CN1876756A - White light diode, synergistic light-transferring powder, fluorescent powder and fluorescent powder preparation method - Google Patents
White light diode, synergistic light-transferring powder, fluorescent powder and fluorescent powder preparation method Download PDFInfo
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- CN1876756A CN1876756A CNA2006100900890A CN200610090089A CN1876756A CN 1876756 A CN1876756 A CN 1876756A CN A2006100900890 A CNA2006100900890 A CN A2006100900890A CN 200610090089 A CN200610090089 A CN 200610090089A CN 1876756 A CN1876756 A CN 1876756A
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Abstract
The invention relates the preparing method of white light diode, synergy luminescent powder and luminescent powder. The chemical formula of fluorescent material is BaalphaY3 betaAl2alpha+5 betaO4alpha+12 beta, and the value of alpha and beta are between 0.01-4. The lattice structure of the luminescent powder changes from cubic lattice to monoclinic system along with the change of value of alpha and beta. The characters are that it expresses strong yellow and it has high luminous emissivity and long luminous emissivity time. The invention provides the synergy luminescent device, composed by high molecular polymer and luminescent powder particle. The filling density of luminescent powder is 1-50%. The white light semi-conductor source has strong luminous intensity and luminous flux, and the luminous efficiency is up to 50lm/w.
Description
Technical field
The present invention relates to the preparation method of a kind of white light-emitting diodes, synergistic light-transferring powder, fluorescent material and fluorescent material, relate in particular to a kind of multiple color of light of energy radiation of having used, the nitride heterojunction that comprises white light, it is showing characteristics is to present intensive yellow and yellowish-orange, has the preparation method of white light-emitting diodes, synergistic light-transferring powder, fluorescent material and the fluorescent material of very high quantum luminosity factor and persistent fluorescent lifetime.
Background technology
From nineteen sixty-eight, beginning widespread use fluorescent material reaches the spectrum transformational structure based on fluorescent material in led technology.Initial what occur is the transfer equipment that improves glow frequency, and the effect by the anti-Stokes fluorescence powder is with the near-infrared luminous redness or the green light (please refer to Berg, Din A., LED, " Mir ", 1975) of changing into of GaAsP diode.Afterwards, numerous research workers attempt changing the weak ultra-violet light-emitting of GaN diode into visible light.
(S.Nakamura S.Shimizu) has obtained breakthrough progress to the expert of Japan Nichia company on this research direction, they have developed GaInN heterojunction and the yellow aluminium yttrogarnet fluorescent material (Y that covers its surface by blue light-emitting
3Al
5O
12) new type light source (please refer to S.Nakamura in 11,05, the 2006 German DE6933829T patents of getting permission, and S.Shimizu Y., in 11,01,2005 TW156177B that get permission) that constitutes.
The application of these two invention achievements has realized being used for illumination, the white light emitting diode of lamp decoration and indication purposes.In photodiode, should be used as detailed description to this aluminium yttrogarnet fluorescent material in the patent document (please refer to S.Shimizu Y., in 11,01,2005 TW156177B that get permission).But we think that the present invention does not have absolute innovative significance.We as prototype, below are the innovation parts of listing in its patent shelves: 1. do the light-emitting diode structure basis with the GaInN heterojunction of blue light-emitting with it; 2. in photodiode, adopted fluorescent powder grain with synergistic light-transferring effect; 3. luminous by with two parts, promptly the GaInN heterojunction semiconductor is directly luminous is mixed by its stimulated luminescence mutually with fluorescent powder grain, finally obtains white light; And 4. to adopt chemical formula be Y
3Al
5O
12: the aluminium yttrogarnet of Ce and derivative thereof (as (Y, Gd)
3(Al, Ga, Sc)
5O
12: the Ce) fluorescent material of particle formation.GaInN heterogeneous semiconductor about blue light-emitting has been knotted lot of documents, but people such as S.Nakamura and G.Fasol (please refer to S.Nakamura and G.Fasol in disclosed technical publications in 1998, The blue laser diodes.Berlin, Springer, 1998) only quoted a wherein part in.The efficient luminous nitride heterojunction achievement on the quantum effect basis of S.Nakamura research and development has been that the whole world is common, and it is not qualified therefore it being given the credit to Nichia company fully.
