CN109219646A - Emit the phosphor and relevant apparatus of feux rouges - Google Patents

Abstract

The present invention provides include the following method: obtaining formula A_x[MF_y]:Mn⁴⁺Phosphor precursors particle, reduce the size of phosphor precursors particle by wet-milling particle, and so that the particle through wet-milling is annealed by making particle and contact containing fluorine oxidiser.Additionally, it is provided the composite fluoride phosphor of the additive Mn prepared by this method.Additionally provide illumination instrument and back lighting device comprising pass through the phosphor of additive Mn prepared by this method.

Description

Emit the phosphor and relevant apparatus of feux rouges

Cross reference to related applications

Present patent application be the U.S. Patent Application Serial Number 14/303,020 submitted on June 12nd, 2014 part after Continuous application, the complete disclosure of the U.S. Patent application are hereby incorporated herein by.

Background technique

Based on by Mn⁴⁺Phosphor (such as the US 7,358,542, US of the transmitting feux rouges of the composite fluoride material of activation Described in 7,497,973 and US 7,648,649 those) can with transmitting yellow/green phosphor such as YAG:Ce or other stones Garnet combination of compositions utilize, with realize from blue LED (LED) warm white (on black body locus (CCT < 5000K, colour rendering index (CRI) > 80), the warm white is equivalent to that generated by current fluorescent lamp, incandescent lamp and halogen lamp Kind.These materials consumingly absorb blue light, and effectively emit between about 610-635nm, have seldom dark red/NIR Transmitting.Therefore, luminous efficiency maximizes compared with red-emitting phosphor, and the red-emitting phosphor has significant deeper feux rouges (wherein the susceptibility of eyes is weaker) transmitting.Quantum efficiency can be more than 85% under blue (440-460nm) excitation.

Although using Mn⁴⁺The effect of lighting system of the fluoride main body of doping and CRI can be quite high, but one potential Limitation is that their degradations of (for example, being exposed to 80 degrees Celsius and 85% relative humidity) under the conditions of high temperature and high humidity (HTHH) are quick Perception.Such as US 8, described in 252,613, this degradation can reduce using synthesis post-processing step.However, the stabilization of material Property in it is further improvement be desired.

Summary of the invention

In one embodiment, it provides for synthesizing manganese (Mn⁴⁺) doping phosphor method.By Formulas I (hereafter) Phosphor precursors are ground to required or specified granularity, then contact at high temperature with containing fluorine oxidiser, to form Mn4+ doping Phosphor

A_x[MF_y]:Mn⁴⁺ (I)

Wherein A represents Li, Na, K, Rb, Cs or combinations thereof, M represent Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or combinations thereof, x have [MF_y] ion charge absolute value value, and y have 5,6 or 7 value.

In one embodiment, the Mn that can be produced by this method is provided⁴⁺The phosphor of doping, and provide including Mn⁴⁺The illumination instrument and back lighting device of the phosphor of doping.

In another embodiment, for synthesizing manganese (Mn⁴⁺) method of phosphor of doping includes abrading type A_x[MF_y]: Mn⁴⁺Phosphor precursors particle, wherein A includes one of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) or caesium (Cs) or more Kind, M includes silicon (Si), germanium (Ge), tin (Sn), titanium (Ti), zirconium (Zr), aluminium (Al), gallium (Ga), indium (In), scandium (Sc), hafnium (Hf), one of yttrium (Y), lanthanum (La), niobium (Nb), tantalum (Ta), bismuth (Bi) or gadolinium (Gd) or a variety of, x have [MF_y] ion Charge absolute value value, and y have at least five and be not more than seven value.This method may also include by make particle with it is fluorine-containing Oxidant contacts come ground particle of annealing, and by making particle and formula B_x[M’F_y] compound in aqueous hydrofluoric acid Saturated solution contact handle the surface of annealed particle, wherein B includes one of Na, K, Rb or Cs or a variety of, and M ' includes one of Si, Ge or Ti or a variety of.This method, which may additionally include by contacting particle with containing fluorine oxidiser, to be located The surface for managing particle makes particle anneal later.In one embodiment, the compound of the additive Mn prepared by this method is provided Fluoride phosphor, illumination instrument and/or back lighting device including such phosphor.

