CN104583365B - Based on the red emitting phosphor of nitride - Google Patents

Based on the red emitting phosphor of nitride Download PDF

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CN104583365B
CN104583365B CN201380044345.0A CN201380044345A CN104583365B CN 104583365 B CN104583365 B CN 104583365B CN 201380044345 A CN201380044345 A CN 201380044345A CN 104583365 B CN104583365 B CN 104583365B
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red emitting
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CN104583365A (en
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陶德节
李依群
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Intematix Corp
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Abstract

The present invention relates to red emitting phosphor, it comprises by chemical formula M(xv)M′2Si5-xAlxN8: the composition based on nitride that RE represents, wherein: M is at least one unit price with chemical valence v, divalence or trivalent metal; M ' is at least one in Mg, Ca, Sr, Ba and Zn; And RE is at least one in Eu, Ce, Tb, Pr and Mn; Wherein x meets 0.1≤x≤0.4, and wherein said phosphor has general crystalline texture M '2Si5N8: RE, Al replaces the Si in described crystalline texture, and M is positioned in fact gap site. In addition, described phosphor is configured to make deviation CIE Δ x and the Δ y of the chromaticity coordinate producing for aging 1,000 hour under 85 DEG C and 85% humidity to be less than approximately 0.03. In addition, described phosphor absorbs UV and blue ray radiation, and launch photoluminescence peak wavelength between about 620nm to the light within the scope of 650nm.

Description

Based on the red emitting phosphor of nitride
Technical field
Embodiments of the invention relate to the red emitting phosphor composition based on nitride.
Background technology
Many red emitting phosphors are to be derived from silicon nitride (Si3N4). The structure of silicon nitride is included in the SiN of distortion a little4On four sidesThe Si layer of combination in body skeleton and N layer. SiN4Tetrahedron is that to engage to make each nitrogen be three by sharing nitrogen angleTetrahedron shares. For example,, referring to hampshire (S.Hampshire), " summary of silicon nitride ceramics-structure, processing and characteristic(Siliconnitrideceramics-reviewofstructure, processing, andproperties) ", material and manufacturing engineeringAchievement magazine (JournalofAchievementsinMaterialsandManufacturingEngineer ing), the 24th volume,The 1st phase, September (2007), 43-50 page. The composition of the red emitting phosphor based on silicon nitride be usually directed to by such asThe elements such as Al replace SiN4The Si of tetrahedron center; This is mainly used in improveing the optical characteristics of phosphor, for example transmittingIntensity and peak emission wavelength.
But the result that aluminium replaces is, due to Si4+By Al3+Replace, be therefore substituted compound and lose a positive electricityLotus. Conventionally substantially adopt and realize in two ways charge balance: in a scheme, Al3+Replace Si4+Follow O2-Replace N3-, so that the negative electrical charge of the positive charge of losing and loss antagonism balance. This makes tetrahedral network have Al3+OrSi4+As the cation at tetrahedron center, and O in structure2-Or N3-Anion is positioned at tetrahedral angle. Due to not yet accurateReally learn which kind of which kind of tetrahedron has and replace, therefore for describing the called after (Al, Si) of this situation3-(N,O)4. ClearlyGround, for realizing charge balance, replaces Si for each Al and all exists an O to replace N.
In addition, these replacement mechanisms for charge balance (O replaces N) can insert to use in conjunction with cationic gap.In other words, upgrading cation is inserted between the existing atom in lattice sites, insert " natural " hole, gap orIn passage. This mechanism does not need to change anion structure (in other words, O replaces N), but this and do not mean that OReplacing N can not occur simultaneously. Replacement mechanism for charge balance can insert and occur in conjunction with the cationic gap of modification agent.
The people such as will Bao Jing (K.Shioi) are at " Sr-α-SiAlON:Eu2+Synthetic, crystal structure and luminescence generated by light (Synthesis,crystalstructure,andphotoluminescenceofSr-α-SiAlON:Eu2+) ", the U.S. pottery (J.Am. of association journalCeramSoc), 93[2] discuss in 465-469 (2010) using upgrading cation containing in Sr α-SiAlON. Will is protectedThe people such as well provide the formula of total composition of this class phosphor: Mm/vSi12-m-nAlm+nOnN16-n:Eu2+, wherein M be such as Li,Mg, Ca, Y and rare earth (except La, Ce, Pr and Eu) etc. " upgrading cation ", and ν is the cationic chemical combination of MValency. As people institute teachings such as will Bao Jing, the crystal structure of α-SiAlON is to be derived from compound α-Si3N4. For from α-Si3N4Produce α-SiAlON, pass through Al3+Ion part replaces Si4+Ion, and in order to compensate because of Al3+Replace Si4+The electricity producingLotus imbalance, replaces some N and by M cation is trapped to (Si, Al)-(O, N) with O4Between in tetrahedral networkIn gap, add some positive charges (people such as will Bao Jing is referred to as " stabilization ").
Broad research has formula M in the industry2Si5N8The alkaline-earth metal of the europium doped of (wherein M is Ca, Sr or Ba)Silicon nitride phosphor, for example referring to model crith Wei Er in the (TechnicalUniversity of Technische Universiteit EindhovenEindhoven), the people such as the PhD paper in January, 2000, United States Patent (USP) 6,649,946 and He Pei, solid-state physics is with solidBody The Chemicals (J.Phys.Chem.Solids.) 2000,61:2001-2006. This phosphor family arrives at 600nmUnder the wavelength of 650nm, launch with high-quantum efficiency. Wherein, pure Sr2Si5N8There is the sub-efficiency of maximum amount and at about 620nmPeak wavelength under launch. Know in the industry, this ruddiness nitride phosphor is in the temperature within the scope of 60 DEG C to 120 DEG CUnder the LED operating condition of degree and the envionmental humidity in 40% to 90% scope, there is bad stability.
Multiple groups have been used based on containing oxygen M2Si5N8Material test, these materials also can contain other metal.For example, referring to United States Patent (USP) 7,671,529 and 6,956247 and the open application case 2010/0288972 of the U.S.,2008/0081011 and 2008/0001126. But known these contain oxygen material in high temperature and high relative humidity (RH) (exampleAs 85 DEG C and 85%RH) combination condition under represent bad stability.
It is believed that, the charge compensation form reported in the industry can not weaken the aging impact on phosphor of heat/humidity, seemsIt can not produce the useful result that improves peak emission wavelength and seldom or in fact do not change light emissive porwer yet.
Stable silicon phosphor that in the industry need to be based on nitride and based on M2Si5N8Stable phosphor, wherein: peak value is sent outEjected wave length is in the relative broad range of red and other color; And the physical characteristic of phosphor (for example temperature and humidity stability)Strengthen.
Summary of the invention
Embodiments of the invention provide the phosphor based on nitride, and it has based on M2Si5N8Chemical composition, whereinWith IIIB row element (especially Al) replacement Si, and cation is included in phosphor crystal structure in replacement mode in factFor charge balance. These phosphor materials can be configured to peak emission wavelength to expand to red more long wavelength, andThe physical characteristic that strengthens phosphor, especially significantly improves temperature and humidity stability.
At least one embodiment of the present invention relates to by formula M 'xM”2A5-yDyE8: the phosphorescence based on nitride that RE representsBody composition. Herein, M ' is at least one in 1+ cation, 2+ cation and 3+ cation, and M " be Mg,At least one in Ca, Sr, Ba and Zn. A is at least one in Si, C and Ge. Element D is in replacement modeReplace A component, wherein D is the group that selects the IIIB row element composition of free periodic table. In one embodiment, DFor at least one in B, Al and Ga. In order to carry out charge compensation to replacing A with D, by modification agent cation M 'Add in phosphor. M ' is Li1+、Na1+、K1+、Sc3+、Ca2+、Mg2+、Sr2+、Ba2+And Y3+In at leastOne, and in fact this modification agent cation is inserted in the gap of phosphor. E be 3-anion, 2-anion andAt least one in 1-anion, and can be O2-、N3-、F1-、Cl1-、Br1-And I1-In at least one. Rare earth-activatedAgent RE is at least one in Eu, Ce, Tb, Pr and Mn; And given y is 0.01≤y < 4, and x is multiplied byThe chemical valence of M ' equals y.
In this article, RE represents that phosphor activator and symbol ": RE " represent doped with rare earth, and it is normally with the side of replacementFormula doping, but also can be included on grain boundaries in the crystalline texture of phosphor material, particle surface and mix in site, gapAssorted. Conventionally, the crystalline texture of the 2-5-8 compound based on nitride can have the Pmn2 of being selected from as described herein1、The space group of Cc, its derivative or its mixture. In some instances, space group is Pmn21. In addition it should be noted that,In material science theory, the vacancy concentration of pure crystalline material can be existing lattice sites according to the thermal balance condition of crystalApproximately every 1,000,100 parts. Therefore, in fact the charge balance ion of less percentage can end at sky metal ion siteIn but not in site, gap, charge balance ion is first filled room and is recharged site, gap.
In alternate embodiment, the modification agent cation M ' residing in crystal gap is the freely group of following composition of choosing:Comprise Ca2+At interior alkaline earth and element Li1+、Y3+、Mn2+、Zn2+With one or more rare earth (RE), between each is placed inModification agent cation in gap all can be individually or to be used in combination. Condition is that the cationic valent summation of modification agent equalsBecause IIIB row element replaces the charge unbalance that A causes.