The synergistic light-transferring powder that is used for photodiode as previously mentioned, adopts anti-Stokes material (please refer to Berg, Din A., LED, " Mir ", 1975) to be made through careful technology.Short-wave radiation is used for exciting that various materials are luminous all has a detailed description at a lot of thematic academic papers (please respectively with reference to P.Pringshein, Phluorescence andphosphorescence, IL, 1950; G.Blasse, P.Grabmaier, Luminescencematerials, Pergamon press, NY, 1995; And S.Shionoja, W.Yen, Handbook of phosphors, NY, 1999.).We think, by means of the photodiode that sends short-wave radiation, realize that obtaining relative long-wave band radiating method from fluorescent material does not have substantial innovative significance and the distinctive feature that is showing.Be used to excite other material luminous light source varied, comprising charging source: 1. the geseous discharge of mercuryvapour; 2. the geseous discharge of nitrogen; And 3. xenons, the geseous discharge of krypton gas.In addition, it is luminous that laser radiation also is widely used in excitated fluorescent powder, as the nitrogen laser apparatus, and the Nd:YAG laser apparatus of output triple-frequency harmonics and four-time harmonic.
Scheme with the semiconductor light-emitting-diode excitated fluorescent powder is mentioned (please refer to S.Nakamura and G.Fasol, The blue laser diodes.Berlin, Springer, 1998) more than once.
Below be about by two or three basic light sources are combined to obtain the problem of white light.The monochromatic ray that light generation chromatic dispersion is obtained synthesizes, as blue light and gold-tinted, and green glow and ruddiness, ruddiness, green glow and blue light etc., the physical basis that finally obtains the way of white light is established by newton the earliest, by the photochromic theoretical developments of his proposition.This physical principle is being widely used in printing 19 and 20th century, photography, especially black and white and color TV technology.As, Zi Woleijin utilization blue light and two kinds of base lights of sodium yellow have been made the monochrome presentation tube display that emits white light and (please refer to H.W.Leverenz, Anintroduction to Luminescence of Solids, NY, 1950), this is complicated technology scheme of color TV technical field: not only need primitive color light to have complete chromatic aberration coefficient, and will quantitatively compensate primary colors to obtain the white light of color standard.
Also solve (please refer to L.M.Kogan LED lighttechnic, Moscow, Ho.5, pp.16-20. (2002)) with the close problem of above-mentioned physical principle in the lighting technical field: mercury vapor discharge sends blue light, excites YVO
4: Eu sends red light, finally obtains and the luminous white light that is close of white light source.The shortwave discharge of xenon and krypton gas guarantees that the gas discharge plasma flat board can produce RGB look and white light.Therefore, replacing glow discharge spot lamp luminous with excitated fluorescent powder with semiconductor light-emitting-diode is to improve illumination, information, and the technical progress that is showing in the indication mechanism process, trend also is inevitable.
The blue light source that can produce multiple optical effect is used widely, such as, the luminous blue light source of steady persistence and overlength afterglow is widely used in the radiolocation technology.Organically combine in a device on the yellow-white twilight sunset optics of original blue light and active display.
Therefore, propose in Nichia company before their achievement in research, by the physical principle of two or three light source synthesizing colourless difference white lights for a long time by known to everybody and use.
Yttrium aluminum garnet a lot of jural disputes have been caused as fluorescent material, because only obtaining just having the right to use under the situation that Nichia company permits this material (thus even occurred the non-yttrium aluminum garnet fluorescence that new research direction one is used for photodiode), this authority was proved to be to lack fully basis afterwards.At first, the fluorescent material that constitutes by yttrium aluminum garnet and the appearance of indicating meter far early than Japanology worker's achievement in research (please respectively with reference to G.Blasse, P.Grabmaier, Luminescence materials, Pergamon press, NY, 1995; S.Shionoja, W.Yen, Handbook ofphosphors, NY, 1999.; H.W.Leverenz, An introduction toLuminescence of Solids, NY, 1950 and V.A.Abramov, patent USSRNo.635813,09,12,1977.).Chemical constitution is Y
3Al
5O
12Or (Y, Gd)
3(Al, Ga)
5O
12: the material of Ce is widely used in the high speed cathode ray tube technologies to detect black and white or color negative film.With Powdered yttrium aluminum garnet or monocrystalline yttrium aluminum garnet is that the scintillator of architecture basics is used in nuclear physics and the nuclear technique by people.Simultaneously, spectrographic physics correction technique is also used by people.Therefore we can say, the Main physical characteristic of YAG fluorescent material, as the luminous efficiency height, blue-greenish colour at visible light, green, yellow and orange wave band broadband band is luminous, and twilight sunset is quite short, optical throughput and power stable high just known by people before Nichia company is used for garnet phosphor powder photodiode.Thereby we think, the expert of Nichia does not exceed about the achievement in research of garnet phosphor powder fluorescent material rationally is used for the required know-how of its direct purposes.Simultaneously, all luminescent materials that do to start agent with cerium all being belonged in the patent claim of Nichia also is to lack basis fully.The known a large amount of fluorescent materials of people are as Al
2O
3: Ce, gelenite:Ce, yttrium, gadolinium, the orthosilicate of lutetium and pyrosilicate Y
2Si
2O
5: Ce, Gd
2SiO
5: Ce, Lu
3Si
2O
7: Ce, they are widely used in the production of fluorescence technique, in the practical experience of life, with the patent achievement of Nichia company without any relation.
