CN1730605A - Fluorescent powder, polymer coat for light transformation, bluegreen LBD, signal apparatus based on bluegreen LBD - Google Patents

Abstract

The invention relates to inorganic fluorescent powder, which is prepare by using silicates of Mg, Ca, Sr, Ba as the basis, charging into zirconium dioxide to form fluorescent powder with the chemical formula of (Mg,Ca,Sr,Ba)2Si1-xZrxO4, then charging rare-earth elements of Eu, Sm, Dy and Yb ions into fluorescent powder as catalyst. The invention also discloses the light-emitting diode with inorganic fluorescent powder coated on the surface, and the signal apparatus equipped with the light-emitting diode.

Description

Fluorescent material, polymerization light conversion coating, blue green LED and based on the telltale of blue green LED

Technical field

The invention belongs to semiconductor electronic and optical tech field, i.e. field of semiconductor illumination.Specifically, the present invention relates to fluorescent material, polymerization light conversion coating, blue green LED and based on the telltale of blue green LED.

Background technology

Technique of display with the directional correlation of this important fast development, semiconductor planar display panel and indicating meter have obtained widespread use in this technical field, and the primary clustering of its formation is based on the semi-conductor of various chemical attribute heterojunction, such as: aluminium phosphide or gan indium nitride.Except that using in technique of display, diode also is widely used in the various signal indicating devices.The radiator that manufacturing is used for signalling set equally also is an important application direction of patent of the present invention.

Telltale is used well-known very extensive, various traffic lights is wherein arranged, semaphore, beacon etc.The main composition of these allied equipments is with the light source based on incandescent light.The semiconductor light source that is used for traffic lights and semaphore code now obtains develop rapidly.Here heterojunction semiconductor uses as transmitting illuminant, such as, be matrix with indium nitride or indium nitride, gan.These semiconductor light sources have very high brightness, and it is more sturdy and durable that very high working life also can manufacture and design.In addition, the characteristics that showing of these light sources are to have high economy, because can need not change in several thousand hours.Although be widely used, semiconductor light source has serious defective, is the inalterability of its emission light color, and this is that energy by the radiation level in the heterojunction semiconductor band structure constitutes decision.The change of heterojunction luminescent spectrum and need a complicated process that makes up semi-conductor newly developed area module based on the corresponding change of the luminaire color of this heterojunction needs to seek new alms giver and is subjected to the main luminescence center with other spectrum composition that makes up.This program that makes up the new semiconductor material of design comes displaced technology complicated equally compared with other diode scheme of employing.

In the similar scheme one is commonly referred to the binary diode, in the patent of V.S Abramov in 1973 and V.P.Sushiv description is arranged.The author advises adopting layered structure to construct photodiode, its luminous direct radiative color of heterojunction semiconductor that is different from, adopt fluorescent material on indium nitride gallium nitride semiconductor surface in the layered structure, fluorescent material initial radiation (blueness) excites various visualization of color.This patent makes can make more long wavelength's photodiode, compares with semiconductor light emitting.Because light-emitting phosphor is generally followed the stokes principle, principle is illustrated, and the radiogenic light wavelength of fluorescent material is longer than the optical excitation wavelength, and similar patented invention author has adopted term " stokes fluorescent material " in the work of oneself.Patent [1] just is used in for a long time makes special display equipment, so restricted on announce.But this patent of invention is conspicuous in the initial property of making on the binary photodiode.1998, the most frequently used binary semiconductor light source of Japanese Ri Ya company's release, ([2] US pat 5998925 was from 1999) emit white light.In the process of the sample of making this patent of invention, patented invention person has adopted following physical phenomenon:

Jet-type electroluminescent in the-nitride heterojunction;

-phosphor material powder absorption portion heterojunction is initially luminous, is absorbed the initial radioactive department of heterojunction by fluorescent material and divides scattering;

The special phosphor material powder photoluminescence that-emission peculiar spectrum is formed, its color are replenishing of the initial glow color of heterojunction.Two kinds of complementary colors are mixed according to newton's principle and are formed homogenous white light.So two kinds of spectral emissions that the 4th physical phenomenon of Ri Ya company diode is heterojunction emission and fluorescent powder grain launches are homogeneity light intimate mixing and constitute unique curve of spectrum not, dark blue and orange two SPECTRAL REGION on the curve show two kinds of main spectrum maximum values clearly.The curve of spectrum of this complexity of visible area is shown as unique white light.Therefore, invention [2] can be considered as solving the trial that fluorescent material that structure adopts heterojunction semiconductor to excite to select for use synthesizes this challenge of light.

Patent [2] part has disclosed based on using aluminium yttrium pomegranate (Y ₃Al ₅O ₁₂What Ce) material was produced white emitting fluorescent powder should the stage.This aluminium yttrium pomegranate component has become the main fluorescent material of binary photodiode in long time.But, the new fluorescent material application of series has been arranged now patent protection, the major ingredient of these fluorescent material is compound silicate metal, has common molecular formula Sr _xBa _yCa _zSiO ₄, x+y+z=2 here, and the main catalysis ion of this matrix is the europium ion of valency+2.[3,4] US application number is № 20040227465A (18.11.2004), EP 1367655A1 (10.12.2004).All patented materials are all made in the sample of fluorescent material chemical composition by me and are adopted.The silicate fluorescent powder preparation is simpler with respect to the pomegranate base fluorescent powder, more cheap.