Because cationic stoichiometry subscript will be greater than 2, therefore can see immediately that checked phosphor has in fact addsBe added to the modification agent cation in phosphor of the present invention gap. Traditional M2Si5N8The subscript of red emitting phosphor equals 2.In the time that this numerical value is greater than 2, deducibility goes out excess cations and does not reside at and occupied in lattice sites; But by addThe modification agent cation that adds inserts in gap, hole or the passage in the crystalline texture that " natural " be present in host phosphor.These gaps can be and not occupy lattice sites.
The modification agent cation that is placed in fact gap by including according to the present invention comes Si4+Replace and carry out charge balanceProduce unexpected benefit, that is, peak emission wavelength is increased towards the red end of spectrum. According to some embodiment, this increaseBe equal to or greater than about 6nm. The afterclap occurring together with emission wavelength increase is to maintain in fact light emissive porwer. RootAccording to some embodiment, follow replace upgrading and the visible intensity of gap upgrading with respect to upgrading before weakening of intensity be less than10％。
The modification agent cation that is placed in fact gap by including according to the present invention comes Si4+Replace and carry out charge balanceProduce unexpected benefit, that is, the stability of phosphor under the aging condition of high temperature and high humility strengthens. The composition of phosphorBe configured to make under 85 DEG C and 85% humidity the deviation of photoluminescence intensity after aging 1,000 hour to be not more than approximately30%. The composition of phosphor is further configured to make under 85 DEG C and 85% humidity after aging 1,000 hour, eachGrid deviation CIE Δ x and the CIE Δ y of chromaticity coordinate are less than or equal to approximately 0.03.
In another embodiment of the present invention, modification agent cation in gap is to Si4+Replace the charge balance carrying out and follow oneDetermine the O of degree2-Replace N3-. In other words, in this embodiment, be placed in fact the modification agent cation in gapThe only imbalance of balancing charge partly of charge balance mechanism, and remainder is by O2-Replace N3-Complete. " not exclusively "The reason of charge balance may be, the cationic chemical valence of modification agent lower than the former chemical valence that should have, for example, makesUse Li+And Ca2+But not Ca2+And Y3+Time. Another is chosen as, the cationic selection of modification agent should make chemical valence higher (2+,3+ or even 5+ cation), and because of the less charge balance that makes of placed upgrading cation incomplete.
According to embodiments of the invention, phosphor is configured to grow up in the light of about 600nm at blue-light excited lower transmitted wave,Wherein blue light may be defined as wavelength and arrives the light within the scope of about 470nm between about 420nm. Phosphor of the present invention also can pass throughThe radiation of wavelength shorter (for example about 250nm is to about 420nm) excites, and is x ray or UV shape but work as exciting radiationWhen formula, provide independent blue light-emitting phosphor with the required white light contribution blue light components to white light source. Common blue light excitation sourceInGaNLED or the GaNLED of emission peak at about 460nm.
Embodiments of the invention also comprise white light illumination source, and it comprises InGaN light emitting diode (LED) and the basis of blue light-emittingThe described arbitrary red emitting phosphor of literary composition. It also can comprise Yellow light-emitting low temperature phosphor and/or green-emitting phosphors. A realityExecute in example, green-emitting phosphors has formula Ce:Lu3Al5O12. Two kinds of exemplary red emitting phosphors of the embodiment of the present inventionFor Eu0.05Ca0.1Sr1.95Si4.8Al0.2N8And Eu0.05Ca0.1Sr1.95Si4.8B0.2N8。
At least one embodiment of the present invention is based on M2Si5N8The upgrading form of (so-called " 258 " compound), wherein MFor alkaline earth. The upgrading of 258 compounds is comprised with periodic table IIIB row element B, Al, Ga and/or In, Al especiallyReplace Si, wherein charge compensation can be by inserting phosphor body crystal knot by substantive so-called modification agent cation gapIn structure, complete. Modification agent cation has multiple chemical valence, and comprises Li+、Ca2+And Y3+. Excellent to 258 upgradingsPoint comprises towards the dark red end of spectrum to be increased peak emission wavelength and strengthens the stability under high temperature and high humidity.
Phosphor can comprise by chemical formula M(x/v)M′2A5-yDyN8-zEp: the composition based on nitride that RE represents, wherein:M is at least one unit price with chemical valence v, divalence or trivalent metal; M ' is in Mg, Ca, Sr, Ba and ZnAt least one; A is at least one in Si, C and Ge; D is at least one in B, Al and Ga; E be toFew a kind of pentavalent, sexavalence or septivalency with chemical valence w is nonmetal; And RE is in Eu, Ce, Tb, Pr and MnAt least one; Wherein x=y-3z+p (8-w), wherein y meets 0.1≤y < 1.1, and wherein phosphor hasM′2A5N8: the general crystalline texture of RE, D replaces the A in described general crystalline texture, and E replaces described general crystallization knotN in structure, and M is positioned in fact the gap site of described general crystalline texture. In addition, red emitting phosphor canThe freely group of following composition: Eu of choosing0.05Ca0.1Sr1.95B0.2Si4.8N8；Eu0.05Ca0.1Sr1.95Al0.2Si4.8N8；Eu0.05Ca0.1Sr1.95Ga0.2Si4.8N8；Eu0.05Sr1.95Al0.2Si4.8N8；Eu0.05Sr1.95B0.2Si4.8N7.93； Eu0.05Sr1.95Al0.2Si4.8N7.93；Eu0.05Sr1.95Ga0.2Si4.8N7.93; Be added with Ca3N2Eu0.05Sr1.95Si5N8; AddBe added with the Eu of BN0.05Sr1.95Si5N8; Be added with the Eu of AlN0.05Sr1.95Si5N8; Be added with GaN'sEu0.05Sr1.95Si5N8。
Red emitting phosphor can comprise by chemical formula M '2Si5-yDyN8-z: the composition based on nitride that RE represents, wherein M 'For at least one in Mg, Ca, Sr, Ba and Zn; D is at least one in B, Al and Ga; And RE isAt least one in Eu, Ce, Tb, Pr and Mn; Wherein y=3z, phosphor has M '2Si5N8: the general knot of RECrystal structure, and Al replaces the Si in described general crystalline texture. In addition, red emitting phosphor can be configured, wherein M 'For Sr, D is Si, and RE is Eu. Red emitting phosphor can be configured, wherein said red emitting phosphor by Sr,Si, Al, N and Eu composition. Red emitting phosphor can be configured, and wherein y meets 0.1≤y < 0.4. Red emitting phosphorCan be configured, wherein z meets 0.05≤z < 0.09. Red emitting phosphor can be configured, wherein phosphor absorbing wavelength betweenAbout 200nm is greater than the light of 623nm to the radiation within the scope of about 470nm and utilizing emitted light photoluminescence peak emission wavelength.Phosphor can be configured, and wherein phosphor is the freely group of following composition: Eu of choosing0.05Sr1.95B0.2Si4.8N7.93；Eu0.05Sr1.95Al0.2Si4.8N7.93; And Eu0.05Sr1.95Ga0.2Si4.8N7.93。
The red emitting phosphor with the composition based on nitride can comprise: element M, wherein M be Li, Na, K,At least one in Sc, Ca, Mg, Sr, Ba and Y; Element M ', wherein M ' is Mg, Ca, Sr, Ba and ZnIn at least one; Silicon; Aluminium; Nitrogen; And elements RE, wherein RE be in Eu, Ce, Tb, Pr and Mn at leastOne; Wherein said red emitting phosphor has M '2Si5N8: the general crystalline texture of RE and M and Al are included,And wherein said red emitting phosphor is configured to make under approximately 85 DEG C and approximately 85% relative humidity aging 1,000 hourAfter, the changes in coordinates CIE Δ x of each chromaticity coordinate and CIE Δ y are less than or equal to approximately 0.03.
Red emitting phosphor can comprise by chemical formula M(x/v)M′2Si5-xAlxN8: the composition based on nitride that RE represents, itsIn: M is at least one unit price with chemical valence v, divalence or trivalent metal; M ' be Mg, Ca, Sr, Ba andAt least one in Zn; And RE is at least one in Eu, Ce, Tb, Pr and Mn; Wherein x meets 0.1≤x < 0.4,And wherein said red emitting phosphor has M '2Si5N8: the general crystalline texture of RE, Al replaces described general crystalline textureInterior Si, and M is positioned in fact the gap site of described general crystalline texture.