Can be drawn to draw a conclusion by above analysis: 1. the technology that fluorescent material and synergistic light-transferring device is used for all kinds photodiode is known by people already; By two or more base light is combined to obtain white light method we also quite understand, its physics and colourity principle are very clear and definite; 3. the fluorescent material of making main composition for the yttrium aluminum garnet compound of startup agent in order to cerium just occurred as far back as nineteen sixty-five, that is to say the invention early than Nichia company far away; 4.Ce
+ 3Be used to start fluorescent material with various crystalline structure; And 5.Nichia company do not have character of innovation about the patent achievement of garnet phosphor powder, and just at the technical solution of current particular problem: obtain white light by blue base light, the real a fly in the ointment that belongs to.
Summary of the invention
For solving the shortcoming of above-mentioned prior art, main purpose of the present invention provides the preparation method of a kind of white light-emitting diodes, synergistic light-transferring powder, fluorescent material and fluorescent material, and it can be used on the photodiode and has new constituent and new features.
Another object of the present invention is to provide the preparation method of a kind of white light-emitting diodes, synergistic light-transferring powder, fluorescent material and fluorescent material, it can be chosen in and adopt radiation wavelength under the situation of the nitride heterojunction of 440nm～475nm, can produce the optimum formula of multiple colour temperature radiating fluorescent material.
Another object of the present invention is to provide the preparation method of a kind of white light-emitting diodes, synergistic light-transferring powder, fluorescent material and fluorescent material, its selection is used in the synergistic light-transferring material on the nitride heterojunction, the research optimum structure.
Another object of the present invention is to provide the preparation method of a kind of white light-emitting diodes, synergistic light-transferring powder, fluorescent material and fluorescent material, it can make the integrally-built optimization of photodiode, the optical thickness that comprises the synergistic light-transferring layer is inserted submergence assembly etc. at the inner chamber of photodiode.
For reaching above-mentioned purpose, a kind of fluorescent material of the present invention, it is used for white light-emitting diodes, it is by II in the periodic table of elements, the oxide compound of III main group element is a matrix, do to start agent with the element of electronics d layer and f layer generation transition, and the matrix of this fluorescent material is made of the solid solution of the similar aluminate of barium and yttrium, its chemical formula is Ba
αY
3 βAl
2 α+5 βO
4 α+12 β, and the crystallographic system of its lattice changes with the change of barium and yttrium proportionlity; When this matrix was excited by a short-wave radiation, the ion of this element can give off green orange-colored light, mixed back formation white light mutually with the short-wave radiation that an InGaN heterojunction semiconductor sends.
For achieving the above object, a kind of white light-emitting diodes of the present invention, it is made of an InGaN heterojunction semiconductor and a synergistic light-transferring powder, wherein this synergistic light-transferring powder system is made of polymeric matrix and fluorescent material, its architecture basics is that the polymerization degree is 100～500, molecular mass is greater than the Resins, epoxy or the silicone resin of 5000 standard carbosilane units, and fill 1%～50% fluorescent material therein, thereby on the light-emitting area of heterojunction, form a layer thickness homogeneous polymer layer, this layer can change into the primary radiation of shortwave heterojunction the white light of colour temperature between 6000K～3200K, and its luminescent chromaticity is Ra 〉=85.
For achieving the above object, the preparation method of a kind of fluorescent material of the present invention, it comprises the following steps: oxide raw material and carbonate are carried out solid state sintering; Under hot environment, continue some hrs; And in reducing environment, carry out the calcination stage with high temperature.