Summary of the invention

The objective of the invention is to design structure binary semiconductor luminous source, that is, based on the photodiode of indium nitride, gallium nitride heterojunction and special fluorescent material, the common luminous composition complex light of this composition is called " cian " or blue green light.In this composite coloured light, should there be blue light and green glow close on two spectrum.Two kinds of distinct colors in luminous and deposit and can only excite the method for green light fluorescent powder to obtain by adopting initial blue ray radiation.Because the wavelength spacing is no more than 70nm (this is green wavelength for 520-on the spectrum axle between standard blue light and the green glow, this is blue light wavelength for 450nm-), that one Si Tuokefu can not surpass 70nm in the displacement that excites and be launched between the light, this is very little value, so be difficult to obtain luminescent material in practice.So another purpose of the present invention is to prepare the bluish-green luminescent material of special little Si Tuokefu displacement.The another one purpose of invention is to prepare the luminescent material of high quantum output usefulness, and this is that to make the high luminous intensity photodiode that accumulates on the relatively little luminous output angle necessary.Do not have essential granularity component as synthetic fluorescent material, that one the present invention just can not realize.Be that synthetizing phosphor powder must have the fineness dispersiveness.Invention must solve problem and the surface that is fixed on heterojunction semiconductor that fluorescent powder grain is firm and the problem on the light emitting end surface of those design structures " binary " photodiode.

Having shown the general color diagram in 1931 of international lighting association in the table-1, is exactly the diagram of so-called XYZ color.Part corresponding with the bluish-green color of standard used in the international railway transport on the figure marks with lines.Table-2 has shown total spectrogram of semi-conductor nitrogen base heterojunction and fluorescent material of the present invention.Can draw from table-1 data, the gap between the maximum light output can be less than 30nm.In the table-3 with the demonstration of XYZ coordinate lumination of light emitting diode cloth prepared in accordance with the present invention office point.

Match with the present invention's purpose, recommend to use the bluish-green inorganic fluorescent powder based on IIA family element to prepare photodiode, fluorescent material has added the element Zr of IVb family so in addition preferably by the divalent ionic catalysis in the component of fluorescent material, the oxide compound of Hf, the chemical formula that constitutes fluorescent material is:

(Me ^II _i) _Xi(Me ^IV _j) _YjSi _ZO ₄TR ^{+ 2}, Me wherein ^II _i=Mg and/or Ca and/or Sr and/or Ba, Me ^IV _j=Zr and/or Hf, $\underset{i=1}{\overset{4}{\mathrm{\Σ}}}{x}_i=2,\underset{j=1}{\overset{2}{\mathrm{\Σ}}}{y}_j=0-0.99,Z=1-\underset{j=1}{\overset{2}{\mathrm{\Σ}}}{y}_j,$ TR ^{+ 2}=Eu ^{+ 2}And/or Sm ^{+ 2}And/or Yb ^{+ 2}And/or Dy ^{+ 2}, in addition, this light-emitting phosphor is between the spectrographic blueish green region, and its stoke shift is equal to or greater than 40nm with respect to semi-conductor nitrogen base heterojunction is luminous, and luminescent spectrum band half range is λ _0,5=40nm is between blue-greenish colour spectrum range λ=500-λ=545nm.Physical essence of the present invention is described now.We know the Jim Glassman principle, that is exactly complicated synthetic light color, can be such as those " cyanogen "-blue-greenish colours by mixing two kinds of luminous obtaining, wherein a kind of formula nitrogen base indium gallium heterojunction is luminous, wavelength is positioned at λ=400-495nm interval, and second kind of luminous heterojunction excited fluorescent powder is luminous, and fluorescent material is made up of the oxide system of II in the periodic table of elements and IV family element complexity.

The significant parameter of fluorescent material prepared in accordance with the present invention is that (η, %), quantum output is generally understood as the proportionlity of optical radiation material quantum and absorbing material quantum in its quantum output.The characteristics that also possess of this fluorescent material are fixed stimulated luminescence spectrum and luminescent spectrum in addition.The characteristics of luminescent spectrum are to cause luminous photon spectral distribution.General this spectral distribution excites the wavelength that fluoresces with respect to a kind of fluorescent material.Be interpreted as the spectral distribution of the luminescent quantum that on the narrow sub-band of excitation wavelength or unit wavelength, is excited for the spectrum that fluoresces.Arrive seen in our work, all properties of fluorescent material depends on its chemical composition on the preparation method of the best.Well-known silicate fluorescent powder component: Sr _xBa _yCa _zSiO ₄: Eu ^{+ 2}, x+y+z=2 here, the maximum emission wavelength of its spectrum fluctuates between λ=520-λ=590nm.Its illuminant colour coordinate in addition _{" X "}Value between x=0.26-0.50.Under this situation, that exert an influence for the luminescent spectrum characteristics is the metal ions M e of distance ^{+ 2}Content, or the crystalline structure of synthetic silicate.We fail to obtain the single-phase and the leggy sample of IIa family ion complete series and utilize them to come proving its influence to positively charged ion or crystalline structure in process of the present invention: whole silicate metal all changes the structure of oneself.So in following form 1, introduced single two metal silicate fluorescent material stimulated luminescence parameters.Conspicuous, (Ba _0,98Eu _0,02) ₂SiO ₄It is λ that very strong green luminescence bandgap wavelength has appearred in the silicate of structure _Max=504nm, quantum output exceeds 50% than standard fluorescence powder.

