CN101967374A - Alkaline-earth metal silicon oxynitride luminescence material, preparation method and application thereof - Google Patents
Alkaline-earth metal silicon oxynitride luminescence material, preparation method and application thereof Download PDFInfo
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- CN101967374A CN101967374A CN2010102532724A CN201010253272A CN101967374A CN 101967374 A CN101967374 A CN 101967374A CN 2010102532724 A CN2010102532724 A CN 2010102532724A CN 201010253272 A CN201010253272 A CN 201010253272A CN 101967374 A CN101967374 A CN 101967374A
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Abstract
The invention discloses an alkaline-earth metal silicon oxynitride luminescence material, and a preparation method and application thereof. The chemical composition and active ion valence of the luminescence material are as follows: Ba(4-y-z)MyLnzSi8O(20-3xN2x) or Ba(4-y-3z)/2MyLnzSi8O(20-3xN2x), wherein M refers to alkaline-earth metals; the valence of Ln is one or greater than or equal to two of divalent or tervalent Eu, Yb, Sm and Mn ions; x refers to the applied amount of nitrogen, y refers to the applied amount of the alkaline-earth metals except Ba, z refers to the adulterating amount of activator ions, and the detailed content scopes thereof are as follows: 0<=x<1, 0<=y<4, and 0 < z < 0.8. The rare earth activated alkaline-earth metal silicon oxynitride luminescence material prepared in the invention is high in purity, chemical stability and thermal stability, and particularly suitable for wavelength conversion materials of a white LED, fluorescent powder for normal lamps and luminescence materials for various displays.
Description
Technical field
The present invention relates to alkaline-earth metal oxynitride luminescent material and its production and application.In particular, the present invention relates to be applicable to fluor, with Ba
4-yM
ySi
8O
20-3xN
2x(M=Mg, Ca, Sr) for matrix, be composition, structure and preparation thereof and the application of the silicon oxynitride luminescent material of main activator with rare earth ion.
Background technology
The oxynitride luminescent material is a kind of novel material for transformation of wave length of developing over past ten years, is specially adapted to the near ultraviolet and the blue-light semiconductor luminous (pcLED) of fluor conversion, is widely used in illumination of LED solid semiconductor and kinds of displays part.The multicomponent system that the matrix of oxynitride material is made up of alkaline-earth metal, silicon, aluminium, oxygen, nitrogen and one or more rare earth metal activator.Because Si-O/N and Al-O/N covalent linkage that the nitrogen electronegativity is strong in the lattice, existence is stronger are compared with oxide compound and sulfide sill, chemical stability height, Heat stability is good, the capability of resistance to radiation of oxynitride base phosphor are strong.In addition, because the rigidity of matrix is big, its luminescent spectrum also shows as less stokes (Stokes) red shift usually.At oxynitride lattice middle-weight rare earths active ions Eu
2+And Ce
3+The 5d electronic level have big chance to be moved to more low-yield (being the long wave spectral region), thereby can absorb UV-light, near-ultraviolet light (370-405nm) becomes green, yellow and red visible light until blue light (450nm) and with the energy transformation that absorbs.
The alkaline-earth metal silicon-oxygen nitride can obtain from two kinds of route of synthesis, is initial parent compound from nitride with from oxide compound promptly.Comparatively speaking, it is considerably less to go out to send the suitable known nitride that synthetic oxynitride can be utilized from pure nitride.And from oxide matrix, a large amount of alkaline earth metal silicate or the alkali earth metal aluminate compound can be utilized to prepare oxynitride material.Its advantage is: one, because these oxide compounds are formed and crystalline structure is known, help to carry out cutting from chemical ingredients, and the solid solubility that improves or improve nitrogen-atoms in the matrix lattice obtains needed oxynitride.Two, the oxynitride chemical stability that is obtained is good.Discovering in recent years, in metal oxynitride silicon system, Rare-Earth Ce
3+Activated Y-Si-O-N ultraviolet and near ultraviolet (~390nm) send blue light under exciting, its emmission spectrum peak value is positioned at longer wavelength scope 440-500nm (referring to document 1).Alkaline-earth metal silicon oxynitride fluor MSi
2O
2N
2: Eu
2+(M=Ca, Sr, matrix Ba) are laminate structure, change with its crystalline structure of variation of alkaline-earth metal.At near ultraviolet or blue-light excited following, CaSi
2O
2N
2: Eu
2+Launch gold-tinted, its emmission spectrum peak value is about 562nm; SrSi
2O
2N
2Transmitting green light, its emmission spectrum peak value is about 540nm; BaSi
2O
2N
2The emission blue green light, its emission wavelength is positioned at about 491-500nm.These three kinds of materials are specially adapted to pcLED wavelength Conversion luminescent material (referring to patent documentation 2-4).And Ce
3+-activated MSi
2O
2N
2: Eu
2+(M=Ca, Sr Ba) then are the fluorescent material (referring to document 5) of one group of blue light-emitting.Eu
2+Activated barium silicon oxynitride Ba
3Si
6O
12N
2, under the exciting of near ultraviolet and blue light, launch the higher green glow of efficient, its emission spectra peak is positioned at about 525nm, and the halfwidth of emmission spectrum is about 68nm (referring to patent documentation 6).Eu
2+Adulterated silicon oxynitride Ba
4Si
6O
16-3x/2N
x(x≤1) launches bluish-green light to green under the exciting of ultraviolet near-ultraviolet light, its excitation wavelength is 515-525nm (referring to a document 7).The barium silicon oxynitride BaSi of rich nitrogen
6N
8O: Eu
2+Excite down at ultraviolet wavelength 310nm, near 500nm, launch blue green light (referring to document 8).
Eu
2+Activated barium disilicate BaSi
2O
5Be green-emitting phosphor, its emmission spectrum is rendered as Eu under ultraviolet excitation
2+4f
65d → 4f
7The broadband emission spectral response curve of conversion, peak value is (referring to patent documentation 9, document 10) about 515nm.But at barium disilicate oxide compound BaSi
2O
5Or Ba
2Si
4O
10Thereby introduce nitrogen preparation rare earth ion in the lattice is the silicon oxynitride luminescent material discovery as yet up to now of luminescence center.
The present invention is with Ba
2Si
4O
10Be parent compound,, utilize nitrogen-atoms partly to replace Sauerstoffatom in the lattice silicate, form limit solid solution and prepare particularly Eu of rare earth by high temperature solid state reaction
2+And Ce
3+Adulterated Ba
4-yM
ySi
8O
20-3xN
2x: Ln silicon oxynitride based luminescent material is that nitrogen is introduced the source with the silicon nitride, and silicon nitride and alkaline earth metal compound, rare earth oxide are burnt till synthetic designed fluor by high temperature.Here, M is the combination of at least a or multiple element among alkali earth metal Mg, Ca, the Sr, and Ln is two valencys or trivalent metal ion activator.
Reference
1.J.W.H.van?Krevel,H.T.Hintzen,R.Metselaar?and?A.Meijerink,Long-wavelengthCe
3+-emission?in?Y-Si-O-N?materials,Journal?of?Alloys?and?Compounds,vol.268,272,1998.
2.WO?2004/030109?A1
3.WO?2004/036962?A1
4.WO?2004/039915?A1
5.Y.Q.Li,G.de?With?and?H.T.Hintzen,Luminescence?of?a?new?class?UV-blue-emitting?phosphorsMSi
2O
2-δN
2+2/3δ∶Ce
3+(M=Ca,Sr,Ba)”,J.Mater.Chem.,Vol.42,4492,2005.
6.WO?2007/088966A1
7.Y.Q.Li,Y.Fang,N.Hirosaki,R.-J.Xie,L.H.Liu,T.Takeda,X.Y.Li,Crystal?and?ElectronicStructures,Photoluminescence?Properties?of?Eu
2+-Doped?Novel?Oxynitride?Ba
4Si
6O1
6-3x/2N
x,Materials,Vol.3,1692-1708,2010.
8.R.-J,Xie,N.Hirosaki,Y.Q.Li,T.Takeda,Photoluminescence?of(Ba
1-xEu
x)Si
6N
8O(0.005≤x≤0.2)phosphors,Journal?of?Luminescence,Vol.130,266-269,2010.
9.US?2006/0055315?A1,2006.3.16
10.T.Nakanishi,S.Tanabe,Preparation?of?BaSi
2O
5∶Eu
2+?glass?ceramic?phosphors?and?luminescentproperties,J.Light?&?Vis.Env.,Vol.32,No.2,93,2008.
Summary of the invention
The luminescent material that the purpose of this invention is to provide usefulness such as being applicable near ultraviolet pcLED illumination, fluorescent lamp, indicating meter, based on the silicon oxynitride fluorophor powder of alkaline-earth metal silicon oxynitride with and its production and application.