For achieving the above object, the preparation method of a kind of fluorescent material of the present invention, it comprises the following steps: with oxyhydroxide to be raw material; And they are joined thorough mixing in the fused hydrated barta in the proper ratio.
Embodiment
The present invention proposes new phosphors and synergistic light-transferring powder on its basis, this fluorescent material is with the period of element Table II, the oxide compound of III main group element is a matrix, do to start agent with the d-f element, have following feature: the matrix of this fluorescent material is made of the solid solution of the similar aluminate of barium and yttrium, and chemical formula is Ba
αY
3 βAl
2 α+5 βO
4 α+12 β, wherein the span of α is α=0～4, preferred α=0.01～4; The value of β is β=0～4, preferred β=0.01～4.The crystallographic system of lattice changes with the change of barium and yttrium proportionlity.When α≤0.1, lattice is an isometric system; When α=1, β≤0.1 o'clock is a hexagonal system; When α=1, β=1,0 o'clock is an oblique system.In above-claimed cpd, add f element and d element: Ce, or Pr, or Eu, or Dy, or Tb, or Sm, or Mn, or Ti, or Fe, they have+2～+ 4 different degree of oxidations, when matrix compounds is excited by the short-wave radiation of λ≤470nm, above-mentioned ion can give off the green orange-colored light of wavelength X=530nm～610nm, and the short-wave radiation that sends with the InGaN heterojunction semiconductor is combined to back formation white light.
Physical chemistry essence of the present invention is as follows.At first, experiment of the present invention finds that the aluminate of II main group element and yttrium aluminate have close optical characteristics, as MeAl
2O
4(when Me=Mg or Ca, formation has MgAl
2O
4Or Me the compound of the cubic crystal structure of spinel type),
4Al
7O
15The compound of type.When these compounds by Ce
+ 3When ion starts, have the very strong characteristics of luminescence, meeting is luminous by the beam excitation of λ=450～470nm that blue light diode sends.
Experiment of the present invention also finds, single aluminate of II main group element and many aluminates with Y
3Al
5O
12Garnet type yttrium aluminate or uhligite YAlO
3When the type yttrium aluminate formed solid solution, its characteristics of luminescence can strengthen.The MeAl that contains integer number in the composition of this solid solution
2O
4The single aluminate of type for example, may contain 1,2,3 or 4 unit list aluminates in the unit yttrium aluminum garnet.Yet, also might obtain containing the solid solution of single aluminate of non-integer unit, as, MeAl
2O
4Quantity can be 0.1,0.25,0.4,0.5 etc.Also can contain a small amount of latter in the solid solution that the aluminate of II main group element and yttrium aluminate form.In this case, when α=1, β≤0.1 o'clock, the crystalline structure of solid solution is near hexagonal system; And when α≤0.1, β=1 o'clock, crystalline structure is near the typical isometric system of yttrium aluminate garnet.This moment lattice parameter near a=12.4A °, the lattice parameter of overgauge yttrium aluminum garnet.Yet, Ce in having the lattice of this parameter values
+ 3The easier dissolving of ion (solubleness can reach more than 15%, and in the standard yttrium aluminum garnet Ce
2O
3Average solubleness be no more than 3%.
When α≤1, and β≤1 o'clock, the crystalline network of solid solution is loose, belongs to oblique system (a, b, c, γ angle).
The solid solution that the aluminate of II main group element and yttrium aluminate form is the bigger ion of volume of dissolution well, as Ce
+ 3With Ce
+ 3Belong to the Pr of light rare earths
+ 3Also easily be dissolved in this solid solution.Dy
+ 3, Tb
+ 3, Eu
+ 3Deng the heavy rare earth element ion and be positioned at light, the Sm of position, heavy rare earth element boundary
+ 3Very easily be dissolved in the synthetic solid solution.At this moment, the Eu that has variable valence state
+ 2And Sm
+ 2May there be two kinds of different states of oxidation simultaneously :+2 and+3 valence states, and Mn
+ 2With Mn
+ 4, Ti
+ 3With Ti
+ 4, Fe
+ 2With Fe
+ 3May simultaneously or separately exist in the crystalline network of solid solution.At this moment all above-mentioned ions all have very strong tuorbillion and revolve opticity (some ion wherein is as Ti
+ 3, be to have regained this tuorbillion to revolve opticity).All are above-mentioned to have strong tuorbillion and revolves the ion of opticity and be excited luminous wave band near ultraviolet band (Dy
+ 3, Tb
+ 3, Mn
+ 4, Ti
+ 3) or visible light in the blue light wave band of λ=440nm.