Brief description of the drawings
After checking by reference to the accompanying drawings the following description of specific embodiment of the present invention, those one of ordinary skill in the art will understandThese and other aspect of the present invention and feature, wherein:
Fig. 1 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 1 to 4;
Fig. 2 shows according to some embodiments of the present invention, the x x ray diffration pattern x of the phosphor of sample 1 to 4;
Fig. 3 shows according to some embodiments of the present invention, compd E u0.05Ca0.1Sr1.95Si4.8Al0.2N8Swashing of (sample 2)Luminous spectrum, described spectrum illustrates phosphor can be had to the radiation between blue region by the UV between electromagnetic spectrumEffect excites;
Fig. 4 shows according to some embodiments of the present invention, compd E u0.05Ca0.1Sr1.95Si4.8B0.2N8Swashing of (sample 3)Luminous spectrum, described spectrum illustrates phosphor can be had to the radiation between blue region by the UV between electromagnetic spectrumEffect excites;
Fig. 5 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 5-8;
Fig. 6 shows according to some embodiments of the present invention, the x x ray diffration pattern x of the phosphor of sample 5-8;
Fig. 7 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 9-12;
Fig. 8 shows according to some embodiments of the present invention, the x x ray diffration pattern x of the phosphor of sample 9 to 12;
Fig. 9 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 13 to 16;
Figure 10 shows according to some embodiments of the present invention, the x x ray diffration pattern x of the phosphor of sample 13 to 16;
Figure 11 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 17 to 21;
Figure 12 shows according to some embodiments of the present invention, the x x ray diffration pattern x of the phosphor of sample 17 to 21;
Figure 13 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 22 to 27;
Figure 14 shows according to some embodiments of the present invention, the x x ray diffration pattern x of the phosphor of sample 22 to 27;
Figure 15 shows according to some embodiments of the present invention, the emission spectrum of white light LEDs (3000K), described white light LEDs(3000K) comprise blue light InGaNLED, there is formula Eu0.05Ca0.1Sr1.95Si4.8Al0.2N8Red phosphor (sample 2)With there is formula Ce:Lu3Al5O12Green glow phosphor;
Figure 16 shows according to some embodiments of the present invention, the emission spectrum of white light LEDs (3000K), described white light LEDs(3000K) comprise blue light InGaNLED, there is formula Eu0.05Ca0.1Sr1.95Si4.8B0.2N8Red phosphor (sample 3) andThere is formula Ce:Lu3Al5O12Green glow phosphor;
Figure 17 A-17C shows according to some embodiments of the present invention, and the phosphor of sample 1 to 3 and 6 is at 85 DEG C and 85%The result of the reliability testing under relative humidity condition, wherein Figure 17 A be photoluminescence intensity (brightness) over time,Figure 17 B be CIEx chromaticity coordinate over time, and Figure 17 C be CIEy chromaticity coordinate over time;
Figure 18 A-18C shows according to some embodiments of the present invention, without coating with through Al2O3/SiO2The sample of coatingThe reliability testing of the phosphor of 33 (they have the composition identical with sample 2) under 85 DEG C and 85% relative humidity conditionAs a result, wherein Figure 18 A be photoluminescence intensity (brightness) over time, Figure 18 B be CIEx chromaticity coordinate at any timeBetween variation, and Figure 18 C be CIEy chromaticity coordinate over time;
Figure 19 shows the gold-tinted YAG phosphor of prior art doped Ce, (650nm) ruddiness of prior art doping EuPhosphor CaAlSiN3Red phosphor Ca with the 630nm doping Eu of the embodiment of the present invention0.1Sr2Si4.8Al0.2N8'sEmission spectrum;
Figure 20 shows according to some embodiments of the present invention, the emission spectrum of the phosphor of sample 28 to 32; And
Figure 21 shows according to some embodiments of the present invention, the x x ray diffration pattern x of the phosphor of sample 28 to 32;
Figure 22 shows the light-emitting device of some embodiments of the present invention; And
Figure 23 A and Figure 23 B show the solid luminous device of some embodiments of the present invention.
Detailed description of the invention
Now, with reference to graphic detailed description embodiments of the invention, described embodiment comes as illustrative example of the present inventionThose one of ordinary skill in the art provide, so that can put into practice the present invention. It should be noted that lower texts and pictures and example notIntend scope of the present invention to be limited to single embodiment, and describe or illustrated wanting by exchange is some or all ofElement can have other embodiment. In addition, if some key element of the present invention can partially or even wholly be come real by known tip assembliesTrample, only describe in these known tip assemblies understanding those parts essential to the invention, and will omit these known groupThe detailed description of the other parts of part, with blur prevention the present invention. In this manual, the embodiment of demonstration single component is notShould be considered as restricted; But, unless clearly state in addition herein, the present invention intends to contain to comprise multiple same componentsOther embodiment, and vice versa. In addition, unless clearly explaination, applicant does not intend description or powerArbitrary term in profit claim is classified as unusual or particular meaning. In addition, the present invention is contained herein and is carried in explanation modeCurrent and the in the future known equivalent of the known tip assemblies arriving.
Some embodiments of the present invention relate to by formula M 'xM”2A5-yDyE8: the phosphor group based on nitride that RE representsBecome. Herein, M ' is at least one in 1+ cation, 2+ cation and 3+ cation, and M " be Mg, Ca,At least one in Sr, Ba and Zn, it is indivedual or to be used in combination. A is C, Si indivedual or to be used in combinationWith at least one in Ge. Element D replaces A component in replacement mode, and wherein D selects of the free periodic table of elementsThe group of IIIB row element composition. The mark of the each row of periodic table in the present invention is those book " solids mark FoxOptical characteristics (OpticalPropertiesofSolids) " (Oxford University Press (OxfordUniversityPress), New York,2001) user of institute in inside front cover, it follows old IUPAC (IUPAC(InternationalUnionofPureandAppliedChemistry)) system. Referring toHttp:// en.wikipedia.org/wiki/Group_ (periodic_table), on January 15th, 2013 up-to-date browsing. At oneIn embodiment, D is indivedual or with at least one in B, the Al and the Ga that are used in combination.
Modification agent cation M ' is added in phosphor and carries out charge compensation so that D is replaced to A. In particular, M 'For Li indivedual or to be used in combination1+、Na1+、K1+、Sc3+、Ca2+And Y3+In at least one. M ' is formula M2Si5N8In the extra cation that uses except the divalent metal M of stoichiometry " 2 ", and therefore claim this modification agent cationInsert in fact in phosphor gap. Will be below further describing in nomenclature part about the character in this site.
E in the general formula of phosphor of the present invention is at least one in 3-anion, 2-anion and 1-anion. Specific, E can be O indivedual or to be used in combination2-、N3-、F1-、Cl1-、Br-And I-In at least one. Rare earth REFor at least one in Eu, Ce, Tb, Pr and Mn; And given y is 0.01≤y≤1.0. The value of parameter y can be sameTime be defined as x value be multiplied by the chemical valence of M '; This is the condition that realizes charge balance.
As discussed above, M ' cation is " modification agent " cation, its be for representing to introduce in fact in gap but notIntroduce to realize the charge balance of crystal structure and/or the cationic buzzword of stabilization by replacement mechanism. GapSite is that (accumulation or stacking) is present in cavity, hole or passage in lattice according to the arrangement mode of main body constituting atom.The atoms of dopant that occupies crystal gap to be separated with these atomic regions of introducing in replacement mode; At described rear a kind of machineIn system, atoms of dopant replaces the main body atom residing in lattice sites. Described two kinds of mechanism realize electricity in phosphorThe difference of the mode of lotus balance will be showed by the stoichiometric equation of main body.
In following disclosure, will discuss known (Sr1-xCax)2Si5N8:Eu2+Composition, then to the embodiment of the present inventionThe character in site, gap is carried out certain brief comment. Subsequently, the present invention will present based on of the present inventionM’xM”2A5-yDyE8: the phosphor of RE embodiment, provides its advantage and characteristic and these phosphors and prior artDifference. To provide particular instance, and comprise and wherein replace Si4+IIIB row element be Al3+And wherein upgrading sun fromSon is Ca2+Phosphor. Finally, discussion is used to form to the nitride phosphor that glows of the present invention of white light LEDs,And the demonstration heat of phosphor of the present invention and the accelerated ageing result of chemical stability.
Known (Sr 1-x Ca x ) 2 Si 5 N 8 :Eu 2+ The discussion of composition
The people such as Piao have been " (Sr at title1-xCax)2Si5N8:Eu2+The preparation of solid solution and its characteristics of luminescence (Preparationof(Sr1-xCax)2Si5N8:Eu2+Solidsolutionsandtheirluminescenceproperties) paper ", electrochemistry associationCan magazine (J.oftheElectrochem.Soc.) 153 (12) H232-H235 (2006) (" preparation paper (PreparationPaper) "), discuss based on (Sr1-xCax)2Si5N8:Eu2+Composition. As the people such as Piao institute's teaching in preparation paper, " ... Ca2+At (Sr1-xCax)2Si5N8:Eu2+In solution be limited to the composition of x=0.5. At (Sr1-xCax)2Si5N8:Eu2+In consist of x=0.6Time there is the first [Ca2Si5N8] phase. Two-phase coexists in the scope of 0.5 < x < 0.75, oblique square structure wherein occurs to monocline knotThe transformation of structure ". The people such as Piao illustrate Ca2+The position of modification agent cation in ruddiness nitride phosphor: " occupy Sr2+/Ca2+The doping Eu of the position of ion2+Ion is arranged in by Si6N6The passage that ring forms along [100] and [010] direction of two-phase respectivelyIn ". When at [Sr2Si5N8] mutually in by Ca2+When content is increased to x=0.5, form SrCaSi5N8, " crystal grain crystallization is better,And [crystal grain] size increases ". This will strengthen optical characteristics. In the time that x is increased to 0.6 (60 atom %), " SEM image refers toShow the phase that exists two to there is different shape ". Referring to Piao Dengren, preparation paper, H233 page.