The present invention is according to chain Ba
2Si
4O
10The crystalline structure characteristics of parent compound are carried out the part displacement to the oxygen of silicon-oxy tetrahedron in the lattice with nitrogen-atoms, utilize high-temperature solid phase reaction method to prepare alkaline-earth metal silicon oxynitride sosoloid and its composition, structure and the characteristics of luminescence have been carried out deep research.Found that, but the process chemical constitution optimizes and revises and by the higher alkaline earth silicon oxynitride substitutional solid solution of high temperature solid state reaction synthetic nitrogen solid solution content, its structure is that spacer is the rhombic system of Pcmn.Nitrogen-atoms partly replaces the bridging oxygen atom in the structure, and the metal activator ion occupies the position of the alkaline-earth metal of two valencys in lattice.
In order to realize the foregoing invention purpose, the invention provides following technical scheme:
1, alkaline-earth metal silicon oxynitride luminescent material chemical constitution and active ions valence state are:
The silica-based green-emitting phosphor of (1) two valence metal ion activated alkaline-earth metal oxynitriding: Ba
4-y-zM
yLn
zSi
8O
20-3xN
2x, wherein M represents alkaline-earth metal, contains Mg at least, Ca, a kind of among the Sr or more than or equal to two kinds.Ln
2+A kind of in the following at least group element comprises Eu, Sm, and Yb, Mn, Bi, Sb, Ce, Tb, Pr, Nd, Gd, Dy, Ho, Eu, Tm, Lu, particularly valency are the Eu of two valencys
2+, Yb
2+, Sm
2+, Mn
2+A kind of in the ion or more than or equal to two kinds.X represents the introducing amount of nitrogen, and y is the addition of other alkaline-earth metal (Mg, Ca, Sr etc.) except that Ba, and z represents the doping of activator ion, and its concrete content range is: 0≤x<1,0≤y<4,0<z<0.8.
(2) trivalent metal ion activated alkaline-earth metal silicon oxynitride base blue colour fluorescent body: Ba
4-y-3z/2M
yLn
zSi
8O
20-3xN
2x, wherein M represents alkaline-earth metal, contains Mg at least, Ca, a kind of among the Sr or more than or equal to two kinds.Ln
3+A kind of in the following at least group element comprises Eu, Sm, and Yb, Mn, Bi, Sb, Ce, Tb, Pr, Nd, Gd, Dy, Ho, Eu, Tm, Lu, particularly valency are tervalent Ce
3+, Tb
3+, Eu
3+, Pr
3+, Gd
3+A kind of in the ion or more than or equal to two kinds.X represents the introducing amount of nitrogen, and y is the addition of other alkaline-earth metal (Mg, Ca, Sr etc.) except that Ba, and z represents the doping of activator ion, and its concrete content range is respectively: 0≤x<1,0≤y<4,0<z<0.8.
2, the feature of alkaline-earth metal silicon oxynitride luminescent material is to adopt to contain M, Si, O, N element at least (wherein; M be a kind of among alkaline-earth metal Ba, Sr, Ca, the Mg or more than or equal to two kinds mixture); these elements and activator metal element burn till in the high temperature reduction protective atmosphere by a certain percentage, generate the fluor of (1) and (2) described alkaline-earth metal silicon oxynitride solid-solution powder form in above-mentioned 1 record.
3, the alkaline-earth metal silicon oxynitride of record has following compound as one or more the mixture in the oxide compound of starting raw material: Ba, Sr, Ca, Mg, carbonate, oxalate, oxyhydroxide, nitrate, muriate, the fluorochemical in above-mentioned 1,2.Si can be following compounds as starting raw material: SiO
2, Si, Si
2N
2O, SiCl
4, Si
3N
4, Si (NH)
2With one or more the mixture in the siliceous organic salt.N can be following nitride: Si
3N
4, Si
2N
2O, Si (NH)
2, one or more the mixture among the BN.Si wherein
3N
4Can be α-crystal formation, beta-crystal, unformed powder or α-and the raw material powder of β-mixing crystal formation.
4, the starting raw material of the metal ion activator Ln that above-mentioned 1-2 put down in writing can be from following listed raw material: the mixture of one or more Eu, Ce, Tb, Yb, Mn, Sm, Bi, Sb, Pr, Nd, Gd, Dy, Ho, Tm, Er oxide compound, nitrate, oxalate, the muriate.Wherein, be main activator raw material of the present invention with the above-mentioned compound of being mentioned that contains Eu, Ce, Tb and Mn, comprise Eu or Ce at least.Eu and Ce are 0.001%-20mol% with respect to the molar content scope of alkaline-earth metal, are preferably in 0.1%-12mol%.
5, the roughly preparation method of the alkaline-earth metal silicon oxynitride fluor of above-mentioned 1-4 record is: various starting raw materials are after suitable drying, press its stoichiometric ratio after weighing, after adopting ball mill manually to mix, grind through dry method or wet ball grinding or with mortar, with mix powder or be pressed into the sheet sample and place porcelain boat or crucible, 1000-1600 ℃ was burnt till tens of hours in the High Temperature Furnaces Heating Apparatus of reducing atmosphere, and preferred temperature is 1200-1450 ℃.Obtain alkaline-earth metal silicon oxynitride luminescent material by solid reaction process.In order further to improve the granular size and the pattern of luminous efficiency, control fluorescent powder, generally need carry out burning till for twice, grind, cross screen sizing and necessary aftertreatment.
The preparation method of the alkaline-earth metal silicon oxynitride fluorescent material of 6, putting down in writing among the above-mentioned 1-5, for improving the solid solubility of nitrogen-atoms in the body material lattice, the alkaline earth metal compound described in the above-mentioned 1-3 preferably is at least two or more and is used by a certain percentage.
7, the ratio of O and N can be higher than the O/N ratio of the final composition that designs in the last resulting material of being put down in writing among the above-mentioned 1-5 of employing of alkaline-earth metal oxonitride phosphor that passes through the high-temperature solid phase reaction method preparation.
8, adopting the alkaline-earth metal oxonitride phosphor particles of powder form of being put down in writing among the above-mentioned 1-5 of passing through the high-temperature solid phase reaction method preparation is sheet, minor axis is tabular or granular, and size is about the 1-30 micron, is preferably in the 3-10 micrometer range.
9, the alkaline-earth metal silicon oxynitride Preparation of Fluorescent Material method of being put down in writing among the above-mentioned 1-6, the reducing atmosphere that is adopted is the mixed-gas atmosphere of nitrogen-hydrogen, nitrogen-ammonia, nitrogen-carbon monoxide, also can refer to powdered graphite is placed formed local reduction atmosphere between the interior outer crucible.
10, the crystalline structure of the prepared silica-based fluorescent material of alkaline-earth metal oxynitriding of above-mentioned every record is a rhombic form, and its spacer is Pcmn.Nitrogen-atoms occupies the position of bridging oxygen in the parent compound at random.
11, the prepared silica-based fluorescent material of alkaline-earth metal oxynitriding under ultraviolet and near ultraviolet excitation, two valency europium Eu
2+Activated alkaline-earth metal silicon oxynitride is launched green glow, Eu
2+Ion is a luminescence center, and its emmission spectrum peak wavelength is positioned at 510-530nm; Trivalent cerium Ce
3+Activated alkaline-earth metal silicon oxynitride is launched blue light, Ce
3+Ion is a luminescence center, and its emmission spectrum peak wavelength is positioned at 410-450nm.The green of this invention and blue emitting material are applicable to the fluorescent material that White LED lighting fixtures, common fluorescent lamp and the various indicating meter of near ultraviolet LED combination are used.
Beneficial effect
Adopt the rare-earth activated alkaline-earth metal silicon oxynitride based luminescent material of the present invention's preparation, its purity height, chemistry temperature is qualitative and thermostability is high, and material for transformation of wave length, general lighting lamp phosphor and the various indicating meter that is particularly suitable as White LED is with luminescent material (CRT, EL, PDP, VFD, FED etc.).This work provides the fluor of the alkaline-earth metal silicon oxynitride with novelty, practicality, for the development of green, energy-conservation related industries such as illumination, display instrument and equipment provides better, more durable, more stable novel wavelength Conversion luminescent material, comprise various lamps for vehicle, the backlight that the liquid-crystal display that TV, mobile telephone, PDA and computer are used, LCD show, various traffic lights especially have broad application prospects in field of semiconductor illumination.
Description of drawings
Fig. 1, Eu activated Ba
4-yM
ySi
8O
20-3xN
2x(embodiment 1-4, x=0.5, y=1, Eu=1mol%, M=Mg, Ca, Sr) and the Ba of standard
2Si
4O
10The X-ray powder diffraction pattern.
Fig. 2, Ba
3MgSi
8O
18.5N: Eu
2+The Rietveld of powder x-ray diffraction (1mol%) measures and the simulation comparison diagram.
Fig. 3, Eu
2+Activated Ba
4-yM
ySi
8O
20-3xN
2x(M=Mg, Ca, Sr) silicon oxynitride crystalline structure synoptic diagram.