The present invention has carried out careful analysis to the radiation spectrum of d element in the synthetic solid solution and f element, has obtained the BaAl by 1/4m
2O
4With 1m Y
3Al
5O
12Spectrum-the color temperature characteristic of synthetic solid solution.By Ce
+ 3Starting luminous obvious characteristics is the bell-shaped curve spectrum with bigger line half-width value.
Also obtained BaAl by 0.5m
2O
4With 1m Y
3Al
5O
12Synthetic fluorescent material is at Ce
+ 3With Pr
+ 3Luminescent spectrum under the double starting effect.Be characterized in that Pr is+3 valence state ions, its luminescent spectrum line is positioned at the long wave band of λ=610nm～615nm.
Use multiple startup agent to have the following advantages in above-mentioned novel cpd: 1. the wave band of light-emitting phosphor spectrum covering is before wideer; 2. can start agent by adding a small amount of second kind even the third, change or revise original luminous color; 3. can change the color of light-emitting phosphor by selecting the exciting light of different frequency.
Stoichiometry parameter alpha and β get arbitrary value in span, above-mentioned advantage all embodies to some extent, as corresponding 1m Y
3Al
5O
12, α=0.25 and α=0.5 o'clock shows particularly outstanding.At this moment, the lattice of fluorescent material matrix is isometric system, compd B aAl
2O
4And Y
3Al
5O
12Respectively by Eu
+ 2And/or Ce
+ 3Start, dissolving mutually generates fluorescent substance.
When stoichiometry parameter alpha=1 and β≤0.1, the formation chemical formula is BaY
0.3Al
2.5O
5.2Fluorescent material, bivalent rare earth element ion Eu
+ 2With Sm
+ 2With its startup, luminous in spectrographic blue-greenish colour wave band narrow band, line half-width λ
0.5=60-70nm.The fluorescent material matrix of this moment has the orthorhombic system crystalline structure, after the blue light of the λ=460nm that is sent by heterojunction excites, launches chromaticity coordinate x=0.17-0.22, the bluish-green coloured light of the intensive of y=0.45-0.55.
Remove traditional startup agent Ce
+ 3Outward, if in the fluorescent material matrix, dissolve in Ti again
+ 3With Fe
+ 3Can make the fluorescent material radiation peak increase 125～130nm, the chromaticity coordinate of this moment has orange red feature: x≤0.40, y≤0.45.
As the BaAl that in the fluorescent material matrix, adds stoichiometry parameter alpha≤1
2O
4, the solid solution crystal has the rhombic system structure.Can use Gd this moment
+ 3Replace part Y
+ 3, the radiation peak of fluorescent material can move to the long wave direction, moves to λ≤570nm wave band from λ=558nm.Luminous chromaticity coordinate sum ∑ (x+y) 〉=0.80.The advantage of this fluorescent material sample shows sends high-temperature red light.
The stoichiometry parameter alpha, β variation in α/β 〉=2 scopes can make the color burn of synthetizing phosphor powder itself.When α=1, β=1 o'clock, it is light yellow that fluorescent material is, and approaches straw yellow, and the increase with the α value fades to gold.The minimum value of this fluorescent material absorbing radiation appears at λ=440-480nm wave band, and the reflection of light value maximum to λ 〉=560nm wave band reaches R=90%-95%.
The front was mentioned, and can use Sr
+ 2Or Ca
+ 2Replace the part Ba in the positively charged ion sublattice
+ 2At this moment, the fluorescent material matrix can be by Eu
+ 2, Sm
+ 2Or Mn
+ 2Start, produce narrow band radiation, Δ λ=100-110nm at spectrographic 505nm～585nm wave band.
Also studied the motion characteristics of light-emitting phosphor in the present invention.When stoichiometry parameter alpha=1, β≤0.5 o'clock, the twilight sunset t of light-emitting phosphor
e=100-150ns, and when beta/alpha 〉=4, twilight sunset can reduce to t=40-50ns.
This fluorescent material that the present invention proposes has some synthetic schemess.The preparation method of fluorescence of the present invention comprises the following steps: oxide raw material and carbonate are carried out solid state sintering (step 1); Under hot environment, continue some hrs (step 2); And in reducing environment, carry out calcination stage (step 3) with high temperature.