The people such as Piao explain to a certain extent between the modification agent cation in ruddiness nitride phosphor of the present invention in paperThe character in gap site. At M2Si5N8In (wherein M=Sr and Ca), each structure cell has two crystallization M sites; This isThese compounds have the reason of two emission bands. But, at (Sr1-xCax)2Si5N8:Eu2+In series, only see one wideBand transmitting. This shows that two sites have closely similar crystalline environment, or is rich in N3-Network in Eu2+Ion pairTwo sites have different coordinations (each M site around and with the N of its combination3-The number of anion) the fact not specialInresponsive. Referring to Piao Dengren, preparation paper, H234 page.
Piao waits people's teaching, when adding Ca2+Replace [Sr2Si5N8] when Sr in mutually, transmitting is displaced to more long wavelength, straightTo (Sr1-xCax)2Si5N8:Eu2+The point of x=0.5 in (thering are 2 atom %Eu) series. Eu2+Emission band is from Sr2Si5N8:Eu2+617nm red shift to SrCaSi5N8:Eu2+632nm, wherein Eu concentration is 2 atom % under two kinds of situations.Under two kinds of situations, the Ca that ligancy is 102+And Sr2+The ionic radius of ion is respectivelyWithCauseThis, at Ca2+Ion replaces [Sr2Si5N8] Sr in mutually2+, in x x ray diffraction (XRD) experiment, can see when in the siteM-N bond distance and lattice parameter reduce. Ca-N key makes Eu with respect to the shorter average distance of Sr-N2+Ion experience is strongerCrystal field strength, described crystal field strength and chemical bond distance's 5 powers are inversely proportional to. Referring to Piao Dengren, preparation paper, theH234 page.
According to people such as Piaos, emissive porwer is with (Sr1-xCax)2Si5N8:Eu2+Ca in phosphor2+Content increases and reduces. This byThe people such as Piao make an explanation at H235 page; Cannot be specified in this although details is too complicated, intensity reduces inevitable and Eu2+The coordination mode of ion is relevant with the energy level diagram relevant with excitation state transition. Referring to Piao Dengren, preparation paper, H235Page.
The character in the site, gap of the embodiment of the present invention
Although do not wish to be limited to the arbitrary concrete reason about the character in the site, upgrading cation gap of the embodiment of the present inventionOpinion, but discuss well-known theory is helpful maybe can be by its derivation. Describe owing to using in the present invention term " site, gap "Insert the cationic site of charge balance modification agent, therefore this relates generally to nomenclature. (reader will remember, such as Ca2+Can be used for because of Al Deng modification agent cation3+Replace Si4+The charge unbalance producing carries out charge balance). Selection term "Gap " emphasize that modification agent cation does not replace or replace the fact of the existing ion in lattice sites conventionally. As previous instituteEmphasize, modification agent cation is the cation adding in existing crystallization agent structure.
, seem in the literature not exist too much the character about these sites, gap (to comprise it through upgradingM2Si5N8:Eu2+Position in structure cell or quantity) information. May exist some data to indicate it is not occupy M site.As thank etc. people title for " for white-light emitting diode based on Sr2Si5N8Eu2+The simple and effective of red phosphor closeOne-tenth approach (Asimple, efficientsyntheticroutetoSr2Si5N8Eu2+-basedredphosphorsforwhiteLight-emittingdiodes) ", chemical journal (Chem.Mater.) 2006,18, institute's teaching in the paper of 5578-5583,At least one synthetic Sr2Si5N8Experiment in, it is 90.7% and for Sr2 site for Sr1 site that site occupies point rateBe 88.9%, thereby remind reader, each structure cell has two M sites. The people such as thank and this is described as to " Sr is two positionsThe light defects at some place ". In material science theory, the vacancy concentration of pure crystalline material is equal according to the heat of produced crystalWeighing apparatus condition should be about every 1,000,100 parts of existing lattice sites. Therefore, the charge balance ion of less percentage can be realIn ending at empty metal ion sites such as Sr/Ca/Eu lattice sites on border, charge balance ion is first filled room againFill site, gap.
Based on M ' x M” 2 A 5-y D y E 8 : the discussion of the phosphor of the present invention of RE
Embodiments of the invention relate to by formula M 'xM”2A5-yDyE8: the composition of the phosphor based on nitride that RE represents.Herein, M ' is at least one in 1+ cation, 2+ cation and 3+ cation, and M " be Mg, Ca, Sr,At least one in Ba and Zn. A is at least one in Si and Ge. Element D replaces A component in replacement mode,Wherein D is the group that selects the IIIB row element composition of free periodic table. In one embodiment, D be B, Al andAt least one in Ga.
Carry out charge compensation for D is replaced to A, modification agent cation M ' is added in phosphor. M ' is Li1+、Na1+、K1+、Sc3+、Ca2+And Y3+In at least one, and this modification agent cation inserts in fact between phosphorIn gap, E is at least one in 3-anion, 2-anion and 1-anion, and can be O2-、N3-、F-、Cl-、Br-And I-In at least one. Rare earth RE is at least one in Eu, Ce, Tb, Pr and Mn; And given yBe 0.01≤y < 1.0, and the chemical valence that x is multiplied by M ' equal y.
In alternate embodiment, the modification agent cation M ' residing in fact in crystal gap is freely following composition of choosingGroup: comprise Ca2+At interior alkaline earth and element Li+、Zn2+、Y3+With one or more rare earth (RE), between these are placed inEach in modification agent cation in gap is indivedual or to be used in combination.
What the alkaline earth atomic time that replaces lattice sites place in rare earths activator ion insertion main body was occurred above discussedReplacement mechanism, converts phosphor to by " conventional ceramic " thus. But replacement event can otherwise be carried out: for example, when placeAt SiN4When being replaced by Al, the Si of tetrahedron center also can replace. This can improve optical characteristics. But, underThose skilled in the art will notice, Al/Si replaces the result presenting and replaces different from Eu/ alkaline earth: due to divalence alkaline earth sun fromSon is replaced by bivalent rare earth cation, and Al3+Replace Si4+Make main body lose a positive charge, therefore under a rear situationBeing substituted by neutral charge replaces. The positive charge of this loss can carry out balance through the further upgrading of phosphor material. SubstitutingIn mechanism, the doping of rare earths activator also can be positioned on site, gap; For example, known Eu resides at β-SiAlON phosphorescenceOn the site, gap of body.
Document has been reported two kinds of modes that are commonly used to carry out losing positive charge charge balance. In a scheme, Al3+Replace Si4+Follow O2-Replace N3-, so that the negative electrical charge of the positive charge of losing and loss antagonism balance. This makes tetrahedronNetwork changeably therein heart place there is Al3+Or Si4+Cation, and there is O at Qi Jiaochu2-To N3-The group of anionClose. Owing to not yet accurately learning which kind of which kind of tetrahedron has and replace, therefore for describing the called after of this situation(Al,Si)-(N,O)4. Clearly, for realizing charge balance, replace Si all to exist an O to replace N for each Al.But embodiments of the invention do not utilize O2-Replace N3-As main charge balance mode, but tend to provideBe positioned in fact the modification agent cation in gap, but this and do not mean that can not in conjunction with modification agent cation use O2-ReplaceN3-。
Carry out the second way of charge balance and the main side that present inventor utilized in the present invention to losing positive chargeMethod is that extra positive charge is fed in fact in crystal gap. Present inventor implements series of experiments, wherein uses IIIBRow element replaces Si, uses Ca2+And/or Sr2+As modification agent cation.
The replacement and the extra cation that comprise N of some embodiments of the invention replace IIIB family element to realizeThe general proxy of the phosphor of the charge balance of Si or isovalent element can comprise by chemical formula M(x/v)M′2A5-yDyN8-zEp:REThe composition based on nitride representing, wherein: M is at least one unit price with chemical valence v, divalence or trivalent metal;M ' is at least one in Mg, Ca, Sr, Ba and Zn; A is at least one in Si, C and Ge; D be B,At least one in Al and Ga; E is that at least one pentavalent with chemical valence w, sexavalence or septivalency are nonmetal; And REFor at least one in Eu, Ce, Tb, Pr and Mn; Wherein x=y-3z+p (8-w), wherein y meets 0.1≤y < 1.1,And wherein phosphor has M '2A5N8: the general crystalline texture of RE, D replaces the A in described general crystalline texture, EReplace the N in described general crystalline texture, and M is positioned in fact the gap site of described general crystalline texture.