Fig. 4, Eu
2+Activated Ba
4-yM
ySi
8O
20-3xN
2xThe stereoscan photograph of silicon oxynitride fluor, (a) M=Mg, (b) M=Ca.
Fig. 5, Ba
3MgSi
8O
18.5N: Eu
2+Excitation spectrum (λ
Em=520nm) and emmission spectrum figure (λ
Exc=315nm) and the Eu change in concentration to spectrographic influence (Eu=1-10mol%, embodiment 1,7,8,9,10,11).
Fig. 6, nitrogen content (x) are to Ba
4-yM
ySi
8O
20-3xN
2x: Eu
2+(a) diffuse reflection spectrum, (b) influence of excitation spectrum and emmission spectrum (M=Mg, Eu=1mol%, x=0,0.2,0.4,0.5, z=1).
Fig. 7, alkaline-earth metal silicon oxynitride Ba
3MSi
8O
18.5N: Eu
2+(1mol%) temperature characteristics figure of fluor (excitation wavelength is 315nm) and alkaline-earth metal kind are to the influence ( embodiment 1,2,3,4) of thermostability.
Fig. 8, Ba
3CaSi
8O
18.5N: Eu
2+Excitation spectrum (λ
Em=520nm) and emmission spectrum figure (λ
Exc=315nm) and Eu
2+Change in concentration is to spectrographic influence (Eu
2+=1-10mol%, embodiment 2,12,13,14,15,16).
Fig. 9, Ba
3(Sr
0.6Mg
0.4) Si
8O
18.5N: Eu
2+Excitation spectrum (λ
Em=520nm) and emmission spectrum figure (λ
Exc=315nm) and Eu
2+Change in concentration is to spectrographic influence (Eu
2+=1-10mol%, embodiment 3,17,18,19,20,21).
Figure 10, Ba
3(Sr
0.6Ca
0.4) Si
8O
18.5N: Eu
2+Excitation spectrum (λ
Em=520nm) and emmission spectrum figure (λ
Exc=315nm) and Eu
2+Change in concentration is to spectrographic influence (Eu
2+=1-10mol%, embodiment 4,22,23,24,25,26).
Figure 11, Ba
4Si
8O
20-3xN
2x: Eu
2+(Eu
2+=3mol%, x=0.25,0.5) the powder x-ray diffraction figure of silicon oxynitride fluor.
Figure 12, Ba
4Si
8O
20-3xN
2x: Eu
2+(Eu=3mol%, excitation spectrum x=0.25) and emmission spectrum figure.
Figure 13, Ce
3+Adulterated Ba
4-yM
ySi
8O
20-3xN
2x(x=0.5, y=1, Ce
3+=1mol%) X-ray powder diffraction pattern (M=Mg, Ca, Sr, embodiment 35,36,37,38).
Figure 14, Ce
3+Activated Ba
4-yM
ySi
8O
20-3xN
2xThe stereoscan photograph of silicon oxynitride fluor, (a) M=Mg, (b) M=Ca.
Figure 15, Ba
3MgSi
8O
18.5N: Ce
3+Excitation spectrum (λ
Em=410nm) and emmission spectrum figure (λ
Exc=325nm) and Ce
3+Change in concentration is to spectrographic influence (Ce
3+=0.5-6mol%, embodiment 35,39,40,41,42).
Figure 16, Ba
3MSi
8O
18.5N: Ce
3+(1mol%) temperature characteristics figure of fluor (excitation wavelength is 330nm) and alkaline-earth metal kind are to the influence ( embodiment 35,36,37,38) of thermostability.
Figure 17, Ba
3CaSi
8O
18.5N: Ce
3+Excitation spectrum (λ
Em=420nm) and emmission spectrum figure (λ
Exc=330nm) and Ce
3+Change in concentration is to spectrographic influence (Ce
3+=0.5-6mol%, embodiment 36,43,44,45,46).
Figure 18, Ba
3(Sr
0.6Mg
0.4) Si
8O
18.5N: Ce
3+Excitation spectrum (λ
Em=420nm) and emmission spectrum figure (λ
Exc=330nm) and the Ce change in concentration to spectrographic influence (Ce=0.5-6mol%, embodiment 37,47,48,49,50).
Figure 19, Ba
3(Sr
0.6Ca
0.4) Si
8O
18.5N: Ce
3+Excitation spectrum (λ
Em=420nm) and emmission spectrum figure (λ
Exc=339nm) and Ce
3+Change in concentration is to spectrographic influence (Ce
3+=0.5-6mol%, embodiment 38,51,52,53,54).
Embodiment
Adopt purity greater than 99.9% BaCO
3, MgO, SiO
2, Si
3N
4And Eu
2O
3Be starting raw material, the raw material that above drying is crossed is by stoichiometric ratio Ba
3MgSi
8O
20-3xN
2x: Eu
2+(Eu=1mol%, x=0.5) after the weighing, uniform mixing or place with the silicon nitride that to be grinding element, organic liquid (ethanol, Virahol, acetone etc.) be the ball grinder ball milling of medium 4 hours in agate mortar.With resulting mixed powder or be pressed into flake shaped base substrate and put into the boron nitride porcelain boat, then porcelain boat is placed the aluminum oxide boiler tube of tube furnace then.Be warming up to 1200-1400 ℃ with about 300 ℃/hour speed, and under this temperature, be incubated 4-8 hour.After this, reduce to room temperature with 500 ℃/hour speed.Atmosphere in the sintering process is reducing atmosphere, imports in the tube furnace as protective atmosphere with the mixed gas form of nitrogen-hydrogen (5%) flow with 15ml/ minute.Product after burning till is ground grinding back sieving for standby in the alms bowl at agate.The alkaline-earth metal silicon oxinitride powder of preparation is analyzed its diffraction peak and Ba through the X-ray powder diffraction
2Si
4O
10PDF-83-1445 card be complementary (Fig. 1).Further Rietveld analysis revealed (table 1 and Fig. 2), the synthetic alkaline-earth metal silicon oxynitride fluorophor powder Ba of institute
3MgSi
8O
18.5N: Eu
2+(1mol%) do not have second and exist mutually, be pure single phase solid solution, its crystalline structure and Ba
2Si
4O
10Has identical structure.As example, table 1 provides typical Eu
2+The crystalline structure of activated alkaline-earth metal silicon oxynitride.Structural analysis shows, the nitrogen of introducing with the silicon nitride source can enter the alternative partial oxygen atom of lattice of barium disilicate and occupy the position of Sauerstoffatom in crystal at random, Si atom in the lattice is joined together to form silica nitrogen mixing tetrahedron chain-like structure, and Fig. 3 is the typical crystalline structure synoptic diagram of alkaline-earth metal silicon oxynitride.The concrete chemical constitution weight percent of its reaction raw materials is as shown in table 2.
Table 1, Ba
3MgSi
8O
18.5N: Eu
2+Crystalline structure data sheet (1mol%)
With the silicon oxynitride powder of scanning electron microscopic observation preparation, shown in Fig. 4 (a), powder particle perfect crystalline, form are the short cylinder structure, and grain size is about the 3-8 micron.
Measure synthetic Ba by fluorescence spectrophotometer
3MgSi
8O
18.5N: Eu
2+(1mol%) the silicon oxynitride fluor draws: excite down in UV-light and near-ultraviolet light (370-405nm), this silicon oxynitride luminescent material sends green light in the 400-700nm scope, and its emmission spectrum presents typical Eu
2+Ionic wideband spectrum fluorescent characteristic (4f
65d → 4f
7Transition), its spectrum peak is positioned at about 520nm, halfwidth (FWHM) is about 120nm (Fig. 5).Its specific absorption is 77%, and luminous quantum yield is about 49%, and the concrete characteristics of luminescence is detailed to be shown in Table 3.
Fig. 6 is that the variation of nitrogen content x is to diffuse reflection spectrum (a) with excite and the influence of emmission spectrum (b).This shows that nitrogen-atoms replaces the Sauerstoffatom in the part matrix lattice, make Eu
2+(Fig. 6 a), red shift (Fig. 6 b) also obviously takes place with the increase of x to the red shift significantly of the absorption edge of spectrographic absorption spectrum in its emmission spectrum simultaneously.Thereby prove that further nitrogen-atoms can enter lattice silicate and form silicon oxynitride part substitutional solid solution.
Fig. 7 is Ba
3MgSi
8O
18.5N: Eu
2+(1mol%) relation curve of the temperature of silicon oxynitride fluor and emmission spectrum relative intensity.By temperature profile as seen, this fluorescent material at high temperature has higher thermal stability.200 ℃ the time, its luminous intensity still maintains about 60% room temperature emissive porwer, is suitable for the requirement of near ultraviolet LED material for transformation of wave length under ultraviolet excitation.