In one embodiment, method includes acquisition formula A_x[MF_y]:Mn⁴⁺Phosphor precursors particle, wherein A include One of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) or caesium (Cs) are a variety of, and M includes silicon (Si), germanium (Ge), tin (Sn), titanium (Ti), zirconium (Zr), aluminium (Al), gallium (Ga), indium (In), scandium (Sc), hafnium (Hf), yttrium (Y), lanthanum (La), niobium (Nb), tantalum (Ta), bismuth (Bi) or one of gadolinium (Gd) or a variety of, x have [MF_y] ion charge absolute value value, and y have at least five and Value no more than seven.This method further includes reducing the size of phosphor precursors particle by wet-milling particle, and by making Grain makes the particle through wet-milling anneal with contact containing fluorine oxidiser.Additionally, it is provided the additive Mn prepared by this method is answered Close fluoride phosphor.Additionally provide illumination instrument and back lighting device comprising pass through the phosphorescence of additive Mn prepared by this method Body.

In one embodiment, method includes obtaining K₂SiF₆:Mn⁴⁺The particle of phosphor precursors, by wet-milling particle come Reduce the size of phosphor precursors particle, and so that the particle through wet-milling is annealed by making particle and contact containing fluorine oxidiser. Additionally, it is provided the composite fluoride phosphor of the additive Mn prepared by this method.Additionally provide illumination instrument and backlight dress It sets comprising pass through the phosphor of additive Mn prepared by this method.

Detailed description of the invention

When reference attached drawing reads following detailed descriptions, these and other features, aspects and advantages of present subject matter will It is better understood, wherein identical appended drawing reference indicates identical component in all the appended drawings, in which:

Fig. 1 is the schematic cross section of the illumination instrument of one embodiment according to the inventive subject matter；

Fig. 2 is the schematic cross section of the illumination instrument of another embodiment according to the inventive subject matter；

Fig. 3 is the schematic cross section of the illumination instrument of another embodiment according to the inventive subject matter；

Fig. 4 is the cross-sectional side elevational view of the illumination instrument of one embodiment according to the inventive subject matter；

Fig. 5 is the perspective schematic view of surface-mount devices (SMD) backlight LED；

Fig. 6 shows the flow chart of one embodiment of the method for providing phosphor particles；

Fig. 7 schematically shows another example of grinding phosphor precursors powder or particle；

Fig. 8 shows the flow chart of the another embodiment of the method for providing phosphor particles；With

Fig. 9-12 is scanning electron microscope (SEM) figure using the various phosphor particles samples of secondary electron mode Picture.

Specific embodiment

As the approximating language used in the whole instruction and claims herein can be applied to modification can Change any quantificational expression changed without will lead to its relevant basic function in a manner of license.Correspondingly, by one or The value of multiple terms such as " about " modification is not limited to specified exact value.In some cases, approximating language can correspond to For measuring the precision of the instrument of described value.Unless the context is clearly stated, otherwise in following description and claim In book, singular "one", "an" and " should/described " include plural referents.

In one or more embodiments of methods described herein, phosphor precursors are ground into particle, be followed by subsequent processing through The particle of grinding, to enhance obtained Mn⁴⁺The performance and stability of the phosphor of doping are (for example, quantum efficiency, thermostabilization Property, humidity stability and/or luminous flux stability).By phosphor precursors grinding (or grinding) to reduce granularity for required property Matter.For example, the granularity with phosphor reduces, the rate of settling of the particle in sealant material (for example, silicone) (or precipitating speed Rate) it reduces.By Control granularity and size distribution, the rate of settling of particle is adjusted, with other phosphors in blend Matching, more slowly or faster than it, and therefore can control the separation of phosphor.The separation of phosphor can be beneficial to protect Mn⁴⁺ The phosphor of doping is from the damage by excitation flux.In addition, the amount of controllable phosphor particles and position are (with LED chip It is closer or farther), to realize required color point.In addition, small grain size (D50 granularity is less than 30 microns) is allowed using simple heavy Product technology, such as spraying technology.Phosphor with smaller particle size, and to being effectively prevented from nozzle in LED packaging process Phosphor apply during be blocked be also it is beneficial.Granularity can indicate to survey along straight line (for example, rather than circumference or perimeter) The largest outer dimension of the particle of amount.