Me ₂SiO ₄: Eu. two metal silicate components

Table-1

Me 2SiO 4:Eu	Crystallographic system	λ max，nm	Intensity of radioactivity .%	Chromaticity coordinates x y
					(Ca 0,98Eu 0,02) 2SiO 4	Single wedge shape	506	45	0,20 0,49
(Sr 0,98Eu 0,02) 2SiO 4	Single wedge shape	545	72	0,35 0,54
					(Ba 0,98Eu 0,02) 2SiO 4	Iris	508-512	150	0,25 0,58
(Mg 0,98Eu 0,02) 2SiO 4	Single wedge shape hexahedron	502-504	40	0,14 0,50

If from t=1,43A is (for Ba with two metal silicate ionic radius ^{+ 2}Ion) is reduced to t=1,27A (Sr ^{+ 2}Ion), in fact the luminous intensity of that one this material can reduce by 2 times, but light-emitting phosphor spectrum maximum value moves to the spectrum long wave.Though this luminous chromaticity coordinates is " green ", be difficult to obtain the required bluish-green coloured light of binary photodiode by this material.Must be pointed out that simultaneously the crystalline structure of the similar Sr of containing ionic species is single wedge shape.

As in silicate with Ba ^{+ 2}(t=1,43A) ion replaces with Ca ^{+ 2}(t=1,06A), that one (Ca _0.98Eu _0.02) ₂SiO ₄The spectrum maximum value will be positioned at the shortwave interval of green glow sub-band, wavelength X=506nm, but the brightness of similar twinkler is very low may be owing to exist single wedge-like crystallographic system to cause in the material.

Mg ^{+ 2}Ion is littler, and (radius is t=0,78A) is used for replacing Ba ^{+ 2}(t=1 43A), causes the spectrum maximum value position to be offset to λ to ion _Max=502-504nm.This saturated green luminescence intensity 40% of the intensity that can not be above standard, _{" X "}Coordinate figure is not less than 0.14.

Single two metal silicates are given information analyze and to reach a conclusion: Ba in the positively charged ion sublattice ^{+ 2}Ion is essential for the fluorescent material of preparation high luminous intensity, but must other conditioning agent emission wavelength be adjusted to the blue green light sub-band in this case.This sensing type conditioning agent can be by small dimension cation ratio such as Ca ^{+ 2}And Mg ^{+ 2}Serve as.These two kinds of cationic existence are suitable for the best blue green light fluorescent material of preparation obviously.Probably, the crystalline structure of this mixing cpd trends towards vertical stratification.Replenish a spot of strontium oxide of interpolation and also be fine in silicate, the existence of strontium oxide can be stablized Eu ^{+ 2}The fusion of ion in silicate fluorescent powder is because the in fact all very close (Sr of the ionic radius of these elements ^{+ 2}T=1,27A, Eu ^{+ 2}T=1,24A).But the important results that we analyze is to determine two kinds of possible fluorescent material component solutions, and wherein a kind of is scheme: have IIa family all four kinds of positively charged ions (Mg, Ca in the positively charged ion sublattice, Sr, Ba), second kind of component can have only three kinds of positively charged ion (Mg of IIa family, Ca, Ba).In fact this possible fluorescent material scheme has been got rid of in the component by the main cation constituent of patent [4,5] protection, so just can prepare independently autonomous patent component.Add those elements in addition, guaranteed the patent requirement that conforms with of the present invention such as Mg.

We adopt a kind of new method to prepare saturated green light fluorescent powder in the invention process.This method is to add Zr in addition in the negatively charged ion sublattice ^{+ 4}And/or Hf ^{+ 4}The series of elements material.We find, use Zr ^{+ 4}(t=0,80A) or Hf ^{+ 4}(t=0 84A) replaces Si ^{+ 4}(t=0 41A) can make its parameter value reach a=6,5A c=5,9A or higher so that lattice is spatially expanded.The result is also to find and original silicate fluorescent powder (Ba in this big specification lattice _0,98Eu _0,02) ₂SiO ₄Compare main catalyzer Eu ^{+ 2}Ion produces other shortwave displacement.The chromaticity coordinates of this material also is subjected to displacement owing to anionic replacement.The chromaticity coordinates value reduces, x=0.15, and slight growth y=0.58 takes place in abscissa value simultaneously.

We also find in the invention process, also can prepare two catalyzer fluorescent material in the single catalyzer silicate fluorescent powder of preparation.As other adding divalent ion, we have used Sm at work ^{+ 2}And/or Dy ^{+ 2}And/or Yb ^{+ 2}In this case, in the fluorescent material component, add Sm in addition ^{+ 2}The fluorescent material spectrum maximum value position generation long wave trend displacement increase of fluorescent material quantum output time the during ion is followed.Dy ^{+ 2}Ionic effect and above-mentioned Sm ^{+ 2}Similar, can cause and produce the long wave displacement on the spectrum maximum value simultaneously.