Adopt purity greater than 99.9% BaCO
3, CaCO
3, SiO
2, Si
3N
4And Eu
2O
3Be starting raw material, the raw material that above drying is crossed is by stoichiometric ratio (table 2) Ba
3CaSi
8O
18.5N: Eu
2+(Eu=1mol% x=0.5) after the weighing, grinds uniform mixing in the alms bowl or places with the silicon nitride that to be grinding element, organic liquid (with embodiment 1) be the ball grinder ball milling of medium 4 hours at agate.With resulting mixed powder or be pressed into flake shaped base substrate and put into the boron nitride porcelain boat, then porcelain boat is placed the aluminum oxide boiler tube of tube furnace then.Be warming up to 1200-1400 ℃ with about 300 ℃/hour speed, and under this temperature, be incubated 4-8 hour.After this, reduce to room temperature with 500 ℃/hour speed.Atmosphere in the sintering process is reducing atmosphere, imports in the tube furnace as protective atmosphere with the mixed gas form of nitrogen-hydrogen (5%) flow with 15-20ml/ minute.Product after burning till is ground the back sieving for standby in agate mortar.The alkaline-earth metal silicon oxinitride powder of preparation is analyzed its diffraction peak and Ba through the X-ray powder diffraction
2Si
4O
10PDF-83-1445 card be complementary (Fig. 1).With example 1, Rietveld analysis revealed, the Eu of acquisition
2+Adulterated silicon oxynitride Ba
3CaSi
8O
18.5N: Eu
2+(1mol%) be even, pure single phase sosoloid, and and Ba
2Si
4O
10Structure is identical.
With the silicon oxynitride powder of scanning electron microscopic observation preparation, shown in Fig. 4 (b), powder particle perfect crystalline, form are approximate isometric texture, and grain size is about the 2-5 micron.
Excite down Ba in UV-light and near-ultraviolet light (370-405nm)
3CaSi
8O
18.5N: Eu
2+(1mol%) fluorescent material sends green light, emmission spectrum in the 400-700nm scope, present typical Eu
2+Ionic wideband spectrum fluorescent characteristic (4f
65d → 4f
7Transition), its spectrum peak is positioned at about 525nm, halfwidth (FWHM) is about 115nm, as shown in Figure 8.The specific absorption of this fluor is about 73%, and quantum yield is about 41%, and the concrete characteristics of luminescence is detailed to be shown in Table 3.
Ba
3CaSi
8O
18.5N: Eu
2+(1mol%) relation curve of the temperature of alkaline-earth metal silicon oxynitride fluor and emmission spectrum relative intensity as shown in Figure 7.Comparatively speaking, this fluor at high temperature has high thermal stability than the material of other alkaline earth metal doping.200 ℃ the time, its luminous intensity still maintains the room temperature emissive porwer more than 60% under ultraviolet excitation.
Embodiment 3
Adopt purity greater than 99.9% BaCO
3, SrCO
3, MgO, SiO
2, Si
3N
4And Eu
2O
3Be starting raw material, the raw material that above drying is crossed is by stoichiometric ratio Ba
3Sr
0.6Mg
0.4Si
8O
18.5N: Eu
2+(Eu
2+=1mol%, x=0.5) weigh after, uniform mixing or place with the silicon nitride that to be grinding element, organic liquid (referring to embodiment 1 and 2) be the ball grinder ball milling of medium 4 hours in agate mortar.With resulting mixed powder or be pressed into flake shaped base substrate and put into the boron nitride porcelain boat, porcelain boat is placed the aluminum oxide boiler tube of tube furnace then thereupon.Be warming up to 1200-1400 ℃ with about 300 ℃/hour speed, and under this temperature, be incubated 4-8 hour.After this, reduce to room temperature with 500 ℃/hour speed.Atmosphere in the sintering process is reducing atmosphere, imports in the tube furnace as protective atmosphere with the mixed gas form of nitrogen-hydrogen (5%) flow with 15-20ml/ minute.Product after burning till is ground grinding back sieving for standby in the alms bowl at agate.The alkaline-earth metal silicon oxinitride powder of preparation is analyzed its diffraction peak and Ba through the X-ray powder diffraction
2Si
4O
10PDF-83-1445 card be complementary (Fig. 1).With example 1, Rietveld analysis revealed, the adulterated silicon oxynitride Ba of the Eu of acquisition
3Sr
0.6Mg
0.4Si
8O
18.5N: Eu
2+(1mol%) be even, pure single phase sosoloid, and and Ba
2Si
4O
10Structure is identical.
Excite down Ba in UV-light and near-ultraviolet light (370-405nm)
3Sr
0.6Mg
0.4Si
8O
18.5N: Eu
2+(1mol%) fluorescent material sends green light, emmission spectrum in the 400-700nm scope, present typical Eu
2+Ionic wideband spectrum fluorescent characteristic (4f
65d → 4f
7Transition), its spectrum peak is positioned at about 520nm, halfwidth (FWHM) is about 110nm (Fig. 9).The specific absorption of fluor is 72%, and under near ultraviolet excitation, the quantum yield of this fluor is about 47%, and the concrete characteristics of luminescence is detailed to be shown in Table 3.
Ba
3Sr
0.6Mg
0.4Si
8O
18.5N: Eu
2+(1mol%) relation curve of the temperature of alkaline-earth metal silicon oxynitride fluor and emmission spectrum relative intensity as shown in Figure 7.Under ultraviolet excitation, in the time of 200 ℃, its intensity of emission spectra still maintains 42% room temperature emissive porwer level.
Adopt purity greater than 99.9% BaCO
3, SrCO
3, CaCO
3, SiO
2, Si
3N
4And Eu
2O
3Be starting raw material, the raw material that above drying is crossed is by stoichiometric ratio (table 2) Ba
3Sr
0.6Ca
0.4Si
8O
18.5N: Eu
2+(Eu
2+=1mol%, x=0.5) weigh after, uniform mixing or place with the silicon nitride that to be grinding element, organic liquid (referring to embodiment 1) be the ball grinder ball milling of medium 4 hours in agate mortar.With resulting mixed powder or be pressed into flake shaped base substrate and put into the boron nitride porcelain boat, porcelain boat is placed the aluminum oxide boiler tube of tube furnace then thereupon.Be warming up to 1200-1400 ℃ with about 300 ℃/hour speed, and under this temperature, be incubated 4-8 hour.After this, reduce to room temperature with 500 ℃/hour speed.Atmosphere in the sintering process is reducing atmosphere, imports in the tube furnace as protective atmosphere with the mixed gas form of nitrogen-hydrogen (5%) flow with 15-20ml/ minute.Product after burning till is ground grinding back sieving for standby in the alms bowl at agate.The alkaline-earth metal silicon oxinitride powder of preparation is analyzed its diffraction peak and Ba through the X-ray powder diffraction
2Si
4O
10PDF-83-1445 card be complementary (Fig. 1).With example 1, Rietveld analysis revealed, the adulterated silicon oxynitride Ba of the Eu of acquisition
3Sr
0.6Ca
0.4Si
8O
18.5N: Eu
2+(1mol%) be even, pure single phase sosoloid, and and Ba
2Si
4O
10Structure is identical.
Excite down Ba in UV-light and near-ultraviolet light (370-405nm)
3Sr
0.6Ca
0.4Si
8O
18.5N: Eu
2+(1mol%) fluorescent material sends green light, emmission spectrum in the 400-700nm scope, present typical Eu
2+Ionic wideband spectrum fluorescent characteristic (4f
65d → 4f
7Transition), its spectrum peak is positioned at about 525nm, halfwidth (FWHM) is about 115nm (Figure 10).Under near ultraviolet excitation, the specific absorption of this fluor is about 67%, and quantum yield is about 70%, and the concrete characteristics of luminescence is detailed to be shown in Table 3.
Ba
3Sr
0.6Ca
0.4Si
8O
18.5N: Eu
2+(1mol%) relation curve of the temperature of alkaline-earth metal silicon oxynitride fluor and emmission spectrum relative intensity as shown in Figure 7.200 ℃ the time, its intensity of emission spectra still maintains 48% room temperature emissive porwer level under ultraviolet excitation.
Embodiment 5-6
Adopt purity greater than 99.9% BaCO
3, SiO
2, Si
3N
4And Eu
2O
3Be starting raw material, the raw material that above drying is crossed is by stoichiometric ratio (table 2) Ba
4Si
8O
20-3xN
2x: Eu
2+(Eu
2+=3mol%, x=0.25,0.5) weigh after, uniform mixing or place with the silicon nitride that to be grinding element, organic liquid (referring to embodiment 1) be the ball grinder ball milling of medium 4 hours in agate mortar.With resulting mixed powder or be pressed into flake shaped base substrate and put into the boron nitride porcelain boat, porcelain boat is placed the aluminum oxide boiler tube of tube furnace then thereupon.Be warming up to 1200-1300 ℃ with about 300 ℃/hour speed, and under this temperature, be incubated 4-8 hour.After this, reduce to room temperature with 500 ℃/hour speed.Atmosphere in the sintering process is reducing atmosphere, imports in the tube furnace as protective atmosphere with the mixed gas form of nitrogen-hydrogen (5%) flow with 15-20ml/ minute.Product after burning till is ground the back sieving for standby in agate mortar.The alkaline-earth metal silicon oxinitride powder of preparation is found diffraction peak and the Ba that it is main through the analysis of X-ray powder diffraction
2Si
4O
10The PDF-83-1445 card be complementary (Figure 11), but also have similar Ba simultaneously
3Si
6O
12N
2The diffraction peak of oxynitride occur.This shows that institute's synthetic oxonitride phosphor is two-phase sosoloid at least, under the Ba ionic situation in not having the partly alternative matrix of Mg, Ca, Sr or Sr-Mg or Sr-Ca, the solid solubility of nitrogen in matrix is lower and be easier to generate the silicon oxynitride compound of above-mentioned second phase of mentioning, thereby nitrogen-atoms is difficult to enter Ba
2Si
4O
10Lattice forms single sosoloid.