Phosphor precursors are the manganese (Mn of Formulas I⁴⁺) doping composite fluoride material.Composite fluoride material or phosphor packet Include complex, the complex includes at least one coordination center, the coordination center be as the fluorine of ligand from Attached bag encloses and as needed by counter ion counterionsl gegenions charge compensation.In one example, K₂SiF₆:Mn⁴⁺, coordination center is Si and resists Weighing apparatus ion is K.Composite fluoride can be write as the combination of simple binary fluoride once in a while, but this expression does not indicate that in coordination The ligancy of ligand around the heart.Square brackets (omitting for the sake of simplicity and sometimes) instruction is included is and letter in complex ion therein The different new chemical species of single fluorine ion.Activator ion (Mn⁴⁺) coordination center is also functioned as, replace the part at host lattice center, Such as Si.Host lattice (including counter ion counterionsl gegenions) can also modify excitation and the emission characteristic of activator ion.

It can be by that will include that the first solution of one or more potassium resources and the second solution including one or more silicon sources add Enter in container and synthesize phosphor precursors, the container has the third solution including one or more manganese sources.Stirring is by these The combination liquid that solution is formed, and K₂SiF₆:Mn⁴⁺Particle is precipitated from the solution mixture of stirring as phosphor precursors. The K of formation₂SiF₆:Mn⁴⁺The size distribution of particle is usually influenced by processing factors, the processing factors such as material solution it is dense Degree, flow velocity, stirring rate, surface appearance of reactor etc..The precipitating particle of phosphor precursors and remaining solution are mixed Object is discharged from container, then filters to separate the solid particle of phosphor precursors from liquid.Then these particles can be existed It is cleaned in acetone and dry.

In a particular embodiment, the coordination center of precursor, i.e. M in Formulas I are Si, Ge, Sn, Ti, Zr or combinations thereof.It is more special Not, coordination center is Si, Ge, Ti or combinations thereof, and counter ion counterionsl gegenions in Formulas I or A are Na, K, Rb, Cs or combinations thereof, and And y is 6.The example of the precursor of Formulas I includes K₂[SiF₆]:Mn⁴⁺、K₂[TiF₆]:Mn⁴⁺、K₂[SnF₆]:Mn⁴⁺、Cs₂[TiF₆]:Mn^{4 +}、Rb₂[TiF₆]:Mn⁴⁺、Cs₂[SiF₆]:Mn⁴⁺、Rb₂[SiF₆]:Mn⁴⁺、Na₂[TiF₆]:Mn⁴⁺、Na₂[ZrF₆]:Mn⁴⁺、K₃ [ZrF₇]:Mn⁴⁺、K₃[BiF₆]:Mn⁴⁺、K₃[YF₆]:Mn⁴⁺、K₃[LaF₆]:Mn⁴⁺、K₃[GdF₆]:Mn⁴⁺、K₃[NbF₇]:Mn⁴⁺And/or K₃[TaF₇]:Mn⁴⁺.In a particular embodiment, the precursor of Formulas I is K₂SiF₆:Mn⁴⁺。

Phosphor precursors can be ground by grinding technique, crushing, ball is sanded in for example planetary grinding of the grinding technique Mill, air jet grinding, crushing technology or combinations thereof.In a particular embodiment, by phosphor precursors ball milling.Other grind can be used (or grinding) technology of mill provides reduced granularity (for example, D50 granularity is less than about 25 microns).In one embodiment, it grinds It is executed in vacuum or inert environments.It will be understood, therefore, that reducing any of the granularity of phosphor precursors by these mechanical means Range of the method without departure from present subject matter.As described below, in one embodiment, it also can be used and be dissolved in HF solution It is saturated K₂SiF₆Wet bulb grinding process grind phosphor precursors, to increase the reliable of the phosphor generated by ground precursor Property (relative to other grindings or attrition techniques are used).

The particle for grinding or grinding the phosphor precursors of Formulas I can carry out the selected period, and rotation speed part takes The size of particle certainly before grinding, together with the required size of particle obtained after grinding.In one embodiment, particle has D50 value (or D50 granularity) is less than about 30 microns of size distribution after grinding.In a particular embodiment, the D50 grain of abrasive grains Spending range is about 10 microns to about 20 microns, and more particularly about 12 microns to about 18 microns.

In some embodiments, liquid medium can be used for grinding.Liquid medium may include ketone such as acetone, alcohol, ester for example Or mixtures thereof tert-butyl acetate, water, acid.During the grinding process, the phosphor composition of Formulas I is usually gone back via hydrolysis and oxidation Original reaction is reacted with liquid medium, and shows the reduction in its performance.For example, table 1 shows the K when being ground with acetone₂ [SiF₆]:Mn⁴⁺(PFS) decline of quantum efficiency at any time.Except Formulas I phosphor to the sensibility of many liquid mediums it Outside, grinding can also introduce a defect into the phosphor precursors of Formulas I, and to reduce the performance of obtained phosphor.At one In embodiment, the liquid medium for grinding phosphor precursors can be by the saturation K that dissolves in HF solution at room temperature₂SiF₆Shape At as described below.