In step 1, oxide raw material and carbonate are carried out solid state sintering; Wherein, this oxide raw material is Y
2O
3, Al
2O
3, CeO
2, this carbonate is BaCO
3
In step 2, under hot environment, continue some hrs; Wherein, this hot environment is 1100 ℃ to 1500 ℃, and continues 2～10 hours.
In step 3, in reducing environment, carry out the calcination stage for 1100 ℃ to 1500 ℃ with high temperature; Wherein, this reducing environment is H
2: N
2=1: 20.
The preparation method of the fluorescent material of another preferred embodiment of the present invention comprises the following steps: with oxyhydroxide to be raw material (step 1); And they are joined thorough mixing (step 2) in the fused hydrated barta in the proper ratio.
In step 1, be raw material with oxyhydroxide; Wherein, this oxyhydroxide is Ba (OH)
28H
2O, Al (OH)
3, Y (OH)
3, CeO
2Deng.
In step 2, they are joined thorough mixing in the fused hydrated barta in the proper ratio; Wherein, be homogeneous solid solution shape, can obtain the product of the higher luminescence technology parameter of having of equal quality with this chemical scorification synthetic fluorescent material.
Embodiment
Embodiment 1
Step 1: weigh following former material and be positioned in the crucible, and fully mixed:
Y
2O
3：33.9g，Al
2O
3：29.7g，CeO
2：1.7g，BaCO
3：5g。
Step 2: crucible is positioned in 1100 ℃ of the High Temperature Furnaces Heating Apparatuss continues 4 hours.
Step 3: carry out the calcination stage for 1450 ℃ with high temperature crucible being positioned in the reducing environment; Wherein, this reducing environment is H
2: N
2=1: 20.
Embodiment 2
Step 1: weigh following former material and be positioned in the crucible, and fully mixed:
Ba(OH)
2·8H
2O：8g，Al(OH)
3：42.9g，Y(OH)
3：42g，，CeO
2：1.7g。
Step 2: carry out the calcination stage for 1350 ℃ with high temperature crucible being positioned in the reducing environment; Wherein, this reducing environment is H
2: N
2=1: 20.
According to above two kinds of methods,, can obtain other fluorescent material of the present invention by changing components in proportions.
Listed the characteristic parameter of scorification gained compound in the table 1.
Table 1
| The stoichiometry parameter value | The crystalline network type | By Ce +3Peak wavelength during startup, nm | x，y | ||
| α | β | ||||
| 1 | 1.0 | 0.1 | Rhombic system | 530 | 0.29，0.32 |
| 2 | 1.0 | 0.25 | Hexagonal system | 540-55- | 0.35，0.39 |
| 3 | 1.0 | 0.5 | Hexagonal system | 545-560 | 0.36，0.42 |
| 4 | 1.0 | 1.0 | Oblique system | 560-570 | 0.38，0.42 |
| 5 | 0.75 | 1.0 | Hexagonal system | 540-560 | 0.34，0.38 |
| 6 | 0.5 | 1.0 | False isometric system | 535-585 | 0.30，0.45 |
| 7 | 0.25 | 1.0 | Isometric system | 545-585 | 0.38，0.44 |
| 8 | 0.1 | 1.0 | Isometric system | 550-560 | 0.36，0.42 |
| 9 | 2.0 | 1.0 | Rhombic system | 545-575 | 0.33，0.43 |
| 10 | 0.10 | 4.0 | Isometric system | 535-575 | 0.30，0.45 |
Approach sheet by scorification synthetic fluorescent powder grain, the variation of granularity is mainly reflected in (1 μ～20 μ) on its planar linear size, and variation in thickness little (1.5 μ～2 μ).This sheet structure of fluorescent powder grain is convenient to be made into the synergistic light-transferring device, and this device is to be made at the inner fluorescent powder grain of evenly filling of polymeric film.Selecting the polymerization degree for use is 100～500, and the molecule quality is 5000～10000 Resins, epoxy or the silicone resin material as polymer thin film.The polymer molecule quality is crossed the influence of generating heat when conference makes it can't bear photodiode work.The filling concentration of fluorescent powder grain in the synergistic light-transferring structure is 1%～50%, optimum concentration is 15%～25%, this moment, this synergistic light-transferring powder formed the uniform tectum of thickness in all light-emitting areas of heterojunction, the geometric thickness of this layer changes with the variation of sheet fluorescent powder grain degree between 50 μ～200 μ.The thickness of synergistic light-transferring layer is generally at 80 μ～120 μ.