Excite down Ba in UV-light and near-ultraviolet light (370-405nm)
4Si
8O
20-3xN
2x: Eu
2+(Eu=3mol%, x=0.25,0.5) fluorescent material sends green light, and emmission spectrum is wideband spectrum, and its spectrum peak is positioned at about 522nm, halfwidth (FWHM) is about 102nm (Figure 12), and other concrete characteristics of luminescence is detailed to be shown in Table 3.
Embodiment 7-11
Adopt raw material, preparation condition and the method identical, synthesize different activator Eu with embodiment 1
2+The alkaline earth silicon oxynitride fluor of content, the chemical constitution of their raw materials is shown in Table 2, and its corresponding excitation spectrum and emmission spectrum are as shown in Figure 5.With Eu
2+The increase of activated ion concentration, the luminous intensity of emmission spectrum increase the threshold concentration until y=0.08 gradually; Work as Eu
2+Concentration when surpassing y=0.08 (2mol%) because the quenching effect of concentration, luminous intensity reduces gradually.The Eu that it is detailed
2+Characteristics of luminescence parameter is shown in Table 3.
Embodiment 12-16
Adopt raw material, preparation condition and the method identical, synthesize different Eu with embodiment 2
2+The alkaline earth silicon oxynitride fluor of content, their composition is shown in Table 2, and its corresponding excitation spectrum and emmission spectrum are as shown in Figure 8.With Eu
2+The increase of activated ion concentration, the luminous intensity of emmission spectrum increase the threshold concentration until y=0.16 gradually; Work as Eu
2+Concentration when surpassing y=0.16 (4mol%) because the quenching effect of concentration, luminous intensity reduces gradually.In addition, with the raising of Eu concentration, the spectrum peak generation red shift of emmission spectrum, the Eu that it is detailed
2+Characteristics of luminescence parameter is shown in Table 3.
Embodiment 17-21
Adopt raw material, preparation condition and the method identical, synthesize different Eu with embodiment 3
2+The alkaline earth silicon oxynitride fluor of content, their composition is shown in Table 2, and its corresponding excitation spectrum and emmission spectrum are as shown in Figure 9.With Eu
2+The increase of activated ion concentration, the luminous intensity of emmission spectrum increase the (Eu until y=0.4 gradually
2+Mol%).In the listed concentration range of this Eu, no Eu concentration quenching takes place.In addition, with the raising of Eu concentration, the spectrum peak generation red shift of emmission spectrum, the Eu that it is detailed
2+Characteristics of luminescence parameter is shown in Table 3.
Embodiment 22-26
Adopt raw material, preparation condition and the method identical, prepare different Eu with embodiment 4
2+The alkaline earth silicon oxynitride fluor of content, their composition is shown in Table 2, and its corresponding excitation spectrum and emmission spectrum are as shown in figure 10.With Eu
2+The increase of activated ion concentration, the luminous intensity of emmission spectrum increase the threshold concentration until y=0.16 gradually; Work as Eu
2+Concentration when surpassing y=0.16 (4mol%) because the quenching effect of concentration, luminous intensity reduces gradually.In addition, with the raising of Eu concentration, the spectrum peak generation red shift of emmission spectrum, the Eu that it is detailed
2+Characteristics of luminescence parameter is shown in Table 3.
Embodiment 27-34
Adopt the raw material identical with embodiment 1,2,3,4 respectively, preparation condition and method prepare activator Eu
2+Four series of the silicate of the identical and nitrogen content x=0 of content and the silicon oxynitride luminescent material of x=0.6 (be M=Mg, Ca, Sr
0.6-Mg
0.4And Sr
0.6-Ca
0.4) Eu activated alkaline-earth metal silicon oxynitride fluor, the chemical constitution of their starting raw material is shown in Table 2 (specimen coding 27-34) successively, and their luminescent properties is detailed to be shown in Table 3.Compare with pure silicate phosphor, after nitrogen-atoms entered lattice silicate and forms silicon oxynitride, owing to have the cause of stronger covalent linkage and higher crystal field in the silicon oxynitride lattice, red shift in various degree all took place in their emmission spectrum.
Table 2, Ba
4-yM
ySi
8O
20-3xN
2x: Eu
z 2+(M=Sr, Ca, Mg) starting raw material chemical constitution (weight percent %)
Embodiment | x | y | z | BaCO 3 | SiO 2 | Si 3N 4 | MgO | CaCO 3 | SrCO 3 | Eu 2O 3 |
1 | 0.5 | 1 | 0.04 | 52.997 | 39.523 | 3.182 | 3.658 | 0 | 0 | 0.639 |
2 | 0.5 | 1 | 0.04 | 50.272 | 37.492 | 3.017 | 0 | 8.612 | 0 | 0.678 |
3 | 0.5 | 1 | 0.04 | 50.074 | 37.343 | 3.007 | 1.380 | 0 | 7.594 | 0.602 |
4 | 0.5 | 1 | 0.04 | 49.068 | 36.592 | 2.944 | 0 | 3.362 | 7.441 | 0.593 |
5 | 0.25 | 0 | 0.12 | 60.450 | 36.290 | 1.389 | 0 | 0 | 0 | 1.673 |
6 | 0.5 | 0 | 0.12 | 60.890 | 34.642 | 2.789 | 0 | 0 | 0 | 1.679 |
7 | 0.5 | 1 | 0.08 | 52.321 | 39.553 | 3.187 | 3.659 | 0 | 0 | 1.280 |
8 | 0.5 | 1 | 0.16 | 50.967 | 39.615 | 3.191 | 3.665 | 0 | 0 | 2.563 |
9 | 0.5 | 1 | 0.24 | 49.609 | 39.677 | 3.195 | 3.670 | 0 | 0 | 3.848 |
10 | 0.5 | 1 | 0.32 | 48.247 | 39.742 | 3.200 | 3.676 | 0 | 0 | 5.136 |
11 | 0.5 | 1 | 0.40 | 46.881 | 39.803 | 3.204 | 3.682 | 0 | 0 | 6.431 |
12 | 0.5 | 1 | 0.08 | 49.630 | 37.518 | 3.021 | 0 | 8.619 | 0 | 1.212 |
13 | 0.5 | 1 | 0.16 | 48.343 | 37.572 | 3.024 | 0 | 8.634 | 0 | 2.427 |
14 | 0.5 | 1 | 0.24 | 47.049 | 37.630 | 3.028 | 0 | 8.644 | 0 | 3.648 |
15 | 0.5 | 1 | 0.32 | 45.752 | 37.686 | 3.032 | 0 | 8.658 | 0 | 4.872 |
16 | 0.5 | 1 | 0.40 | 44.451 | 37.739 | 3.040 | 0 | 8.673 | 0 | 6.097 |
17 | 0.5 | 1 | 0.08 | 49.432 | 37.370 | 3.007 | 1.382 | 0 | 7.600 | 1.209 |
18 | 0.5 | 1 | 0.16 | 48.145 | 37.424 | 3.015 | 1.386 | 0 | 7.611 | 2.420 |
19 | 0.5 | 1 | 0.24 | 46.862 | 37.480 | 3.018 | 1.385 | 0 | 7.622 | 3.633 |
20 | 0.5 | 1 | 0.32 | 45.570 | 37.534 | 3.022 | 1.389 | 0 | 7.634 | 4.852 |
21 | 0.5 | 1 | 0.40 | 44.275 | 37.589 | 3.026 | 1.392 | 0 | 7.645 | 6.073 |
22 | 0.5 | 1 | 0.08 | 48.439 | 36.617 | 2.948 | 0 | 3.367 | 7.446 | 1.183 |
23 | 0.5 | 1 | 0.16 | 47.182 | 36.670 | 2.951 | 0 | 3.371 | 7.457 | 2.369 |
24 | 0.5 | 1 | 0.24 | 45.916 | 36.726 | 2.955 | 0 | 3.375 | 7.468 | 3.560 |
25 | 0.5 | 1 | 0.32 | 44.648 | 36.778 | 2.962 | 0 | 3.380 | 7.479 | 4.753 |
26 | 0.5 | 1 | 0.40 | 43.378 | 36.830 | 2.966 | 0 | 3.384 | 7.489 | 5.953 |
27 | 0 | 1 | 0.04 | 52.524 | 48.222 | 0 | 3.623 | 0 | 0 | 0.631 |
28 | 0.6 | 1 | 0.04 | 53.096 | 38.778 | 3.825 | 3.662 | 0 | 0 | 0.639 |
29 | 0 | 1 | 0.04 | 49.845 | 41.015 | 0 | 0 | 8.540 | 0 | 0.600 |
30 | 0.6 | 1 | 0.04 | 50.357 | 36.778 | 3.627 | 0 | 8.631 | 0 | 0.607 |
31 | 0 | 1 | 0.04 | 49.647 | 40.855 | 0 | 1.369 | 0 | 7.531 | 0.598 |
32 | 0.6 | 1 | 0.04 | 50.160 | 36.633 | 3.612 | 1.384 | 0 | 7.605 | 0.606 |
33 | 0 | 1 | 0.04 | 48.658 | 40.040 | 0 | 0 | 3.337 | 7.379 | 0.585 |
34 | 0.6 | 1 | 0.04 | 49.151 | 35.894 | 3.540 | 0 | 3.370 | 7.452 | 0.593 |
Table 3, Ba
4-yM
ySi
8O
20-3xN
2x: Eu