In single catalyzer fluorescent material component, add Yb ^{+ 2}Spectral displacement can be do not produced, but shortening time of persistence of dual catalyst light-emitting phosphor can be caused.This material is for promoting the heterojunction semiconductor excitation intensity that remarkable effect is arranged.This our first observed to the test fact be very important for the high brightness LED that preparation is used for the luminous output equipment of Small angle.As the Si in the fluorescent material ^{+ 4}Ion is by the Hf of bigger specification ^{+ 4}Ion is replaced, and the reduction of slight luminous intensity can appear in that youngest in this fluorescent material when producing the shortwave displacement.

All above-mentioned fluorescent materials all have a spot of spectrum stoke shift.For series phosphor powder positional value Δ _CT. equal 40nm ± 5nm.In equivalence was replaced, this value may be reduced to Δ _CT.=40nm.The fluorescent material of recommending also has very important advantage to be except little stoke shift, and its luminescent spectrum maximum value is usually located between λ=500nm-λ=525nm sub-band.

Above-mentioned 3 or the advantage of 4 metal metasilicate zirconate be the material of its use.Because above-mentioned fluorescent material uses Eu, Sm, Dy, Yb are as catalyzer, and these divalent ions form the green emitting phosphor powder, and its reflection coefficient is at interval at R ₄₀₀=20%, R ₄₅₀=25%, R ₅₀₀=50%, form thin particulate coating, initial luminous of absorbed nitrogen base heterojunction also makes its decay 5-20 doubly, in addition, mix with the fluorescent material secondary is luminous by the initial blue light of the heterojunction of above-mentioned thin particulate coating, form integrated blue green light, this blue green light chromaticity coordinates is x=0.02 y=0.5-x=0 in the interval of colour band, 22 y=0,39.

We studies show that, this integrated light is on the composition of its blue light and green glow, and actual can not the decomposition by the simplest optical module (white flakes, glass), these main wavelength of forming light are λ _Mainly=490-495 brings up to λ _Mainly=520nm.Described above us, and be bound to take place the initial luminous absorbing phenomenon of heterojunction semiconductor in the photodiode that we recommend, this phenomenon self can atarting material intensive fluorescent material stimulated luminescence.In order to absorb initial luminous fluorescent material should be painted.Test as us shows that this painted reason is at first, to have catalyzer Eu in the phosphor material powder component ^{+ 2}Ion.We determine color by changing phosphor powder layer particulate reflection coefficient.Long under the situation of λ=400 purple lights at fluorescent coating surface upslide ejected wave, the reflected light part can be above 20%.Wavelength be λ=450nm reflection coefficient some can rise to R=25%, be elevated to R=50% and wavelength is the reflection coefficient at the blue green light sub-band center of λ=500nm.This is engraved in the 400-500nm sub-band with luminescent decay 5-20 doubly the fluorescent powder grain thin layer.So initial blue light has only 5-16% penetration phosphor thin layer (remaining light absorbed by fluorescent powder grain and cause its tangible fluorescence radiation).The initial blue light penetrating component of heterojunction mixes with the fluorescent material fluorescence excitation, constitutes new synthetic blue green light.Blue green light its chromaticity coordinates fluorescence in actual applications meets previously described chromaticity coordinates value.Luminous have two listed main spectrum maximum values of table-2, but disperse assembly by the simplest optics, such as, the creamy white glass flake, light can not decompose.This specific character of synthetic light be for will being equipped with those optical modules, and these optical modules show may have frosted or the sedimentary blue green LED application of mist is extremely important in vain.We studies show that fluorescent material, and its luminous predominant wavelength is between sub-band λ=490nm-λ=520nm, that is, to compare wavelength shorter with its spectrum maximum value position.This is that this fluorescent material and the photodiode that adopts this fluorescent material are compared the most important properties that has with the standard photodiode, and the predominant wavelength of standard photodiode is longer, no matter be peak value or maximum value.Adopt us to recommend this unusual advantage of the photodiode of fluorescent material, as we the invention process showed, be because the essential difference of phosphor material powder component reaches.Determining by optimizing moiety: Mg: Ca: Sr of light-emitting phosphor saturated green: the Ba concentration ratio was from 0.01: 0.01: 1.5: 0.5 to 0.05: 0.05: 1.45: 0.45. reached.As our finding, fluorescent material component (Mg _0,01Ca _0,01Sr _0,75Ba _0,23) ₂Zr _0,2Si _0,8O4: Eu _0.02At spectral wavelength is under the state of λ=504nm, and very bright twilight sunset is arranged, as improving the content of MgO and CaO, (Mg _0,05Ca _0,05Sr _0,70Ba _0,20) ₂Zr _0,2Si _0,8O ₄: Eu _0,02The fluorescent material of component then can produce emission wavelength to shortwave displacement λ=499nm.We are also noted that a key property, and this specific character can often take place when fluorescent material is synthetic.Materials chemistry equivalent component promptly comprises catalyzer Eu ^{+ 2}Stoichiometric index sum of element should be higher than calculated value, i.e. Me in interior positively charged ion lattice _Ij=2.Similarly positively charged ion does not meet the chemical dose method, as studies show that, has improved luminosity in single wedge shape phase bit position in having increased fluorescent powder grain yet.As at the analysis revealed that the synthetizing phosphor powder dispersivity test is carried out, the average diameter of particles value reduces when single wedge phase bit position of material volume improves.This analytical results sees Table-2.