In First Series experiment (being expressed as sample 1-4), assessment is as the IIIB of the periodic table of the potential substituent of SiRow element. Parent material for the synthesis of " basic compound " (not containing the phosphor of the capable content of IIIB) is to do respectivelyFor the EuCl in europium source, strontium source, calcium source, silicon source3、Sr3N2、Ca3N2And Si3N4Powder. Certainly arbitrary nitride salt,Nitrogen all can be provided. Be Al, B and Ga for replacing three kinds of Si from the capable element of periodic table III. About thisThe experimental detail of series compound is provided in to show in 2A and table 2B. The sample 1-4 that comprises the IIIB row element that replaces siliconThe stoichiometric composition of compound by the atomic weight incremental order of B, Al and Ga be: for boron-containing compound beEu0.05Ca0.1Sr1.95B0.2Si4.8N8; Be Eu for containing Al compound0.05Ca0.1Sr1.95Al0.2Si4.8N8, and for containing GaCompound is Eu0.05Ca0.1Sr1.95Ga0.2Si4.8N8。
With reference to figure 1, in this series samples 1-4, having the phosphor of high photoluminescence intensity is boron-containing compound; ThisIndividual sample is also shown the phosphor with the shortest peak emission wavelength (launching under about 623nm). This group is containing the exhibition of aluminium phosphorNow comprise the contrast of this group compound (not containing the capable substituent 2-5-8 phosphor (Eu of IIIB0.05Sr1.95Si5N8)) lightPhotoluminescence intensity is at interior minimum photoluminescence intensity. In other words, control compound Eu even0.05Sr1.95Si5N8Also exhibitionNow higher than the photoluminescence intensity of aluminum contained compound. In testing separately, can pass through containing the photoluminescence intensity of aluminium sampleUnder higher temperature, sintering further increases. It shall yet further be noted that the sample that contains B and Ga does not show in XRD dataRemarkable 2 θ degree offset, this can indicate the replacement that Si may not occur in these samples. For example, B may beEvaporate or may form impurity phase with other element such as such as Sr, and 2-5-8 material (seldom or without B replacing Si) is stillPrincipal phase.
In second series experiment (being expressed as sample 5-8), assessment is as the IIIB of the periodic table of the potential substituent of SiRow element, but in described second group calcic not. But for realizing charge balance, replace nitrogen with oxygen. Oxygen is with raw materialPowder SiO2And Al2O3Form supply. Certainly, in these cases, material powder SiO2And Al2O3Also as silicon andThe source of the source of aluminium or potential source and oxygen. Thin about utilizing oxygen to carry out the experiment of this series compound of charge balanceJoint is provided in to show in 3A and table 3B. Replacing nitrogen by oxygen replaces Si to B, Al and/or Ga and carries out charge balanceThe stoichiometric composition of sample 5-8 compound by described order is: for boron-containing compound beEu0.05Sr1.95B0.2Si4.8O0.2N7.8; Be Eu for containing Al compound0.05Sr1.95Al0.2Si4.8O0.2N7.8, and for containing GaCompound is Eu0.05Sr1.95Ga0.2Si4.8O0.2N7.8。
With reference to figure 5, in this series (sample 5-8), having the phosphor of high photoluminescence intensity is control compoundEu0.05Sr1.95Si5N8. This seems to indicate, and at least for this serial experiment, adds oxygen and can weaken luminescence generated by lightIntensity.
In the 3rd serial experiment (being expressed as sample 9-12), the compound that relatively carries out charge balance by clearance C a is to logicalCross the compound that replaces oxygen and carry out charge balance, two kinds of charge balances are Al, and to replace Si institute essential. Further compare thisA little compounds with containing Al but do not cause and have a mind to the phosphor of charge balance mechanism. Experiment about this series compound is thinJoint is provided in to show in 4A and table 4B. The stoichiometric composition of the compound of sample 9-12 is:Eu0.05Ca0.1Sr1.95Al0.2Si4.8N8, in described compound, replace Si with IIIB row element Al, and by clearance C aRealize charge balance; Eu0.05Sr1.95Al0.2Si4.8O0.2N7.8, in described compound, also get with IIIB row element AlFor Si, but be to realize charge balance by replacing nitrogen with oxygen specifically; Eu0.05Sr1.95Al0.2Si4.8N7.93, described compoundIn utilize nitrogen lack to Al replace Si carry out charge balance; Finally, contrast as Eu0.05Sr1.95Si5N8。
With reference to figure 7, in this series (sample 9-12), having the phosphor of high photoluminescence intensity is also control compoundEu0.05Sr1.95Si5N8, but the compound replacing through Al that utilizes clearance C a to carry out charge balance represents height about the samePhotoluminescence intensity. Data further show, the replacement of this compound and charge balance subsequently make peak emission strongDegree is to more long wavelength shifted. This and " routine " Sr2Si5N8The wavelength shift of seeing while replacing Sr with Ca in compound is contrary.After described, an observation has multiple favourable parts for color rendition when from white light LEDs generation white-light illuminating. From the present inventionThe experiment deducibility that person implements goes out, and because Al replaces Si, the charge balance of intermittence in fact completing by Ca is mustNeed.
In Quaternary system row experiments (being expressed as sample 13-16), assessment is as the IIIB of the periodic table of the potential substituent of SiRow element, but in this series unrealized have a mind to charge balance. After described, a statement means, does not add such as CaDeng gap cation; Do not replace nitrogen (therefore these formulas show that the stoichiometry content of nitrogen is 8) with oxygen. About this seriesThe experimental detail of compound is provided in to show in 5A and table 5B. In this serial experiment, present inventor thinks, some nitrogenSite can be room with balancing charge. Utilize nitrogen defect to realize the hypothesis of charge balance based on this, expection sample 13-16The stoichiometric composition of compound be: Eu0.05Sr1.95B0.2Si4.8N7.93, in described compound, IIIB row element BReplace Si, and further do not attempt charge balance; Eu0.05Sr1.95Al0.2Si4.8N7.93, the capable unit of IIIB in described compoundElement Al has also replaced Si, and does not also attempt charge balance; And Eu0.05Sr1.95Ga0.2Si4.8N7.93, in described compoundIIIB row element Ga has replaced Si, and does not also further attempt charge balance. The contrast of this series is alsoEu0.05Sr1.95Si5N8。
The N that comprises of some embodiments of the invention lacks to realize the electric charge that IIIB family element is replaced to Si or isovalent elementThe general proxy of the red emitting phosphor of balance can comprise by chemical formula M '2Si5-yDyN8-z: RE represent based on nitrideComposition, wherein M ' is at least one in Mg, Ca, Sr, Ba and Zn; D is at least one in B, Al and GaPerson; And RE is at least one in Eu, Ce, Tb, Pr and Mn; Wherein y=3z, phosphor has M '2Si5N8:REGeneral crystalline texture, and Al replaces the Si in described general crystalline texture. In addition, red emitting phosphor can be configured,Wherein M ' is Sr, and D is Si, and RE is Eu. Red emitting phosphor can be configured, wherein said red emitting phosphorFormed by Sr, Si, Al, N and Eu. Red emitting phosphor can be configured, and wherein y meets 0.1≤y < 0.4. GlowPhosphor can be configured, and wherein z meets 0.05≤z < 0.09.
With reference to figure 9, in this series (sample 13-16), having the phosphor of high photoluminescence intensity is boron-containing compound.Intensity time high person is two kinds and has the compound of same intensity in fact: containing gallium compound and contrast. Aluminum contained compound hasSignificantly lower photoluminescence intensity. Interestingly, it should be noted that, in this series, contrast, contain BWith the peak emission wavelength representing containing Ga sample (sample 15 and 16) be about 624nm. According to some embodiment, B andGa may not replace Si, but as flux. Described statement is to make according to experiment, and wherein x ray diffraction peaks alsoNot because replacement is offset; In addition peak emission wavelength also not skew in these experiments. Interestingly, peopleNotice, compared with sample (sample 2) through Ca charge balance, the described Al that lacks charge balance through N replaces sampleHave compared with small wavelength skew and lower photoluminescence intensity. This may indicate, and is placed in the Ca of gap for charge balanceMake wavelength shift farther and improve photoluminescence intensity.
In the 5th serial experiment (being expressed as sample 17-21), assessment is as removing stoichiometric equation Sr2Si5N8Element in additionPeriodic table IIIB row element. The amount of adding the IIIB row element in raw material powder mixture to is about sample 13-16The twice (low by 50% than the sample of those IIIB replacement silicon) of middle consumption. The amount of Ca that sample 21 adds and interpolation IIIBSample identical. If owing to especially not using single-crystal x Diffraction, be difficult to accurately to measure sintered compoundComposition, therefore this serial stoichiometric equation is by Ca, B, Al and Ga cation form are shown to its corresponding raw material" additive " of powder salt shows. Therefore, the stoichiometric equation of the compound of sample 17-21 can be expressed as: be added withCa3N2Eu0.05Sr1.95Si5N8; Be added with the Eu of BN0.05Sr1.95Si5N8; Be added with the Eu of AlN0.05Sr1.95Si5N8；Be added with the Eu of GaN0.05Sr1.95Si5N8; With contrast Eu0.05Sr1.95Si5N8. Experiment about this series compound is thinJoint is provided in to show in 6A and table 6B.
With reference to Figure 11, it is strong that each phosphor in this series (sample 17-21) all represents identical in fact luminescence generated by lightDegree and similar in fact peak emission wavelength (about 624nm), the simple IIIB row element adding of this instruction may be notReplace silicon.
In the 6th serial experiment (being expressed as sample 22-27), from the capable selection of the IIIB boron of periodic table for further grindingStudy carefully. For example,, referring to the boron-containing sample in Fig. 1 and this group sample 1-4. In this group experiment, boron content is with stoichiometryMode is expressed as parameter " y ", and described parameter " y " has following value: y=0; Y=0.2; Y=0.3; Y=0.4; Y=0.5 and y=1.0.Charge compensation is to add gap calcium by the amount to increase progressively respectively to complete. Experimental detail about this series compound is carriedIn table 7A and table 7B. The emission spectrum of the phosphor of sample 22-27 is shown in Figure 13.