z 2+(M=Mg, Ca, luminescent spectrum characteristic Sr)
Adopt purity more than or equal to 99.9% BaCO
3, MgO, SiO
2, Si
3N
4And CeO
2Be raw material, above drying raw material is later pressed stoichiometric ratio (table 4) Ba
3MgSi
8O
18.5N: Ce
3+(Ce=1mol%, x=0.5, i.e. Ba
2.94MgCe
0.04Si
8O
18.5N) after the weighing, grinding uniform mixing in the alms bowl or place with the silicon nitride at agate is that organic solutions such as grinding element, acetone are the ball grinder ball milling 4 hours of medium.With resulting mixed powder or be pressed into flake shaped base substrate and put into the boron nitride porcelain boat, then porcelain boat is placed the aluminum oxide boiler tube of tube furnace then.Be warming up to 1100-1400 ℃ with about 300 ℃/hour speed, and under this temperature, be incubated 4-6 hour.After this, reduce to room temperature with 500 ℃/hour speed.Atmosphere in the sintering process is reducing atmosphere, imports in the tube furnace as protective atmosphere with the mixed gas form of nitrogen-hydrogen (5%) flow with 15-20ml/ minute.Product after burning till is ground the back sieving for standby in agate mortar.The Ce of preparation
3+Activated alkaline-earth metal silicon oxinitride powder is analyzed its diffraction peak and Ba through the X-ray powder diffraction
2Si
4O
10PDF-83-1445 card be complementary (Figure 13).The Ce that shows acquisition
3+Adulterated silicon oxynitride Ba
3CaSi
8O
18.5N: Ce
3+(1mol%) be and Ba
2Si
4O
10The single phase solid solution fluorophor powder that structure is identical.Different are Ce with embodiment 1
3+Ion occupies lattice Ba
2+Ion position is the non-equivalence displacement.
Ce with the scanning electron microscopic observation preparation
3+Activated silicon oxynitride powder, shown in Figure 14 (a), the powder particle crystallization is comparatively complete, form is similar granular, and grain size is about the 4-10 micron.
Excite down Ba in UV-light and near-ultraviolet light (370-405nm)
3MgSi
8O
18.5N: Ce
3+(1mol%) fluorescent material sends the UV-blue light, emmission spectrum in the 350-600nm scope, present typical Ce
3+Wideband spectrum fluorescent characteristic (5d → 4f transition), Ce
3+Spectrum peak be positioned at about 410nm, halfwidth (FWHM) is about 110nm, as shown in figure 15.The specific absorption of this blue emitting phophor is 63%, and quantum yield is about 34%, its Ce
3+Characteristics of luminescence parameter is detailed to be shown in Table 5.
Ba
3MgSi
8O
18.5N: Ce
3+The temperature of alkaline-earth metal silicon oxynitride fluor and the relation curve of emmission spectrum relative intensity are as shown in figure 16.This fluor is under ultraviolet excitation, and emissive porwer is non-linear successively decreases, and when the fluor temperature was 200 ℃, its luminous intensity was kept the room temperature emissive porwer more than 32%.
Adopt BaCO
3, CaCO
3, SiO
2, Si
3N
4And CeO
2Be raw material (purity 〉=99.9%), above drying raw material is later pressed stoichiometric ratio (table 4) Ba
3CaSi
8O
18.5N: Ce
3+(Ce=1mol%, x=0.5, i.e. Ba
2.94CaCe
0.04Si
8O
18.5N) after the weighing, grinding uniform mixing in the alms bowl or place with the silicon nitride at agate is that organic solutions such as grinding element, acetone are the ball grinder ball milling 4 hours of medium.With resulting mixed powder or be pressed into flake shaped base substrate and put into the boron nitride porcelain boat, then porcelain boat is placed the aluminum oxide boiler tube of tube furnace then.Be warming up to 1100-1400 ℃ with about 300 ℃/hour speed, and under this temperature, be incubated 4-6 hour.After this, reduce to room temperature with 500 ℃/hour speed.Atmosphere in the sintering process is reducing atmosphere, imports in the tube furnace as protective atmosphere with the mixed gas form of nitrogen-hydrogen (5%) flow with 15-20ml/ minute.Product after burning till is ground the back sieving for standby in agate mortar.Prepared silicon oxynitride fluorophor powder is analyzed its diffraction peak and Ba through the X-ray powder diffraction
2Si
4O
10PDF-83-1445 card be complementary (Figure 13).The Ce that shows acquisition
3+-adulterated silicon oxynitride Ba
3CaSi
8O
18.5N: Ce
3+(1mol%) be and Ba
2Si
4O
10The single phase solid solution fluorophor powder that structure is identical.
Ce with the scanning electron microscopic observation preparation
3+Activated silicon oxynitride powder Ba
3CaSi
8O
18.5N: Ce
3+(1mol%), shown in Figure 14 (b), powder particle perfect crystalline, form are for approximate granular, and grain size is about the 3-6 micron.
Excite down Ba in UV-light and near-ultraviolet light (370-405nm)
3CaSi
8O
18.5N: Ce
3+(1mol%) fluorescent material sends the UV-blue light, emmission spectrum in the 350-600nm scope, present typical Ce
3+Wideband spectrum fluorescent characteristic (5d → 4f transition), Ce
3+Spectrum peak be positioned at about 420nm, halfwidth (FWHM) is about 107nm, as shown in figure 17.The specific absorption of this UV-blue emitting phophor is 64%, and quantum yield is about 34%, and its characteristics of luminescence parameter is detailed to be shown in Table 5.
Ba
3CaSi
8O
18.5N: Ce
3+The temperature of alkaline-earth metal silicon oxynitride fluor and the relation curve of emmission spectrum relative intensity are as shown in figure 16.This fluor is under ultraviolet excitation, and the emissive porwer of Ce is non-linear successively decreases, and when temperature was 200 ℃, its luminous intensity maintained the room temperature emissive porwer more than 32%.
Embodiment 37
Adopt BaCO
3, SrCO
3, MgO, SiO
2, Si
3N
4And CeO
2Be raw material (purity 〉=99.9%), above drying raw material is later pressed stoichiometric ratio (table 4) Ba
3Sr
0.6Mg
0.4Si
8O
20-3xN
2x: Ce
3+(Ce=1mol%, x=0.5, i.e. Ba
2.94Sr
0.6Mg
0.4Ce
0.04Si
8O
18.5N) after the weighing, grinding uniform mixing in the alms bowl or place with the silicon nitride at agate is that organic solutions such as grinding element, acetone are the ball grinder ball milling 4 hours of medium.With resulting mixed powder or be pressed into flake shaped base substrate and put into the boron nitride porcelain boat, then porcelain boat is placed the aluminum oxide boiler tube of tube furnace then.Be warming up to 1100-1400 ℃ with about 300 ℃/hour speed, and under this temperature, be incubated 4-6 hour.After this, reduce to room temperature with 500 ℃/hour speed.Atmosphere in the sintering process is reducing atmosphere, imports in the tube furnace as protective atmosphere with the mixed gas form of nitrogen-hydrogen (5%) flow with 15-20ml/ minute.Product after burning till is ground the back sieving for standby in agate mortar.Prepared silicon oxynitride fluorophor powder is analyzed its diffraction peak and Ba through the X-ray powder diffraction
2Si
4O
10The PDF-83-1445 card be complementary (Figure 13), show the adulterated silicon oxynitride Ba of Ce-
3Sr
0.6Mg
0.4Si
8O
20-3xN
2x: Ce
3+(1mol%) be and Ba
2Si
4O
10The single phase solid solution fluorophor powder that structure is identical.