Table-2

The fluorescent material component	The material phase place is formed	Particles dispersed, micron
					(Mg 0,02Ca 0,02Sr 0,74Ba 0,22) 2 Zr 0,2Si 0,8O 4:Eu 0,02	Oblique side's phase place	d 10	d 50	d 90
1,8	22	40
			(Mg 0,02Ca 0,02Sr 0,74Ba 0,22) 2 Zr 0,2Si 0,8O 4:Eu 0,02	Single wedge shape phase place and rhombus phase place vestige			1,0	16	30
(Mg 0,02Ca 0,02Sr 0,74Ba 0,22) 2 Zr 0,2Si 00,8O 4:Eu	Single wedge shape phase place, rhombus phase place vestige	0,6			12	24

The data of introducing shows that the geometrical dimension of fluorescent powder grain can improve the wavelength 10-80 of luminophore on its spectrum maximum value doubly.Be under the green emitting phosphor dispersed component situation of λ=0.5 μ m at the weighted mean wavelength like this, grain graininess d ₅₀=12 μ m promptly are 24 times of emission wavelength peak value.For big dispersed fluorescent material parameter value d ₉₀Be 80 times of twilight sunset wavelength peak.Certainly, similar high dispersive material is difficult to use in producing photodiode because macrobead fluorescent material rapid precipitation in the essential suspended substance of the preparation luminescent coating of preparing.So the fluorescent material of this batch of preparation is necessarily essential by synthetic sieve or the settled method fractionation of liquid.

The specific embodiment of the present invention

We describe fluorescent material in detail and prepare the aspect now, fluorescent material by in advance and zirconium dioxide, silicon-dioxide by forming by mixed oxygenant solid state sintering.

Use following batching in order to prepare first kind of fluorescent material:

MgO-0.05m

CaCO ₃-0.05m

Sr(OH) ₂·8H ₂O-1.5m

Ba(OH) ₂·8H ₂O-0.45m

Eu ₂O ₃-0.01m

SiO ₂-0.8m

ZrO ₂-0.2m，

Batching and magnesium chloride and NH ₄Careful evenly stir (dosage is to 0.1m) of CL.The batching alundum crucible of packing into, compacting and 400 ℃ of heating 1 hour in stove, 800 ℃ of heating 1 hour, 1200 ℃ of heating 3 hours.In stove, keep H ₂-5%, N ₂-95% reducing atmosphere.After cooling off with 5 ℃/second speed, product is come out of the stove, and cleans in the hydrochloric acid HCl (1: 20) of dilution, filters the back and dries by the fire 2 hours in 125 ℃ temperature.

The measurement of synthetizing phosphor powder optical technology parameter is carried out in special equipment, and it is λ=465nm that luminous here excitation light source adopts the wavelength of standard, and the half range curve of spectrum is λ _0,5The photodiode of=32nm.Photodiode is by constant voltage U=3.26V, and the current stabilization precision is Δ I=± 110 ^-4A, current value are I=20mA.Table-3.1, in listed above-mentioned component and the fluorescent material optical technology parameter card by the preparation of three sections synthetic methods.

Fluorescent material optical technology parameter

Mg _0.05Ca _0.05Sr _4.5Ba _0.45Si _0.8Zr _0.2O ₄:Eu _0,02

Table-3.1

№ item/item	Parameter	Parameter value
			1	Chromaticity coordinates	x＝0.203 y＝0.506
2	Colour temperature ° K	9810
			3	The spectrum maximum wavelength, nm	519
4	Predominant wavelength, nm	506
			5	Optical purity	036
6	Spectrum half range value, nm	45.0nm
			7	After-glow brightness, relative unit	24750
8	The colour system number, R a	35
			9	Radiance, relative unit	68500

Use following batching in order to prepare second kind of fluorescent material:

MgO-0.1m

CaCO ₃-0.1m

Sr(OH) ₂·8H ₂O-0.5m

Ba(OH) ₂·8H ₂O-1.4m

Eu ₂O ₃-0.02m

SiO ₂-0.8m

ZrO ₂-0.2m，

Batching and magnesium chloride and NH ₄Careful evenly stir (dosage is to 0.1m) of CL.The batching alundum crucible of packing into, compacting and 400 ℃ of heating 1 hour in stove, 800 ℃ of heating 1 hour, 1200 ℃ of heating 3 hours.In stove, keep H ₂-5%, N ₂-95% reducing atmosphere.After cooling off with 5 ℃/second speed, product is come out of the stove, and cleans in the hydrochloric acid HCl (1: 20) of dilution, filters the back and dries by the fire 2 hours in 125 ℃ temperature.

The measurement of synthetizing phosphor powder optical technology parameter is carried out in special equipment, and it is λ=465nm that luminous here excitation light source adopts the wavelength of standard, and the half range curve of spectrum is λ _0,5The photodiode of=32nm.Photodiode is by constant voltage U=3.26V, and the current stabilization precision is Δ I=± 110 ^-4A, current value are I=20mA.Table-3.2, in listed above-mentioned component and the fluorescent material optical technology parameter card by the preparation of three sections synthetic methods.