Designed the scheme of multiple making white light emitting diode in the process of the test of the present invention.Its technical parameter is as follows: luminous intensity I 〉=100cd, luminous efficiency η 〉=35lm/w.Compare with traditional garnet phosphor powder, this novel fluorescent material has higher color index R 〉=85 owing to luminescent spectrum is wideer, thereby is applied to building in the photodiode of comfortable illumination.
In sum, the preparation method of white light-emitting diodes of the present invention, synergistic light-transferring powder, fluorescent material and fluorescent material, it has used the multiple color of light of energy radiation, the nitride heterojunction that comprises white light, it is showing characteristics is to present intensive yellow and yellowish-orange, have very high quantum luminosity factor and persistent fluorescent lifetime, therefore, can improve the shortcoming of prior art white light-emitting diodes and fluorescent material making method thereof really.
Though the present invention with preferred embodiment openly as above; right its is not in order to limit the present invention; any those of ordinary skills; without departing from the spirit and scope of the present invention; when the change that can do a little and retouching, so protection scope of the present invention should limit according to the appended claim book.
Claims (20)
1. fluorescent material that is used for white light-emitting diodes, it is by II in the periodic table of elements, and the oxide compound of III main group element is a matrix, does to start agent with the element of electronics d layer and f layer generation transition, and the matrix of this fluorescent material is made of the solid solution of the similar aluminate of barium and yttrium, and its chemical formula is Ba
αY
3 βAl
2 α+5 βO
4 α+12 β, wherein the span of α is α=0～4, preferred α=0.01～4; The value of β is β=0～4, and preferably β=0.01～4, and the crystallographic system of its lattice changes with the change of barium and yttrium proportionlity; When this matrix was excited by a short-wave radiation, the ion of this element can give off green orange-colored light, mixed back formation white light mutually with the short-wave radiation that an InGaN heterojunction semiconductor sends.
2. fluorescent material as claimed in claim 1, wherein in this compound add the f element and the d element is respectively: Ce, or Pr, or Eu, or Dy, or Tb, or Sm, or Mn, or Ti, or Fe, they have+2～+ 4 different degree of oxidations.
3. fluorescent material as claimed in claim 1, wherein this short-wave radiation has the wavelength of λ≤470nm; And this green orange-colored light has the wavelength of λ=530nm～610nm.
4. fluorescent material as claimed in claim 1, wherein when α=0.25 or 0.5, β=1 o'clock, the lattice of fluorescent material matrix is isometric system, compd B aAl
2O
4And Y
3Al
5O
12Respectively by Eu
+ 2And/or Ce
+ 3Start, dissolving mutually generates fluorescent substance.
5. fluorescent material as claimed in claim 1, wherein when α in the chemical formula=1 and β≤0.1, fluorescent material matrix chemical formula is BaY
0.3Al
2.5O
5.2, have the rhombic system structure; When it by Eu
+ 2And/or Sm
+ 2During startup, the narrow band radiation of peak value half-breadth Δ λ=60-70nm can take place, thereby guarantee that producing chromaticity coordinate after the radiation excitation of λ=460nm of being sent by the shortwave heterojunction is x=0.17～0.22, the bluish-green coloured light of y=0.45～0.55.
6. fluorescent material as claimed in claim 1, wherein α increases to 1 in chemical formula, and when β=1 remained unchanged, fluorescent material was by Ce
+ 3, and/or Ti
+ 3, and/or Fe
+ 3Start, send peak value half-breadth Δ λ=118～122nm, chromaticity coordinate is x=0.36～0.42, and the broadband band radiation of y=0.41～0.44 is excited the luminous colour temperature in back will reduce to T≤5000K by blue short-wave radiation.
7. fluorescent material as claimed in claim 1, wherein when α in the chemical formula＞1.5, gained compound solid solution has the rhombic system structure, adds Gd in it is formed
+ 3Replace the part Y in the negatively charged ion sublattice
+ 3, the fluorescent material radiation peak can move (moving to λ=570nm place from λ=558nm) to the long wave direction, and the chromaticity coordinate sum also increases to ∑ (x+y)＞0.80 thereupon simultaneously.
8. fluorescent material as claimed in claim 1, wherein when α/β 〉=2, it is bright light yellow that the gained compound is, and absorption peak reflects at 545～585nm wave band at 440～480nm wave band.