Excite down Ba in UV-light and near-ultraviolet light (370-405nm)
3Sr
0.6Mg
0.4Si
8O
20-3xN
2x: Ce
3+(1mol%) fluorescent material sends the UV-blue light, emmission spectrum in the 350-600nm scope, present typical Ce
3+Wideband spectrum fluorescent characteristic (5d → 4f transition), Ce
3+Spectrum peak be positioned at about 420nm, halfwidth (FWHM) is about 110nm, as shown in figure 18.The specific absorption of this UV-blue emitting phophor is 52%, and quantum yield is about 39%, and its characteristics of luminescence parameter is detailed to be shown in Table 5.
Ba
3Sr
0.6Mg
0.4Si
8O
20-3xN
2x: Ce
3+The temperature of alkaline-earth metal silicon oxynitride fluor and the relation curve of emmission spectrum relative intensity are as shown in figure 16.This fluor is non-linear with temperature rising emissive porwer and successively decreases under ultraviolet excitation, maintains room temperature luminous intensity more than 30% 200 ℃ of its luminous intensities.
Adopt BaCO
3, SrCO
3, CaCO
3, SiO
2, Si
3N
4And CeO
2Be raw material (purity 〉=99.9%), above drying raw material is later pressed stoichiometric ratio (table 4) Ba
3Sr
0.6Ca
0.4Si
8O
20-3xN
2x: Ce
3+(Ce=1mol%, x=0.5, i.e. Ba
2.94Sr
0.6Ca
0.4Ce
0.04Si
8O
18.5N) after the weighing, grinding uniform mixing in the alms bowl or place with the silicon nitride at agate is that organic solutions such as grinding element, acetone are the ball grinder ball milling 4 hours of medium.With resulting mixed powder or be pressed into flake shaped base substrate and put into the boron nitride porcelain boat, then porcelain boat is placed the aluminum oxide boiler tube of tube furnace then.Be warming up to 1100-1400 ℃ with about 300 ℃/hour speed, and under this temperature, be incubated 4-6 hour.After this, reduce to room temperature with 500 ℃/hour speed.Atmosphere in the sintering process is reducing atmosphere, imports in the tube furnace as protective atmosphere with the mixed gas form of nitrogen-hydrogen (5%) flow with 15-20ml/ minute.Product after burning till is ground the back sieving for standby in agate mortar.Prepared silicon oxynitride fluorophor powder is analyzed its diffraction peak and Ba through the X-ray powder diffraction
2Si
4O
10The PDF-83-1445 card be complementary (Figure 13), show the adulterated silicon oxynitride Ba of Ce-
3Sr
0.6Ca
0.4Si
8O
20-3xN
2x: Ce
3+(1mol%) be and Ba
2Si
4O
10The single phase solid solution fluorophor powder that structure is identical.
Excite down Ba in UV-light and near-ultraviolet light (370-405nm)
3Sr
0.6Ca
0.4Si
8O
20-3xN
2x: Ce
3+(1mol%) fluorescent material sends the UV-blue light, emmission spectrum in the 355-650nm scope, present typical Ce
3+Wideband spectrum fluorescent characteristic (5d → 4f transition), Ce
3+Spectrum peak be positioned at about 420nm, halfwidth (FWHM) is about 105nm, as shown in figure 19.The specific absorption of this UV-blue emitting phophor is 54%, and quantum yield is about 38%, and its characteristics of luminescence parameter is detailed to be shown in Table 5.
Ba
3Sr
0.6Ca
0.4Si
8O
20-3xN
2x: Ce
3+The temperature of alkaline-earth metal silicon oxynitride fluor and the relation curve of emmission spectrum relative intensity are as shown in figure 16.This fluor is non-linear with temperature rising emissive porwer and successively decreases under ultraviolet excitation, maintains room temperature luminous intensity more than 44% 200 ℃ of its luminous intensities.
Embodiment 39-54
Adopt raw material, preparation condition and the method identical respectively, prepare Ce with embodiment 35,36,37,38
3+Different four series of content (be M=Mg, Ca, Sr
0.6-Mg
0.4And Sr
0.6-Ca
0.4) alkaline-earth metal silicon oxynitride luminescent material, the chemical constitution of their raw materials is shown in Table 4, and its corresponding excitation spectrum and emmission spectrum figure are respectively in Figure 15,17,18,19.With Ce
3+The increase of activated ion concentration, the luminous intensity of emmission spectrum improves gradually, at the Ce that is adopted
3+In the concentration range, in above-mentioned four series, all do not observe the Ce that concentration quenching causes
3+The luminous intensity decay.In addition, with Ce
3+The raising of concentration, the spectrum peak of emmission spectrum is because Stokes displacement and Ce
3+Interionic energy absorbs or transmission ofenergy again, and produces relative and Eu
2+Bigger spectral red shift.The Ce that it is detailed
3+Characteristics of luminescence parameter is shown in Table 5.
Table 4, Ba
4-yM
ySi
8O
20-3xN
2x: Ce
z 3+(M=Sr, Ca, Mg) starting raw material chemical constitution (weight percent %)
Embodiment | x | y | z | BaCO 3 | SiO 2 | Si 3N 4 | MgO | CaCO 3 | SrCO 3 | CeO 2 |
35 | 0.5 | 1 | 0.04 | 52.840 | 39.673 | 3.193 | 3.669 | 0 | 0 | 0.626 |
36 | 0.5 | 1 | 0.04 | 50.108 | 37.623 | 3.030 | 0 | 8.644 | 0 | 0.595 |
37 | 0.5 | 1 | 0.04 | 49.911 | 37.475 | 3.017 | 1.385 | 0 | 7.619 | 0.593 |
38 | 0.5 | 1 | 0.04 | 48.905 | 36.716 | 2.958 | 0 | 3.376 | 7.464 | 0.580 |
39 | 0.5 | 1 | 0.02 | 53.258 | 39.583 | 3.185 | 3.661 | 0 | 0 | 0.313 |
40 | 0.5 | 1 | 0.08 | 51.992 | 39.853 | 3.207 | 3.689 | 0 | 0 | 1.259 |
41 | 0.5 | 1 | 0.16 | 50.286 | 40.217 | 3.237 | 3.719 | 0 | 0 | 2.540 |
42 | 0.5 | 1 | 0.24 | 48.543 | 40.586 | 3.266 | 3.756 | 0 | 0 | 3.849 |
43 | 0.5 | 1 | 0.02 | 50.512 | 37.543 | 3.023 | 0 | 8.625 | 0 | 0.297 |
44 | 0.5 | 1 | 0.08 | 49.293 | 37.784 | 3.043 | 0 | 8.683 | 0 | 1.196 |
45 | 0.5 | 1 | 0.16 | 47.651 | 38.112 | 3.070 | 0 | 8.758 | 0 | 2.408 |
46 | 0.5 | 1 | 0.24 | 45.979 | 38.446 | 3.094 | 0 | 8.835 | 0 | 3.646 |
47 | 0.5 | 1 | 0.02 | 50.314 | 37.395 | 3.010 | 1.384 | 0 | 7.603 | 0.294 |
48 | 0.5 | 1 | 0.08 | 49.102 | 37.634 | 3.031 | 1.392 | 0 | 7.653 | 1.188 |
49 | 0.5 | 1 | 0.16 | 47.460 | 37.959 | 3.058 | 1.405 | 0 | 7.717 | 2.401 |
50 | 0.5 | 1 | 0.24 | 45.792 | 38.289 | 3.082 | 1.419 | 0 | 7.787 | 3.632 |
51 | 0.5 | 1 | 0.02 | 49.298 | 36.641 | 2.951 | 0 | 3.369 | 7.450 | 0.290 |
52 | 0.5 | 1 | 0.08 | 48.106 | 36.873 | 2.967 | 0 | 3.390 | 7.498 | 1.167 |
53 | 0.5 | 1 | 0.16 | 46.494 | 37.184 | 2.993 | 0 | 3.418 | 7.560 | 2.350 |
54 | 0.5 | 1 | 0.24 | 44.848 | 37.501 | 3.020 | 0 | 3.446 | 7.627 | 3.558 |
55 | 0.6 | 1 | 0.04 | 52.936 | 38.922 | 3.840 | 3.677 | 0 | 0 | 0.626 |
56 | 0.6 | 1 | 0.04 | 50.198 | 36.908 | 3.641 | 0 | 8.659 | 0 | 0.595 |
57 | 0.6 | 1 | 0.04 | 49.996 | 36.762 | 3.626 | 1.389 | 0 | 7.634 | 0.593 |
58 | 0.6 | 1 | 0.04 | 48.987 | 36.020 | 3.554 | 0 | 3.380 | 7.480 | 0.580 |
Table 5, Ba
4-yM
ySi
8O
20-3xN
2x: Ce
z 3+(M=Sr, Ca, luminescent spectrum characteristic Mg)
Embodiment 55-58
Adopt raw material and the synthetic method identical respectively with embodiment 35,36,37,38, prepare the silicon oxynitride luminescent material of nitrogen content x=x=0.6 four series (be M=Mg, Ca, Sr
0.6-Mg
0.4And Sr
0.6-Ca
0.4) Ce
3+-activated alkaline-earth metal silicon oxynitride fluor, the chemical constitution of their starting raw material is shown in Table 4 (specimen coding 55-58) successively, and its luminescent properties is detailed to be shown in Table 5.As seen because Ce
3+Solid solubility is less, increases the amount of nitrogen in lattice silicate to Ce
3+The spectrographic influence is also less relatively.