In the 7th serial experiment (being expressed as sample 28-32), from the capable selection of the IIIB aluminium of periodic table for further grindingStudy carefully. For example, referring in Fig. 1 and this group sample 1-4 containing aluminium sample. In this group experiment, boron content is with stoichiometryMode is expressed as parameter " y ", and described parameter " y " has following value: y=0.15; Y=0.2; Y=0.25; Y=0.3 and y=0.4.Charge compensation is to add gap calcium by the amount to increase progressively respectively to complete. Experimental detail about this series compound is carriedIn table 8A and table 8B. The emission spectrum of the phosphor of sample 28-32 is shown in Figure 20.
The general introduction of experiment concept
Experimental result instruction as described above, for these experiments (may indicate general trend), finds the capable unit of IIIBElement Al replacement Si and Ca be the skew maximum to longer emission wavelength as the cationic combination of upgrading, and follows photicLuminous intensity is minimum to be weakened. The stoichiometry of the amount of the parent material that uses, peak wavelength emission, phosphor and to being substitutedThe general introduction of thing/additive is shown in following table 1.
Amount, stoichiometry and the peak emission wavelength of the parent material of table 1 sample 2 and 6.
In the first experiment of being given prominence in table 1, Al3+Replace Si4+Cause charge unbalance. The phosphor of sample 2 is logicalCross the Ca adding in fact in gap2+Modification agent cation solves charge unbalance; This makes sample 2 phosphorsPeak emission wavelength is with respect to not increasing 6nm containing Al or the cationic contrast of modification agent. Sample 2 phosphors have formula Eu0.05Ca0.1Sr1.95Al0.2Si4.8N8, and contrast is Eu0.05Sr1.95Si5N8。
In the second experiment of being given prominence in table 1, Al3+Replace Si4+Also cause charge unbalance. But, real at thisIn testing, use relatively large Al, and some Al are Al2O3Form (source of oxygen). Herein, O2-Replace N3-For electricityLotus balancing, and therefore do not have extra calcium or do not add calcium. Result is also the peak emission wavelength of sample 6 phosphorsIncrease 6nm with respect to sample 5 contrasts. The formula of sample 6 compounds is Eu0.05Sr1.95Al0.2Si4.8N7.8O0.2, and contrastAlso be Eu0.05Sr1.95Si5N8。
But as discussed below, Reliability Test Data shows, according to calcium, the phosphor of the present invention of charge balance is carriedSupply or approach very much the needed extent of stability to humidity and temperature of Lighting Industry, and making the phosphorus of charge balance according to oxygenLight body has relatively poor stability.
Figure 19 shows the comparison of the emission spectrum to following phosphor: the gold-tinted YAG phosphorescence of the doped Ce of prior artBody; (650nm) red phosphor CaAlSiN of doping Eu3Ruddiness with the 630nm doping Eu of the embodiment of the present inventionPhosphor Ca0.1Sr2Si4.8Al0.2N8(sample 2). Each spectrum is all to measure under 450nm blue-ray LED excitaton source.
As the ruddiness nitride of the present invention of a white light LEDs part
Figure 15 shows the spectrum of white light LEDs (3000K), described white light LEDs (3000K) comprise blue light InGaNLED,There is formula Eu0.05Ca0.1Sr1.95Si4.8Al0.2N8Red phosphor (from sample 2) and there is formula Ce:Lu3Al5O12GreenLight phosphor; And Figure 16 shows the spectrum of white light LEDs (3000K), described white light LEDs (3000K) comprises blue light InGaNLED, there is formula Eu0.05Ca0.1Sr1.95Si4.8B0.2N8Red phosphor (from sample 3) and there is formula Ce:Lu3Al5O12Green glow phosphor.
Reliability testing
Comprising the U.S. in interior many areas, regulator is for replacing LED lamp to set performance standard. For example, U.S.(the US of associating USDOE of Bureau for Environmental Protection of state (USEnvironmentalProtectionAgency, EPA)DepartmentofEnergy, DOE) announce and for example identified power supply instructions for use, minimum light output requirement, luminous intensityThe specification of requirement, luminous efficacy requirement, the life expectancy etc. of distributing, the lamp that meets described specification can be described as " ENERGYSTAR" qualified products. ENERGY" to the requirements of plan of integral LED lamp " requirement, institute" within the minimum lumen depreciation testing period (6000 hours), the colourity on CIE1976 (u ', v ') figure changes LED lampShould be no more than 0.007 ", and to determine according to lamp type, described lamp must " have in the time of work 15,000 or 25,000 hours>=70% lumen depreciation (L70) ". ENERGYRequire for lamp behaviour and all component that comprises lamp, exampleAs LED, phosphor, electronic drive circuit, optical module and mechanical component. In principle, the brightness of white light LEDs withAging and weaken and can be not only due to phosphor, and or due to blue-light LED chip. Other source of weakening can be fromPackaging material (for example substrate), closing line and other assembly being encapsulated through silicone. By contrast, affecting hue coordinate changesPrincipal element be phosphor degradation. About phosphor performance, it is believed that in order to meet ENERGYRequirement,Need to be under the accelerated test of 85 DEG C and 85% relative humidity, the colourity of phosphor each coordinate in 1000 hours changes(CIE Δ x, CIE Δ y)≤0.01. The LED through phosphor-coating being prepared as follows is carried out to accelerated test: combination phosphorusLight body particle with such as the adhesive such as epoxy resin or silicone, and be then coated to LED chip. To put through coating LEDIn baking oven under assigned temperature and humidity and continued operation within the testing period.
The reliability of the phosphor of Figure 17 A-17C show sample 1 to 3 and 6 under 85 DEG C and 85% relative humidity conditionThe result of test. Figure 17 A-17C is presented under the acceleration environment of 85 DEG C and 85% relative humidity, 3000K white light LEDs (asShown in the spectrum of Figure 15 and Figure 16) photoluminescence intensity (brightness) over time with cie color coordinate at any timeBetween variation. There is the Sr of LED conversion2Si5N8The phosphor of control sample and sample 6(Eu0.05Sr1.95Si4.8Al0.2N7.8O0.2) the two shows industrial common unacceptable result. As by maintaining intensity and lookThe significantly improvement of spending defined stability is unexpectedly by Ca as illustrated in sample 2 gap charge balanceReplacing Si (referring to table 2A) with Al realizes. The less relative improvement of sample 3 exhibit stabilizations; Sample 3 is for containing B sampleProduct.
For further improved performance is to meet ENERGYRequirement, can be used (for example) one or more SiO2、Al2O3And/or TiO2Coating is coated with the phosphor particles of the composition with sample 2, if common patent application case co-pending is for useIn the U.S. of the coating (COATINGSFORPHOTOLUMINESCENTMATERIALS) of embedded photoluminescent materialApplication case the 13/671st, No. 501 and for the reliable embedded photoluminescent material of the height with thick and uniform coating of titanium dioxide(HIGHLYRELIABLEPHOTOLUMINESCENTMATERIALSHAVINGATHICKANDUNIFORMTITANIUMDIOXIDECOATING) U. S. application case the 13/273rd, institute's teaching in No. 166, thisIn a little application cases, the content of each is incorporated herein by reference in full. Figure 18 A-18C shows to haveAl2O3/SiO2The phosphor (it has the composition identical with sample 2) of the sample 33 of coating. As graphic from these,Meet for establishing ENERGY through coated phosphorThe accelerated test standard of qualification.
Synthesizing of phosphor of the present invention
For each example described herein and comparative example, parent material comprises at least one in following compound:Si3N4、AlN、Ca3N2、Sr3N2、BN、GaN、SiO2、Al2O3And EuCl3。
Sample 1 to 4
For obtaining the required composition of illustrated phosphor in sample 1 to 4, weigh according to the composition listing in table 2APressed powder. Then described mixture of raw material is loaded in plastics grinding bottle together with grinding bead, is sealed in glovesIn case, then carry out the ball-milling technology of approximately 2 hours. Then mixed-powder to be loaded into internal diameter be 30mm and be highlyIn the molybdenum crucible of 30mm; Crucible through loading is covered and is placed in molybdenum lid the gas sintered stove that is equipped with graphite heaterIn.
Load after crucible, stove is evacuated to 10-2Pa, and sample is heated to 150 DEG C under these vacuum conditions. 150At DEG C temperature, by high purity N2Gas is introduced in chamber; Then the constant in fact heating with 4 DEG C/min by the temperature of stoveSpeed is elevated to approximately 1700 DEG C. Sample is maintained at 1700 DEG C to approximately 7 hours.
After roasting, cut off the electricity supply and make sample cooling in stove. The phosphor of former state after grinding and sintering gently, ball milling is to certainOne particle size, then washs, is dried and screening program. Use marine optics (OceanOptics) USB4000Spectrometer is tested the photoluminescence intensity (PL) of end product and colourity (CIE coordinate x and y). Use the K of Cu targetαLine is measured x x ray diffraction (XRD) figure of the phosphor of sample 1 to 4.
