates of fullness of shade and orthoboric acid salt green-light radiation fluorescent material, for intensive geseous discharge influence in the plasma radiation screen, advantages such as fluorescent material of the present invention should keep stablizing more equally, therefore, really can improve the shortcoming of known green light fluorescent powder and preparation method thereof.
Though the present invention discloses as above with preferred embodiment; yet it is not in order to limit the present invention; anyly have the knack of this skill person; without departing from the spirit and scope of the present invention when can doing a little change and retouching, so protection scope of the present invention is when looking being as the criterion that the accompanying Claim book defined.
[brief description of drawingsfig]
Fig. 1 is a synoptic diagram, and it illustrates the schematic flow sheet of the making method of the green light fluorescent powder that is used for the plasma radiation screen of the present invention.
[primary clustering nomenclature]
Step 1: the oxide compound by yttrium, gadolinium and terbium mixes with boric acid and sintering;
Step 2: in strainer, mix continually and wash; And
Step 3: carry out the calcination of two stages again.
Claims (15)
1. green light fluorescent powder that is applied to the plasma radiation screen, it is to be matrix with yttrium-terbium orthoboric acid salt, it is characterized in that: added the oxide compound of III family element gadolinium and aluminium in this fluorescent material composition, total chemometric equation is: Y
1-x-yGd
xTb
yB
1-zAl
zO
3, x=0.001～0.4 wherein, y=0.001～0.2, z=0.01～0.1.
2. the green light fluorescent powder that is used for the plasma radiation screen as claimed in claim 1, wherein this fluorescent material has triangular lattice, belongs to three-dimensional R3c group.
3. the green light fluorescent powder that is used for the plasma radiation screen as claimed in claim 1, wherein the thin divided powder of this fluorescent material is circular or oval, it piles up quality density p 〉=2.5g/cm
3
4. the green light fluorescent powder that is used for the plasma radiation screen as claimed in claim 1, wherein this fluorescent material has absorption band in the zone of 130～150nm and 165-200nm, and main radiation spectral line is positioned at λ=540～550nm, the zone of λ=580～590nm.
5. the green light fluorescent powder that is used for the plasma radiation screen as claimed in claim 4, wherein the short-wave radiation intensity of this fluorescent material is along with the Tb that adds
+ 3Ionic concentration increases and is linear growth, and at this moment, long-wave radiation intensity is inversely proportional to the oxide concentration that joins terbium in the fluorescent material composition; At this moment, in described spectrum sub-band, the radiation belt intensity rate changes simultaneously along with the oxide concentration that joins the aluminium in the composition, J
540: J
580It is 200: 1 to 8: 1.
6. the green light fluorescent powder that is used for the plasma radiation screen as claimed in claim 5, wherein this Tb
+ 3Ionic concentration is 0.01～0.1 atomic fraction.
7. the green light fluorescent powder that is used for the plasma radiation screen as claimed in claim 5, wherein this radiation ion Tb
+ 3Main can tape lifetime τ
eReduce according to equation τ
e=b-k[Tb]
0.5, and be positioned at 6～3.5 milliseconds interval, for concentration [Tb]=0.1 atomic fraction, life value τ
e=5 milliseconds.
8. the green light fluorescent powder that is used for the plasma radiation screen as claimed in claim 1, wherein the concentration ratio of the oxide compound of this gadolinium and aluminium is [Gd
2O
3]/[Al
2O
3]=100: 1～10: 1, it is along with the oxide concentration of the terbium that adds in the fluorescent material composition increases and increases simultaneously.
9. the green light fluorescent powder that is used for the plasma radiation screen as claimed in claim 1, wherein this phosphor powder mean diameter exceeds 1.5～4 times than the main spectrum maximum value of λ=540nm, simultaneously, the variance that is evenly distributed of this phosphor powder changes in interval 2≤σ≤5.