Fluorescent material optical technology parameter

Mg _0.1Ca _0.1Sr _0.5Ba _1.4Zr _0.2Si _0.8O ₄:Eu _0.02

Table-3.2

№ item/item	Parameter	Parameter value
			1	Chromaticity coordinates	x＝0.14 y＝0.54
2	Colour temperature ° K	11200
			3	The spectrum maximum wavelength, nm	499
4	Predominant wavelength, nm	492
			5	Optical purity	032
6	Spectrum half range value, nm	42.0nm
			7	After-glow brightness, relative unit	20400
8	The colour system number, R a	31
			9	Radiance, relative unit	62500

Use following batching in order to prepare the third fluorescent material:

MgO-0.1m

CaCO ₃-0.1m

Sr(OH) ₂·8H ₂O-0.4m

Ba(OH) ₂·8H ₂O-1.4m

Eu ₂O ₃-0.02m

SiO ₂-1.0m

Batching and magnesium chloride and NH ₄Careful evenly stir (dosage is to 0.1m) of CL.The batching alundum crucible of packing into, compacting and 400 ℃ of heating 1 hour in stove, 800 ℃ of heating 1 hour, 1200 ℃ of heating 3 hours.In stove, keep H ₂-5%, N ₂-95% reducing atmosphere.After cooling off with 5 ℃/second speed, product is come out of the stove, and cleans in the hydrochloric acid HCl (1: 20) of dilution, filters the back and dries by the fire 2 hours in 125 ℃ temperature.

The measurement of synthetizing phosphor powder optical technology parameter is carried out in special equipment, and it is λ=465nm that luminous here excitation light source adopts the wavelength of standard, and the half range curve of spectrum is λ _0,5The photodiode of=32nm.Photodiode is by constant voltage U=3.26V, and the current stabilization precision is Δ I=± 110 ^-4A, current value are I=20mA.Table-3.3, in listed above-mentioned component and the fluorescent material optical technology parameter card by the preparation of three sections synthetic methods.

Fluorescent material optical technology parameter

Mg _0.1Ca _0.1Sr _0.4Ba _1.4Si _1.0O ₄:Eu _0.02

Table-3.3

№ item/item	Parameter	Parameter value
			1	Chromaticity coordinates	x＝0.2 y＝0.55
2	Colour temperature ° K	9630
			3	The spectrum maximum wavelength, nm	510
4	Predominant wavelength, nm	498
			5	Optical purity	034
6	Spectrum half range value, nm	43.0nm
			7	After-glow brightness, relative unit	23000
8	The colour system number, R a	33
			9	Radiance, relative unit	67800

The optical tech parameter of all chemical ingredientss is all measured with similar approach, and test-results sees Table-4.

Table-4

The № item	Material component	The λ maximum value, nm	Chromaticity coordinates x y	The luminosity relative unit
					1	Mg 0.02Ca 0.02Sr 0.5Ba 1.4Zr 0.2Si 0.8O 4:Eu 0.02	504	0.16 0.52	22500
2	Mg 0.1Ca 0.1Sr 0.5Ba 1.4Zr 0.2Si 0.8O 4:Eu 0.02	499	0.14 0.54	20400
					3	Mg 0.1Ca 0.1Sr 0.4Ba 1.4Si 1.0O 4:Eu 0.02	510	0.20 0.55	23000
4	Mg 0.05Ca 0.05Sr 0.2Ba 1.7Zr 0.2Si 0.8O 4:Eu 0.02	502	0.15 0.52	20800
					5	Mg 0.05Ca 0.05Sr 0.3Ba 1.6Zr 0.1Si 0.9O 4:Eu 0.01Sm 0.01	509	0.19 0.56	21750
6	Mg 0.05Ca 0.05Sr 0.3Ba 1.6Zr 0.1Si 0.9O 4:Eu 0.05Yb 0.05	514	0.22 0.56	24800
					7	Mg 0.05Ca 0.05Sr 0.3Ba 1.6Zr 0.01Si 0.99O 4:Eu 0.05Dy 0.01	516	0.24 0.51	25250
8	Mg 0.05Ca 0.05Sr 0.2Ba 1.7ZrHf 0.01Si 0.99O 4:Eu 0.01 Sm 0.05Yb 0.01	526	0.25 0.54	24890
					9	Mg 0.05Ca 0.05Sr 0.2Ba 1.7Hf 0.05Zr 0.05Si 0.9O 4: Eu 0.02Sm 0.02	501	0.12 0.58	19990
10	Mg 0.2Ca 0.08Sr 1.4Ba 0.5Hf 0.01Zr 0.09Si 0.9O 4:Eu 0.02 Sm 0.02	538	0.29 0.55	28000
					11	Mg 0.05Ca 0.05Sr 0.4Ba 1.5Hf 0.4Zr 0.4Si 0.2O 4:Eu 0.02 Sm 0.02	514	0.19 0.58	21450

Obviously, the fluorescent material chemical equivalent formula of suggestion can synthesize the material of those luminous covering spectrum maximum value wavelength ~ 40nm, and color is sky blue, blue and bluish-green coloured light.The also suitable height of the brightness of synthetic materials is at 19990-28000 relative unit.Aluminium yttrium pomegranate standard fluorescence powder (Y, Gd, Ce) ₃Al ₅O ₁₂,, having luminous intensity under the state that excites by the InGaN heterojunction is 26500 relative units.