The test result of the phosphor of sample 1 to 4 is shown in table 2B. Fig. 1 shows emission spectrum result. Fig. 2 is aobviousShow XRD figure. It should be noted that phosphor sample 33 is to use the method identical with sample 2 to manufacture.
The initial raw-material composition of table 2A sample 1 to 4.
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN BN GaN SiO2 Al2O3
Sample 1 2.5833 37.8131 - 46.7629 - - - - -
Sample 2 2.5833 37.8131 0.987 44.8915 1.6396 - - - -
Sample 3 2.5833 37.8131 0.987 44.8915 - 0.9928 - - -
Sample 4 2.5833 37.8131 0.987 44.8915 - - 3.3492 - -
Composition and peak emission wavelength, intensity and the CIE. of table 2B sample 1 to 4
Sample 5 to 8
For obtaining the design composition of phosphor, weigh pressed powder according to the compositions of mixtures listing in table 3A, makeWith with synthesis program identical described in sample 1 to 4. Test result is shown in table 3B.
Fig. 5 is the emission spectrum of the phosphor of sample 5 to 8. Use the K of Cu targetαThe phosphorescence of line to sample 5 to 8The powder x ray diffraction measurement that body carries out is shown in Fig. 6.
The initial raw-material composition of table 3A sample 5 to 8.
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN BN GaN SiO2 Al2O3
Sample 5 2.5833 37.8131 - 46.7629 - - - - -
Sample 6 2.5833 37.8131 - 44.8915 0.5468 - - - 1.3602
Sample 7 2.5833 37.8131 - 43.9572 - 0.9928 - 1.2017 -
Sample 8 2.5833 37.8131 - 43.9572 - - 3.3492 1.2017 -
Composition and peak emission wavelength, intensity and the CIE. of table 3B sample 5 to 8
Sample 9 to 12
For obtaining the design composition of phosphor, weigh pressed powder according to the compositions of mixtures listing in table 4A, makeWith with synthesis program identical described in sample 1 to 4. Test result is shown in table 4B.
Fig. 7 is the emission spectrum of the phosphor of sample 9 to 12. Use the K of Cu targetαThe phosphorus of line to sample 9 to 12The powder x ray diffraction measurement that light body carries out is shown in Fig. 8.
The initial raw-material composition of table 4A sample 9 to 12.
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN BN GaN SiO2 Al2O3
Sample 9 2.5833 37.8131 - 46.7629 - - - - -
Sample 10 2.5833 37.8131 0.987 44.8915 1.6395 - - - -
Sample 11 2.5833 37.8131 - 44.8915 0.5468 - - - 1.3602
Sample 12 2.5833 37.8131 - 44.8915 1.6396 - - - -
Composition and peak emission wavelength, intensity and the CIE. of table 4B sample 9 to 12
Sample 13 to 16
For obtaining the design composition of phosphor, weigh pressed powder according to the compositions of mixtures listing in table 5A, makeWith with synthesis program identical described in sample 1 to 4. Test result is shown in table 5B.
Fig. 9 is the emission spectrum of the phosphor of sample 13 to 16. Use the K of Cu targetαLine is to sample 13 to 16The powder x ray diffraction measurement that phosphor carries out is shown in Figure 10.
The initial raw-material composition of table 5A sample 13 to 16.
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN BN GaN SiO2 Al2O3
Sample 13 2.5833 37.8131 - 46.7629 - - - - -
Sample 14 2.5833 37.8131 - 44.8915 1.6396 - - - -
Sample 15 2.5833 37.8131 - 44.8915 - 0.9928 - - -
Sample 16 2.5833 37.8131 - 44.8915 - - 3.3492 - -
Composition and peak emission wavelength, intensity and the CIE. of table 5B sample 13 to 16
Sample 17 to 21
For obtaining the required composition of this group phosphor, weigh pressed powder according to the compositions of mixtures listing in table 6A,Use and synthesis program identical described in sample 1 to 4. Test result is shown in table 6B.
Figure 11 is the emission spectrum of the phosphor of sample 17 to 21. Use the K of Cu targetαLine is to sample 17 to 21The powder x ray diffraction measurement that carries out of phosphor be shown in Figure 12.
The initial raw-material composition of table 6A sample 17 to 21.
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN BN GaN SiO2 Al2O3
Sample 17 2.5833 37.8131 - 46.7629 - - - - -
Sample 18 2.5833 37.8131 - 46.7629 0.8198 - - - -
Sample 19 2.5833 37.8131 - 46.7629 - 0.4064 - - -
Sample 20 2.5833 37.8131 - 46.7629 - - 1.6746 - -
Sample 21 2.5833 37.8131 0.494 46.7629
Composition and peak emission wavelength, intensity and the CIE. of table 6B sample 17 to 21
Sample 22 to 27
For obtaining the required composition of phosphor of sample 22 to 27, weigh solid according to the composition listing in table 7APowder. Use and the identical synthesis program that uses in sample 1 to 4. Test result is shown in table 7B.
Figure 13 is the emission spectrum of the phosphor of sample 22 to 27. Use the K of Cu targetαLine obtains X-ray diffractionMeasure, and the XRD figure of sample 22 to 27 is shown in Figure 14.
The initial raw-material composition of table 7A sample 22 to 27.
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN BN GaN SiO2 Al2O3
Sample 22 2.5833 37.8131 - 46.7629 - - - - -
Sample 23 2.5833 37.8131 0.987- 44.8915 - 0.9928 - - -
Sample 24 2.5833 37.8131 1.4825 43.9572 - 1.4892 - - -
Sample 25 2.5833 37.8131 1.9776 43.0201 - 1.9856 - - -
Sample 26 2.5833 37.8131 2.4698 42.0858 - 2.482 - - -
Sample 27 2.5833 37.8131 4.9426 37.4087 - 4.964 - - -
Composition and peak emission wavelength, intensity and the CIE. of table 7B sample 22 to 27
Sample 28 to 32
For obtaining the required composition of phosphor of sample 28 to 32, weigh solid according to the composition listing in table 8APowder. Use and the identical synthesis program that uses in sample 1 to 4. Test result is shown in table 8B. It should be noted thatIonization meter in table 8B is to use from the ionization meter different equipment used of the sample that lists in other table to carry out;Use the absolute intensity of described distinct device to measure the absolute intensity measurement lower than equipment that other sample uses.
Figure 20 is the emission spectrum of the phosphor of sample 28 to 32. Use the K of Cu targetαLine obtains X-ray diffractionMeasure, and the XRD figure of sample 28 to 32 is shown in Figure 21.
The initial raw-material composition of table 8A sample 28 to 32.
Compound EuCl3 Sr3N2 Ca3N2 Si3N4 AlN
Sample 28 2.5833 37.8131 0.7412 45.3600 1.2296
Sample 29 2.5833 37.8131 0.987 44.8915 1.6396
Sample 30 2.5833 37.8131 1.2356 44.4228 2.0496
Sample 31 2.5833 37.8131 1.4824 43.9572 2.4596
Sample 32 2.5833 37.8131 1.9768 43.0200 3.2792
Composition and peak emission wavelength, intensity and the CIE. of table 8B sample 28 to 32
Those one of ordinary skill in the art will understand, and can use method as described above according to some different choice of elementPrepare the composition that exceeds the composition of clearly describing above. For example, can prepare by chemical formula M(x/v)M′2A5-yDyN8-zEp:RERepresent composition, wherein: M is at least one unit price with chemical valence v, divalence or trivalent metal, for example Li,Na, K, Sc, Ca, Mg, Sr, Ba and Y; M ' is at least one in Mg, Ca, Sr, Ba and Zn; A isAt least one in Si, C and Ge; D is at least one in B, Al and Ga; E is that at least one has chemical valencePentavalent, sexavalence or the septivalency of w are nonmetal, for example O, N, F, Cl, Br and I; And RE is Eu, Ce, Tb, PrWith at least one in Mn; Wherein x=y-3z+p (8-w), and wherein phosphor has M '2A5N8: the general crystallization of REStructure.
Figure 22 illustrates the light-emitting device according to some embodiment. Device 10 can comprise be contained in (for example) packaging inBlue light-emitting (450nm is within the scope of 470nm) GaN (gallium nitride) LED chip 12. Can comprise (for example) low temperature concurrent roastingThe packaging of pottery (LTCC) or high temperature polymer comprises upper and lower body part 16,18. Upper body parts 16 boundariesFixed rounded recess 20 conventionally, it is configured to receive LED chip 12. Described packaging further comprises electrical connectionDevice 22 and 24, it also defines the respective electrode contact pad 26 and 28 on the base plate of recess 20. Can use adhesive agent orScolder is installed on LED chip 12 heat conductive pad on the base plate that is positioned at recess 20. Use closing line 30 and 32 willThe electronic pads of LED chip is electrically connected to the respective electrode contact pad 26 and 28 on packaging bottom, and uses transparent polymer materialMaterial 34 (being generally silicone) are filled up recess 20 completely, and described transparent polymer material 34 is mounted with gold-tinted and/or greenThe mixture of light phosphor and red phosphor material of the present invention is to make the exposed surface of LED chip 12 by phosphor/ polymeric material material mixture covers. For strengthening the transmitting brightness of described device, make the wall of recess tilt and there is light reflectionSurface.