9. fluorescent material as claimed in claim 1 wherein ought be used Sr
+ 2With Ca
+ 2Replace the part Ba in the positively charged ion sublattice
+ 2The time, by Eu
+ 2, and/or Sm
+ 2, and/or Mn
+ 2Start the radiation that takes place and have the narrow band feature, peak value half-breadth Δ λ=100～110nm, luminous at λ=505～585nm wave band.
10. fluorescent material as claimed in claim 1, wherein when it during by the short pulse excitation of shortwave heterojunction luminous persistence length between t=120ns～40ns, increase in the scope of beta/alpha 〉=4 with the ratio of beta/alpha and to reduce.
11. fluorescent material as claimed in claim 1, wherein when 0.05≤α/β≤0.25, fluorescent material has the double frequency-band emitting characteristics.
12. fluorescent material as claimed in claim 1, wherein this matrix is synthesized and is that platy shaped particle form, planar diameter are 10～20 times of unit grain thickness.
13. synergistic light-transferring powder that is used for the nitride-based semiconductor heterojunction, it is to be made of polymeric matrix and fluorescent material, its architecture basics is that the polymerization degree is 100～500, molecular mass is greater than the Resins, epoxy or the silicone resin of 5000 standard carbosilane units, and fill 1%～50% fluorescent material therein, thereby form a layer thickness homogeneous polymer layer on the light-emitting area of heterojunction, this layer can change into the primary radiation of shortwave heterojunction the white light of colour temperature between 6000K～3200K.
14. white light emitting diode, it is made of an InGaN heterojunction semiconductor and a synergistic light-transferring powder, wherein this synergistic light-transferring powder system is made of polymeric matrix and fluorescent material, its architecture basics is that the polymerization degree is 100～500, molecular mass is greater than the Resins, epoxy or the silicone resin of 5000 standard carbosilane units, and fill 1%～50% fluorescent material therein, thereby on the light-emitting area of heterojunction, form a layer thickness homogeneous polymer layer, this layer can change into the primary radiation of shortwave heterojunction the white light of colour temperature between 6000K～3200K, and its luminescent chromaticity is Ra 〉=85.
15. the preparation method of a fluorescent material, it comprises the following steps:
Oxide raw material and carbonate are carried out solid state sintering;
Under hot environment, continue some hrs; And
In reducing environment, carry out the calcination stage with high temperature.
16. preparation method as claimed in claim 15, wherein this oxide raw material is Y
2O
3, Al
2O
3, Ce
2O
3, this carbonate is BaCO
3
17. preparation method as claimed in claim 15, wherein this hot environment is 1100 ℃ to 1500 ℃, and continues 2～10 hours.
18. preparation method as claimed in claim 15, wherein this reducing environment is H
2: N
2=1: 20.
19. the preparation method of a fluorescent material, it comprises the following steps:
With oxyhydroxide is raw material; And
They are joined thorough mixing in the fused hydrated barta in the proper ratio.
20. preparation method as claimed in claim 19, wherein this oxyhydroxide is Ba (OH)
28H
2O, Al (OH)
3, Y (OH)
3, CeO
2
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936497A (en) * | 2012-11-08 | 2013-02-20 | 广州有色金属研究院 | Main emission peak changeable and adjustable fluorescent material and preparation method thereof |
| CN103270138A (en) * | 2010-12-16 | 2013-08-28 | 宇部兴产株式会社 | Ceramic composite for photoconversion, method for producing same, and light-emitting device comprising same |
| CN103627399A (en) * | 2013-12-13 | 2014-03-12 | 中国科学院长春应用化学研究所 | Semiconductor/fluorescent powder heterostructure and preparation method thereof |
-
2006
- 2006-06-27 CN CNA2006100900890A patent/CN1876756A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103270138A (en) * | 2010-12-16 | 2013-08-28 | 宇部兴产株式会社 | Ceramic composite for photoconversion, method for producing same, and light-emitting device comprising same |
| CN103270138B (en) * | 2010-12-16 | 2015-04-29 | 宇部兴产株式会社 | Ceramic composite for photoconversion, method for producing same, and light-emitting device comprising same |
| CN102936497A (en) * | 2012-11-08 | 2013-02-20 | 广州有色金属研究院 | Main emission peak changeable and adjustable fluorescent material and preparation method thereof |
| CN103627399A (en) * | 2013-12-13 | 2014-03-12 | 中国科学院长春应用化学研究所 | Semiconductor/fluorescent powder heterostructure and preparation method thereof |
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