Recommend the above-mentioned advantage of fluorescent material to be embodied in especially in this case, when the phosphor powder with above-mentioned component serves as that the basis forms the light conversion coating, coating is distributed in above the polymkeric substance linking agent that comprises following chemical group with particle form.

{ C-C-} _mOr { C-Si-O-Si-} _mO

Polymerization degree 250＜m＜1500, described in addition fluorescent powder grain is formed the total number of plies quantity of the single-layer coating 3-6 layer of lining up one by one, the quality total amount concentration of fluorescent material in coating is 5-75%, and the geometric thickness with heterojunction semiconductor basal plane and the contacted coating of light emitting end surface is the 10-200 micron respectively.

Our test shows, changes the quality of luminescent coating by adding fluorescent powder grain, can successfully control the luminosity of whole device.Because forming the coating luminosity by the fluorescent powder grain that accounts for total amount 10% of three single-layer coatings and filling is 10 units, and if coating quantity is brought up to 4-x simultaneously the total amount concentration of fluorescent material is brought up to 35%, then luminosity can reach 150 units.If the fluorescent material total amount reaches 60%, will make luminosity drop to 100 units.So the fluorescent material extreme care is not only that the mass concentration of control fluorescent powder grain also has total geometric thickness of coating in the process of preparation luminescent coating, is d adopting mean diameter ₅₀Under the situation of=12 microns fluorescent powder grain, the optimum thickness of coating should be 120 microns, and single-layer coating quantity is 3-4.At this moment luminosity is 220 units, and this is very high value.

The high optical technology parameter of this luminescent coating embodies during based on the photodiode of InGaN base heterojunction in preparation, heterojunction contacts with luminescent conversion layer, and the luminescent coating that this external heterojunction surface forms is for all heterojunction surfaces and 5 light-emitting areas on follow-up optical waveguide layer (2-prototype) surface that is positioned at described printing opacity and the geometric specifications that all has same thickness.This printing opacity leaded light coating imitates epoxy by heat or thereby organosilicon polymer is formed the matrix that constitutes luminescent coating.This coating is the symmetric cylindrical shape of axis in addition, contacts with light-emitting diodes tube shell lens cap internal surface on the optics.Lens cap is made and is equipped optical focus spherical optics instrument or Frenel opticinstrument by polycarbonate.Photodiode lid enclosure interior volume filled polymer is finished by final assembling instrument.This program can be removed the optical surface of boundary in the photodiode, can make the luminous light output of instrument total amount improve 1.25-1.5 doubly.

In table-5, listed light emitting diode (LED) light technical feature parameter testing result prepared in accordance with the present invention.

Table-5

The № item	Light emitting diode construction	Chromaticity coordinates x y	Luminescent spectrum, nm		The light intensity milli is burnt	Luminous output angle 2 θ 1/2	The power milliwatt
								Maximum value	Leading value
			1 2 3	Standard standard standard						0.10 0.57 0.10 0.57 0.10 0.57	505 505 505	510 510 510	9200 3920 3920	15 30 30	80 80 80
4 5 6	Photodiode (465nm)+light-emitting phosphor diode (465 nm)+light-emitting phosphor diode (465 nm)+fluorescent material	0.14 0.58 0.18 0.58 0.10 0.65			505 505 506	503 503 503	1030 0 4200 4200	15 30 30	80 80 80

Gained is given out light purity above a＞0.75, and this has illustrated the high optical technology quality of recommending contrive equipment.Must be pointed out that the light intensity value that this photodiode reached (milli is burnt) surpasses based on 1 of sky blue-indigo plant-green luminous heterojunction instrument light intensity, 5-2 times, this just means the luminescent coating that not employing recommends invention fluorescent material to make.

Recommend photodiode to make and these instruments can be used for the special telltale of railway traffic in the open high light intensity of optics transfer Small angle.Telltale has luminous output 2 θ of Small angle _1/2Also can on far distance, can see that for example, the current lamp of bluish-green color can be seen in the 1000m distance for=15 °.So long distance is observed the telltale that adopts incandescent lamp can only realize that this work-ing life that will shorten incandescent lamp significantly was to 200-300 hour by the power that improves incandescent lamp.Use the application test of blue green LED in traffic lights of recommending to show that can reach 10000 hours work-ing life.The difference of the photodiode that the fluorescent material that the telltale of railway uses us to invent recommendation is made is, the telltale of chatting with 48-64 formal group layout photodiode, in this case, photodiode is positioned on the same conductive soleplate, this conductive soleplate adopts the paper tinsel matter dielectric medium printed circuit board (PCB) of band geometric specifications d=1.0mm conductive rubber to make, and contact-be connected in parallel with photodiode and form same electrical network, voltage of supply is the U=8-12 volt, electric current in full is J=2A, this moment, be that the multiple group changes opticinstrument on distance light-emitting diodes tube outer surface, focus on each photodiode image, make it can estimate with synthetic blue-greenish colour standard signal lamp form.

Now in the model trial of the telltale of recommending that is used for railway traffic.Its suitability for industrialized production is expected to be 2006-2007.

Document:

1、V.S.Abramov and V.P.Sushkov，Soviet Union № 635813 in1973.

2, Shimizu et all.US pat.5998925 is published in 1999

3, US application № 20040227465A OT 18.11.2004.