Alternatively, when dry grinding in dry air or other environment, the rupture of phosphor particles increases these Sensibility of the grain to hydrolysis and with the redox reaction of the moisture in air.This can also reduce the performance of phosphor.Therefore, root According to one or more embodiments of present subject matter, after milling, particle is handled to enhance obtained Mn⁴⁺The phosphorescence of doping The performance and stability (quantum efficiency, thermal stability, humidity stability, flux stability and colour stability) of body.At one In embodiment, ground particle is contacted with gaseous form containing fluorine oxidiser at high temperature.

Particle its it is lower be about 200 DEG C to about 700 DEG C during contact, particularly from about containing the temperature that fluorine oxidiser contacts 350 DEG C to about 600 DEG C, and in some embodiments, any temperature within the scope of about 200 DEG C to about 700 DEG C.Of the invention In various embodiments, temperature is at least 100 DEG C, especially at least 225 DEG C, and more particularly at least 350 DEG C.Phosphor precursors Grain contacts a period of time for being enough to increase the performance and stability of obtained phosphor with oxidant.Time and temperature are mutual It is associated, and can adjust together, such as increase the time while reducing temperature, or increase temperature while reducing the time Degree.In a particular embodiment, the time is at least one hour, especially at least four hours, more particularly at least six hours, and it is most special It is not at least eight hours.

After keeping required period at high temperature, the rate that temperature can be controlled is reduced, while oxidizing atmosphere being tieed up It holds in the initial cooling phase.After the initial cooling phase, cooling rate can be controlled with identical rate or different rates, or It can be uncontrolled.In some embodiments, cooling rate at least controls the temperature until reaching 200 DEG C.In other embodiments, It is safe temperature that cooling velocity, which is at least controlled until reaching purging atmosphere under it,.For example, the purging in fluorine atmosphere starts it Before, temperature can be reduced to about 50 DEG C.

Compared with reducing temperature with 10 DEG C/min of rate, reducing temperature with≤5 DEG C/min of controllable rate be can get Phosphor product with excellent properties.In various embodiments, controllable-rate system is at≤5 DEG C/min, especially≤3 DEG C/minute Clock, rate more particularly≤1 DEG C/min.

It is related with Contact Temperature and cooling rate with the period that controllable rate reduces temperature.For example, when Contact Temperature is 540 DEG C, and when cooling rate is 10 DEG C/min, the time for controlling cooling rate can permit less than one hour, after this Perhaps temperature is down to purging or environment temperature and is controlled without outside.When Contact Temperature be 540 DEG C, and cooling rate be≤5 DEG C/minute Zhong Shi is then smaller than two hours cooling time.It is when Contact Temperature is 540 DEG C, and cooling rate is≤3 DEG C/min, then cold But the time is smaller than three hours.When Contact Temperature is 540 DEG C, and cooling rate is≤1 DEG C/min, then cooling time can Less than four hours.For example, temperature can be reduced to about 200 DEG C by controlled cooling, then can stop controlling.In controlled cooling phase Afterwards, the speed decline that temperature can be more higher or lower than initial controllable rate.

It can be AlF containing fluorine oxidiser₃、SbF₅、ClF₃、BrF₃、KrF、XeF₂、XeF₄、NF₃、SiF₄、PbF₂、ZnF₂、SnF₂、 CdF₂Or combinations thereof.It in one or more embodiments, is F containing fluorine oxidiser₂.The amount of oxidant in atmosphere is changeable, with spy It is not to be combined to obtain stable phosphor particles with the variation of time and temperature.It is F when containing fluorine oxidiser₂When, it can wrap in atmosphere Include at least 0.5%F₂Although lower concentration may be effective in some embodiments.Particularly, may include in atmosphere to Few 5%F₂And more particularly at least 20%F₂.Atmosphere can also comprise with the nitrogen of any combination containing fluorine oxidiser, helium, neon, argon, Krypton, xenon.In a particular embodiment, atmosphere is by about 20%F₂About 80% nitrogen composition.

Ground particle is set to be enough to convert precursor granules to required with containing the mode that fluorine oxidiser contacts Any mode of the stable phosphor of property is realized.In some embodiments, the room containing precursor granules can be measured (dosed) it and seals, so that superpressure develops as room is heated, and in other embodiments, fluorine and nitrogen mixture are moving back Fiery process flows from beginning to end, it is ensured that pressure more evenly.In some embodiments, other dosage can be introduced over time Contain fluorine oxidiser.