More than the present invention is described in further detail based on some specific embodiments, but these embodiment are some limited in this invention examples, only are in order to illustrate main points of the present invention better, so the present invention is not subjected to the restriction of these embodiment.
Claims (12)
1. alkaline-earth metal silicon oxynitride luminescent material is characterized in that, the chemical constitution of alkaline-earth metal silicon oxynitride luminescent material and metal active ions valence state are:
The silica-based green-emitting phosphor of (1) two valency metal active ions activated alkaline-earth metal oxynitriding: Ba
4-y-zM
yLn
zSi
8O
20-3xN
2xWherein M represents alkaline-earth metal, contains Mg at least, Ca, a kind of among the Sr or more than or equal to two kinds; Ln
2+A kind of in the following at least group element comprises Eu, Sm, and Yb, Mn, Bi, Sb, Ce, Tb, Pr, Nd, Gd, Dy, Ho, Eu, Tm, Lu, particularly valency are the Eu of two valencys
2+, Yb
2+, Sm
2+, Mn
2+A kind of in the ion or more than or equal to two kinds; X represents the introducing amount of nitrogen, and y is the addition of other alkaline-earth metal except that Ba, and z represents the doping of metal active ions, and its concrete content range is: 0≤x<1,0≤y<4,0<z<0.8;
Perhaps
(2) trivalent metal active ions activated alkaline-earth metal silicon oxynitride base blue colour fluorescent body: Ba
4-y-3z/2M
yLn
zSi
8O
20-3xN
2xWherein M represents alkaline-earth metal, contains Mg at least, Ca, a kind of among the Sr or more than or equal to two kinds; Ln
3+A kind of in the following at least group element comprises Eu, Sm, and Yb, Mn, Bi, Sb, Ce, Tb, Pr, Nd, Gd, Dy, Ho, Eu, Tm, Lu, particularly valency are tervalent Ce
3+, Tb
3+, Eu
3+, Pr
3+, Gd
3+A kind of in the ion or more than or equal to two kinds; X represents the introducing amount of nitrogen, and y is the addition of other alkaline-earth metal except that Ba, and z represents the doping of metal activator ion, and its concrete content range is respectively: 0≤x<1,0≤y<4,0<z<0.8.
2. alkaline-earth metal silicon oxynitride luminescent material according to claim 1 is characterized in that, the particle form of described alkaline-earth metal silicon oxynitride luminescent material is a sheet, minor axis is tabular or granular, and size is about the 1-30 micron, is preferably in the 3-10 micrometer range.
3. alkaline-earth metal silicon oxynitride luminescent material according to claim 1 is characterized in that the crystalline structure of described alkaline-earth metal silicon oxynitride luminescent material is a rhombic form, and its spacer is Pcmn; Nitrogen-atoms occupies the position of bridging oxygen in the parent compound at random.
4. alkaline-earth metal silicon oxynitride luminescent material according to claim 1 is characterized in that, described alkaline-earth metal silicon oxynitride luminescent material under ultraviolet and near ultraviolet excitation, two valency europium Eu
2+Activated alkaline-earth metal silicon oxynitride is launched green glow, Eu
2+Ion is a luminescence center, and its emmission spectrum peak wavelength is positioned at 510-530nm; Trivalent cerium Ce
3+Activated alkaline-earth metal silicon oxynitride is launched blue light, Ce
3+Ion is a luminescence center, and its emmission spectrum peak wavelength is positioned at 410-450nm.
5. the method for preparing the described alkaline-earth metal silicon oxynitride of claim 1 luminescent material; it is characterized in that; starting raw material adopts and contains M, Si, O, N element at least; wherein; M is a kind of among alkaline-earth metal Ba, Sr, Ca, the Mg or more than or equal to two kinds mixture, these elements and metal activator ion burn till in the high temperature reduction protective atmosphere.
6. the preparation method of alkaline-earth metal silicon oxynitride luminescent material according to claim 5 is characterized in that starting raw material comprises:
Alkaline earth metal compound, that is, and one or both in the oxide compound of Ba, Sr, Ca, Mg, carbonate, oxalate, oxyhydroxide, nitrate, muriate, the fluorochemical or two or more mixtures;
SiO
2, Si, Si
2N
2O, SiCl
4, Si
3N
4, Si (NH)
2With one or both or the two or more mixtures in the siliceous organic salt;
Si
3N
4, Si
2N
2O, Si (NH)
2, one or more the mixture among the BN.
7. the preparation method of alkaline-earth metal silicon oxynitride luminescent material according to claim 6 is characterized in that, described Si
3N
4Be α-crystal formation, beta-crystal, unformed powder or α-and the raw material powder of β-mixing crystal formation.
8. the preparation method of alkaline-earth metal silicon oxynitride luminescent material according to claim 5, it is characterized in that the starting raw material of described metal active ions Ln is: the mixture of one or more in Eu, Ce, Tb, Yb, Mn, Sm, Bi, Sb, Pr, Nd, Gd, Dy, Ho, Tm, Er oxide compound, nitrate, oxalate, the muriate; Wherein, be main activator raw material of the present invention with the above-mentioned compound of being mentioned that contains Eu, Ce, Tb and Mn, comprise Eu or Ce at least; Eu and Ce are 0.001%-20mol% with respect to the molar content scope of alkaline-earth metal, are preferably in 0.1%-12mol%.
9. according to the preparation method of claim 5,6,7 or 8 described alkaline-earth metal silicon oxynitride luminescent materials, it is characterized in that, various starting raw materials after drying, press its stoichiometric ratio after weighing, after adopting ball mill manually to mix, grind through dry method or wet ball grinding or with mortar, with mix powder or be pressed into the sheet sample and place porcelain boat or crucible, 1000-1600 ℃ was burnt till tens of hours in the High Temperature Furnaces Heating Apparatus of reducing atmosphere, and preferred temperature is 1200-1450 ℃; Obtain alkaline-earth metal silicon oxynitride luminescent material by solid reaction process; In order further to improve the granular size and the pattern of luminous efficiency, control fluorescent powder, need carry out burning till for twice, grind, cross screen sizing and necessary aftertreatment.
10. the preparation method of alkaline-earth metal silicon oxynitride luminescent material according to claim 5, it is characterized in that, for improving the solid solubility of nitrogen-atoms in the body material lattice, described alkaline earth metal compound is to be at least two or more to be used by a certain percentage.
11. preparation method according to claim 5,6,7 or 8 described alkaline-earth metal silicon oxynitride luminescent materials; it is characterized in that; described reduction protection atmosphere is the mixed-gas atmosphere of nitrogen-hydrogen or nitrogen-ammonia or nitrogen-carbon monoxide, or powdered graphite is placed formed local reduction atmosphere between the interior outer crucible.
12. the application of alkaline-earth metal silicon oxynitride luminescent material is characterized in that, alkaline-earth metal silicon oxynitride luminescent material is applicable to the fluorescent material that White LED lighting fixtures, common fluorescent lamp and the various indicating meter of near ultraviolet LED combination are used.
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CN105932142A (en) * | 2016-06-02 | 2016-09-07 | 安徽众博新材料有限公司 | White LED (Light-Emitting Diode) nano-phosphor powder |
CN109593522A (en) * | 2018-12-04 | 2019-04-09 | 广东工业大学 | A kind of near ultraviolet excitated silicate blue-green fluorescent powder and its preparation method and application |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050230689A1 (en) * | 2004-04-20 | 2005-10-20 | Gelcore Llc | Ce3+ and Eu2+ doped phosphors for light generation |
WO2007007240A1 (en) * | 2005-07-14 | 2007-01-18 | Philips Intellectual Property & Standards Gmbh | Electroluminescent light source |
JP2009209192A (en) * | 2008-02-29 | 2009-09-17 | Nichia Corp | Phosphor and light-emitting device using the same |
-
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WO2007007240A1 (en) * | 2005-07-14 | 2007-01-18 | Philips Intellectual Property & Standards Gmbh | Electroluminescent light source |
JP2009209192A (en) * | 2008-02-29 | 2009-09-17 | Nichia Corp | Phosphor and light-emitting device using the same |
Cited By (2)
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---|---|---|---|---|
CN105932142A (en) * | 2016-06-02 | 2016-09-07 | 安徽众博新材料有限公司 | White LED (Light-Emitting Diode) nano-phosphor powder |
CN109593522A (en) * | 2018-12-04 | 2019-04-09 | 广东工业大学 | A kind of near ultraviolet excitated silicate blue-green fluorescent powder and its preparation method and application |
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