4、EP 1367655A1 OT 10.12.2004.

Claims (12)

1, the fluorescent material that is used for photodiode, the chemical formula of this fluorescent material is:

(Me ^II _i) _Xi(Me ^IV _j) _YjSi _ZO ₄TR ¹², Me wherein ^II _i=Mg and/or Ca and/or Sr and/or Ba, Me ^IV _j=Zr and/or Hf, $\underset{i=1}{\overset{4}{\mathrm{\Σ}}}{x}_i=2,\underset{j=1}{\overset{2}{\mathrm{\Σ}}}{y}_i=0-0.99,Z=1-\underset{j=1}{\overset{2}{\mathrm{\Σ}}}{y}_j,$ TR ^{+ 2}=Eu ^{+ 2}And/or Sm ^{+ 2}And/or Yb ^{+ 2}And/or Dy ^{+ 2}

2, according to the fluorescent material of claim 1, wherein said fluorescent material sends on the spectrum blue green light its stoke shift with respect to indium nitride, gallium heterojunction are luminous and is equal to or greater than 40nm in photodiode, luminescent spectrum district half range λ 0,5=40nm, be positioned at the blue green light interval on the spectrum, wavelength X=500-525nm.

According to the fluorescent material of claim 1, be characterised in that 3, this fluorescent material is using Eu, Sm, Dy forms the green fluorescence powder particles during divalent ion excitations such as Yb, and reflection coefficient is at R ₄₀₀=20%, R ₄₅₀=25%, R ₅₀₀=50% interval change, form the particle shallow layer, absorb the initial blue ray radiation of InGaN base heterojunction, and optically doubly with its weak 5-20, initial blue light by above-mentioned shallow layer mixes with fluorescent material secondary excitation fluorescence in addition, form synthetic green glow, it is x that the green light color coordinate is positioned at look district color coordinates ₁=0.02y ₁=0,5, x ₂=0.225 y ₂=0.39, x ₃=0,28 y ₃=0,45, x ₄=0,02 y ₄=0,74, form the stable blue green light that can not be decomposed by opticinstrument, predominant wavelength is at λ _Main=490-520nm.

According to the fluorescent material of claim 1, be characterised in that 4, this fluorescent material is at the element M g of IIa family: Ca: Sr: Ba nucleidic mass concentration ratio is 0,01: 0,01: 1,5: 0,5-0 05: 0,05: 1,41: 0, sends saturated green glow under 45 the situation.

5, according to the fluorescent material of claim 1, be characterised in that, this fluorescent material is shaped as a phase place or the two phase lamellar morphology of oblique side and/or single wedge structure, and in addition, the particle specification of above-mentioned fluorescent material surpasses 20-80 times of its luminescent spectrum maximum value wavelength and forms 2.2-2.8g/cm ³Closely knit quality packing.

6, be used for photodiode based on silicon and/or contain the synthetics of Resins, epoxy and fill each the light conversion polymer layer of fluorescent material of claim 1-5.

7, change polymer layer according to the light of claim 1, be characterised in that, described polymer layer is distributed in heat with the dispersive form and imitates on the fluoropolymer resin, the single fluorescent powder grain of polymerization degree M=1500y.e, described in addition fluorescent powder grain is formed the total number of plies quantity of the single-layer coating 3-6 layer of lining up one by one, the quality total amount concentration of fluorescent material in coating is 5-75%, and the geometric thickness with heterojunction semiconductor basal plane and the contacted coating of light emitting end surface is the 10-200 micron respectively.

8, the blue-greenish colour photodiode based on the heterojunction semiconductor of InGaN of equipment claim 7 described smooth conversion coating.

9, blue-greenish colour photodiode according to Claim 8 based on the heterojunction semiconductor of InGaN, be characterised in that, the described luminescent coating that forms on the heterojunction surface based on the light conversion layer of silicon and/or Resins, epoxy is for 5 light-emitting areas on all heterojunction surfaces and the geometric specifications that all has same thickness, and be the symmetric cylindrical shape of axis, contact with light-emitting diodes tube shell lens cap internal surface on the optics, lens cap is made and is equipped optical focus spherical optics instrument or Frenel opticinstrument by polycarbonate.

10, the described photodiode of claim 9 is characterised in that, this photodiode is at narrow dual angle 2 θ _1/2=15-2 θ _1/2Luminous light intensity is the 4.2-10.0 kilojoule in=30 scopes, excite the electric power of single photodiode this moment is 80mW, in addition, lumination of light emitting diode predominant wavelength is than the short 2-5nm of led lighting maximum wavelength, chromaticity coordinates is x=0.10y=0.65-x=0.2y=0.4, and bluish-green colour purity is higher than a=0.75.

11, the telltale of the railway traffic application of the photodiode of each of employing claim 8-10.

12, according to the telltale of claim 11, be characterised in that, this device is with 48-64 formal group layout photodiode, in addition, described photodiode and unitary opticinstrument are positioned on the same conductive base, this conductive base adopts the paper tinsel matter dielectric medium printed circuit board (PCB) of band geometric specifications d=0.55mm conductive rubber to make, this moment, distance at distance light-emitting diodes nest of tubes 10-60 micron is a quadratic gropup conversion opticinstrument, make described each photodiode unit's image form the synthetic blue-greenish colour, visual distance surpasses 1000m.