Figure 23 A and 23B illustrate the solid luminous device according to some embodiment. Device 100 is configured to produceCCT (correlated colour temperature), for about 3000K and luminous flux are the warm white of approximately 1000 lumens, and can be used as lower illuminator or otherA part for ligthing paraphernalia. Device 100 comprises hollow o cylindrical body 102, and it is by disc substrate 104, hollowCylindrical wall portion 106 and detachable annular top 108 form. For help heat radiation, substrate 104 preferably from aluminium,Aluminium alloy or arbitrary material manufacture with high thermal conductivity. Can be by screw or bolt or by other securing member or according to glutinousAgent substrate 104 is attached to wall part 106.
Device 100 further comprises multiple (being 4 in illustrated example) blue light-emitting LED112 (blue lightLED), these blue light-emittings LED112 is through installing and circular MCPCB (metallic core printed circuit board (PCB)) 114 thermal communications.Blue-ray LED 112 can comprise the ceramic package battle array of 12 0.4W blue-light LED chips based on GaN (based on gallium nitride)Row, described array is configured the rectangular array that is 3 row × 4 row.
For the transmitting that makes light maximizes, device 100 can further comprise the face and the top 108 that cover respectively MCPCB114The light reflective surface 116 and 118 on interior curve surface. Device 100 further comprises photoluminescence wavelength transition components120, the mixture that it comprises gold-tinted and/or green glow phosphor and red phosphor material of the present invention, it can operate to inhaleA part of blue light that receipts LED112 produces the light that converts thereof into different wave length by photoluminescent process. Device 100Transmitting product comprise the combined light being produced by LED112 and photoluminescence wavelength transition components 120. Described wavelength conversionThe location of assembly is also spatially divided out with LED away from LED112. In patent specification, " remotely " and " distantFar away " mean to be interval or apart relation. Wavelength transition components 120 is configured to complete covering shell opening, so that lampAll light of transmitting are all through assembly 120. As shown in scheming, wavelength transition components 120 can use top 108 with removableThe mode of unloading is installed on the top of wall part 106, to make to be easy to change the transmitting color of assembly and lamp.
Although specifically described the present invention with reference to some embodiment of the present invention, one of ordinary skill in the art are by easySeparate, can in the situation that not deviating from the spirit and scope of the present invention, make change and amendment to form and details.

Claims (30)

1. a red emitting phosphor with the composition based on nitride, it comprises:
Element M, wherein M is at least one in Li, Na, K, Sc, Ca, Mg, Sr, Ba and Y;
Element M ', wherein M ' is at least one in Mg, Ca, Sr, Ba and Zn;
Silicon;
Aluminium;
Nitrogen; With
Elements RE, wherein RE is at least one in Eu, Ce, Tb, Pr and Mn;
Wherein said red emitting phosphor has M '2Si5N8: the general crystalline texture of RE and M and Al are included, itsMiddle M is positioned in fact the Si of gap site and the described general crystalline texture of Al replacement of described general crystalline texture,And wherein said red emitting phosphor is configured to make under 85 DEG C and 85% relative humidity after aging 1,000 hour, everyThe changes in coordinates CIE Δ x of one chromaticity coordinate and CIE Δ y are less than or equal to 0.03.
2. red emitting phosphor according to claim 1, wherein M is Ca.
3. red emitting phosphor according to claim 1, wherein M ' is Sr.
4. red emitting phosphor according to claim 1, wherein said red emitting phosphor be by Ca, Sr, Si,Al, N and Eu composition.
5. red emitting phosphor according to claim 1, wherein RE is Eu.
6. red emitting phosphor according to claim 1, wherein said red emitting phosphor is configured to makeUnder the exciting of blue-ray LED, the weakening of photoluminescence intensity after aging 1,000 hour under 85 DEG C and 85% relative humidityBe not more than 30%.
7. red emitting phosphor according to claim 1, wherein said red emitting phosphor absorbing wavelength is between 200Nm is greater than the light of 623nm to the radiation within the scope of 420nm and utilizing emitted light photoluminescence peak emission wavelength.
8. red emitting phosphor according to claim 1, wherein said red emitting phosphor is Ca0.1Sr2.0Al0.20Si4.80N8:Eu。
9. red emitting phosphor according to claim 1, wherein said red emitting phosphor isEu0.05Ca0.1Sr1.95Al0.20Si4.80N8。
10. a red emitting phosphor, it comprises by chemical formula M(x/v)M′2Si5-xAlxN8: RE represent based on nitrideComposition, wherein:
M is at least one unit price with chemical valence v, divalence or trivalent metal;
M ' is at least one in Mg, Ca, Sr, Ba and Zn; And
RE is at least one in Eu, Ce, Tb, Pr and Mn;
Wherein x meets 0.1≤x < 0.4, and wherein said red emitting phosphor has M '2Si5N8: the general crystallization knot of REStructure, Al replaces the Si in described general crystalline texture, and M is positioned in fact the gap digit of described general crystalline texturePoint place.
11. red emitting phosphors according to claim 10, wherein M be Li, Na, K, Sc, Ca, Mg,At least one in Sr, Ba and Y.
12. red emitting phosphors according to claim 10, wherein M is Ca, M ' is that Sr and RE are Eu.
13. red emitting phosphors according to claim 10, wherein said red emitting phosphor be by Ca, Sr,Si, Al, N and Eu composition.
14. red emitting phosphors according to claim 10, wherein x meets 0.10≤x < 0.25.
15. red emitting phosphors according to claim 14, wherein M is Ca, M ' is that Sr and RE are Eu.
16. red emitting phosphors according to claim 10, wherein said red emitting phosphor is configured to makeUnder the exciting of blue-ray LED, the weakening not of photoluminescence intensity after aging 1,000 hour under 85 DEG C and 85% humidityBe greater than 30%.
17. red emitting phosphors according to claim 10, wherein said red emitting phosphor is configured to makeUnder 85 DEG C and 85% relative humidity after aging 1,000 hour, the grid deviation CIE Δ x of each chromaticity coordinate and CIE Δ yBe less than or equal to 0.03.
18. red emitting phosphors according to claim 10, wherein said red emitting phosphor absorbing wavelength between200nm is greater than the light of 623nm to the radiation within the scope of 420nm and utilizing emitted light photoluminescence peak emission wavelength.
19. red emitting phosphors according to claim 10, wherein said red emitting phosphor is below choosing freelyThe group of composition:
Eu0.05Ca0.075Sr1.95Al0.15Si4.85N8；
Eu0.05Ca0.1Sr1.95Al0.20Si4.80N8；
Eu0.05Ca0.125Sr1.95Al0.25Si4.75N8；
Eu0.05Ca0.15Sr1.95Al0.30Si4.70N8; With
Eu0.05Ca0.2Sr1.95Al0.40Si4.60N8。
20. red emitting phosphors according to claim 10, wherein said red emitting phosphor isCa0.1Sr2.0Al0.20Si4.80N8:Eu。
21. 1 kinds of white light illumination source, it comprises:
Excitaton source, its emission wavelength arrives within the scope of 480nm between 200nm;
Red emitting phosphor, it comprises by chemical formula M(x/v)M′2Si5-xAlxN8: the composition based on nitride that RE represents,Wherein:
M is at least one unit price with chemical valence v, divalence or trivalent metal;
M ' is at least one in Mg, Ca, Sr, Ba and Zn; And
RE is at least one in Eu, Ce, Tb, Pr and Mn;
Wherein x meets 0.1≤x < 0.4, and wherein said red emitting phosphor has M '2Si5N8: the general crystallization knot of REStructure, Al replaces the Si in described general crystalline texture, and M is positioned in fact the gap digit of described general crystalline texturePoint place, described red emitting phosphor is configured to absorb the exciting radiation from described excitaton source, and launches peak emission rippleLength arrives the light within the scope of 650nm between 620nm; With
At least one in Yellow light-emitting low temperature phosphor and green-emitting phosphors.
22. white light illumination source according to claim 21, wherein said red emitting phosphor is configured to absorbFrom the exciting radiation of described excitaton source, and launch peak emission wavelength and arrive the light within the scope of 634nm between 628nm.
23. white light illumination source according to claim 21, wherein said red emitting phosphor has formulaEu:Ca0.1Sr2.0Al0.20Si4.80N8。
24. white light illumination source according to claim 21, wherein said Yellow light-emitting low temperature phosphor and described green light phosphorusDescribed at least one in light body has formula Ce:Lu3Al5O12。
25. white light illumination source according to claim 21, the emission wavelength of wherein said excitaton source is between 420nmWithin the scope of 470nm.
26. white light illumination source according to claim 21, wherein M be Li, Na, K, Sc, Ca, Mg,At least one in Sr, Ba and Y.
27. white light illumination source according to claim 21, wherein M is Ca, M ' is that Sr and RE are Eu.
28. white light illumination source according to claim 21, wherein said red emitting phosphor be by Ca, Sr, Si,Al, N and Eu composition.
29. white light illumination source according to claim 21, wherein x meets 0.10≤x < 0.25.
30. white light illumination source according to claim 21, wherein said red emitting phosphor is configured to makeUnder 85 DEG C and 85% relative humidity after aging 1,000 hour, the grid deviation CIE Δ x of each chromaticity coordinate and CIE Δ yBe less than or equal to 0.03.
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