10. the green light fluorescent powder that is used for the plasma radiation screen as claimed in claim 1, wherein this fluorescent material has following composition:
Y
0.62Gd
0.3Tb
0.08B
0.96Al
0.04O
3。
11. plasma radiation screen, it has green light fluorescent powder as claimed in claim 1, it is characterized in that: can be made into multiwalled green light fluorescent powder layer, and its reflection efficiency is positioned at interval 30%＜R＜60%, and the unit volume quality of above-mentioned green light fluorescent powder is 1.5～2.5mg/cm in the plasma radiation screen
2
12. a making method that is used for the green light fluorescent powder of plasma radiation screen, it comprises the following steps:
Oxide compound by yttrium, gadolinium and terbium mixes with boric acid and sintering;
In strainer, mix continually and wash; And
Carry out the calcination of two stages again.
13. the making method that is used for the green light fluorescent powder of plasma radiation screen as claimed in claim 12, wherein mix with boric acid also and use the precursor compound of the liquid substance of the nitrate that comes from yttrium, gadolinium, terbium in the agglomerating step as described element in this oxide compound by yttrium, gadolinium and terbium, and in containing the boric acid alcohol aqueous solution of some amount, interact, temperature is T=50～100 ℃.
14. the making method that is used for the green light fluorescent powder of plasma radiation screen as claimed in claim 12, wherein carry out in the step of two stages calcination at this, when temperature T=600～750 ℃, the time is 1～2 hour, when temperature is T=1150～1250 ℃, the time is 1～3 hour.
15. the making method that is used for the green light fluorescent powder of plasma radiation screen as claimed in claim 12, wherein the total chemometric equation of the composition of this green light fluorescent powder is: Y
1-x-yGd
xTb
yB
1-zAl
zO
3, x=0.001～0.4 wherein, y=0.001～0.2, z=0.01～0.1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011097826A1 (en) * | 2010-02-12 | 2011-08-18 | 海洋王照明科技股份有限公司 | Borosilicate luminescent material and preparing method thereof |
| EP2489644A1 (en) * | 2009-08-26 | 2012-08-22 | Ocean's King Lighting Science&Technology Co., Ltd. | Luminescent element, producing method thereof and luminescence method using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW526254B (en) * | 2000-03-23 | 2003-04-01 | Toshiba Corp | Phosphor excited by vacuum ultraviolet ray and light emitting apparatus using thereof |
| JP4244727B2 (en) * | 2003-06-30 | 2009-03-25 | パナソニック株式会社 | Plasma display device |
| KR100651277B1 (en) * | 2003-07-25 | 2006-11-28 | 엘지전자 주식회사 | Green phosphor and plasma display panel |
| US8896004B2 (en) * | 2005-04-26 | 2014-11-25 | Kabushiki Kaisha Toshiba | White LED, backlight using the same, and liquid crystal display device |
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2007
- 2007-02-05 CN CN2007100032619A patent/CN101016457B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2489644A1 (en) * | 2009-08-26 | 2012-08-22 | Ocean's King Lighting Science&Technology Co., Ltd. | Luminescent element, producing method thereof and luminescence method using the same |
| EP2489644A4 (en) * | 2009-08-26 | 2014-02-26 | Oceans King Lighting Science | Luminescent element, producing method thereof and luminescence method using the same |
| US9000667B2 (en) | 2009-08-26 | 2015-04-07 | Ocean's King Lighting Science & Technology Co., Ltd. | Luminescent element, preparation method thereof and luminescence method |
| WO2011097826A1 (en) * | 2010-02-12 | 2011-08-18 | 海洋王照明科技股份有限公司 | Borosilicate luminescent material and preparing method thereof |
| CN102575164A (en) * | 2010-02-12 | 2012-07-11 | 海洋王照明科技股份有限公司 | Borosilicate luminescent material and preparing method thereof |
| CN102575164B (en) * | 2010-02-12 | 2014-04-30 | 海洋王照明科技股份有限公司 | Borosilicate luminescent material and preparing method thereof |
| US8980132B2 (en) | 2010-02-12 | 2015-03-17 | Ocean's King Lighting Science & Technology Co., Ltd. | Borosilicate luminescent material and preparing method thereof |
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