In one embodiment, after contacting particle with containing fluorine oxidiser, such as US 8, described in 252,613, Formula II is used Saturated solution of the composition in aqueous hydrofluoric acid is further processed ground particle.

A_x[MF_y] (II)

Phosphor is about 20 DEG C to about 50 DEG C in its lower temperature range contacted with solution.Time needed for handling phosphor Segment limit is about one minute to about five hours, particularly from about five minutes to about one hour.The concentration model of hydrofluoric acid in HF aqueous solution Enclosing is about 20%w/w to about 70%w/w, particularly from about 40%w/w to about 70%w/w.The solution of low concentration can lead to lower Phosphor yield.

Any numerical value described herein includes using a unit as all values slave lower limit value to upper limit value of increment, only It will there are the intervals of at least two unit between any lower limit value and any upper limit value.For example, if the amount of statement component Or the value of process variable (such as temperature, pressure, time etc.) is such as 1 to 90, preferably 20 to 80, more preferable 30 to 70, then Desired value such as 15 to 85,22 to 68,43 to 51,30 to 32 etc. is clearly enumerated in the present specification.For the value less than one, fit At that time, a unit was considered as 0.0001,0.001,0.01 or 0.1.These are only specific expected example, and between The all possible combination of numerical value between cited minimum and peak should be considered in this application in a similar manner Clearly state.

On the other hand, present subject matter provides method, this method includes grinding the particle of phosphor precursors, so Contact ground precursor granules with containing fluorine oxidiser afterwards, to form Mn⁴⁺The phosphor of doping.Precursor is selected from:

(A)A₂[MF₅]:Mn⁴⁺(wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof, and M is selected from Al, Ga, In and its group Close),

(B)A₃[MF₆]:Mn⁴⁺(wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof, and M is selected from Al, Ga, In and its group Close),

(C)Zn₂[MF₇]:Mn⁴⁺(wherein M is selected from Al, Ga, In and combinations thereof),

(D)A[In₂F₇]:Mn⁴⁺(wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof),

(E)A₂[MF₆]:Mn⁴⁺(wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof, and M is selected from Ge, Si, Sn, Ti, Zr And combinations thereof),

(F)E[MF₆]:Mn⁴⁺(wherein E is selected from Mg, Ca, Sr, Ba, Zn and combinations thereof, and M is selected from Ge, Si, Sn, Ti, Zr And combinations thereof),

(G)Ba_0.65Zr_0.35F_2.70:Mn⁴⁺, and

(H)A₃[ZrF₇]:Mn⁴⁺) (wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof).

Described above is for the time of this method, temperature and containing fluorine oxidiser.Mn4+ in Formulas I and group (A)-(H) mixes Manganese amount in miscellaneous precursor and product phosphor be about 0.3 weight percent (weight %) of the total weight based on precursor or phosphor extremely About 2.5 weight % (about 1.2 molar percentages (mole %) to about 10 moles of %).In some embodiments, the amount range of manganese is About 0.3 weight % to about 1.5 weight % (about 1.2 moles of % to about 6 moles of %), particularly from about 0.50 weight % to about 0.85 weight It measures % (about 2 moles of % to about 3.4 moles of %), and more particularly about 0.65 weight % to about 0.75 weight % (about 2.6 moles of % To about 3 moles of %).In other embodiments, the amount range of manganese is that (about 3 moles of % are to about by about 0.75 weight %-2.5 weight % 10 moles of %), particularly from about 0.9 weight % to 1.5 weight % (about 3.5 moles of % to about 6 moles of %), more particularly about 0.9 Weight % to about 1.4 weight % (about 3.0 moles of % to about 5.5 moles of %), and even more particularly from about 0.9 weight % is to about 1.3 weight % (about 3.5 moles of % to about 5.1 moles of %).In a specific embodiment being described below, Mn is 0.7 weight Measure % to 0.9 weight %.

Show that the illumination instrument 10 of one embodiment according to the inventive subject matter (is optionally known as the group that shines in Fig. 1 Part or lamp).Illumination instrument 10 includes the semiconductor radiant source for being shown as LED chip 12, and is electrically attached to drawing for LED chip 12 Line 14.Lead 14 can be able to be self-supporting electrode for the filament or lead supported by thicker lead frame 16, and can omit Lead frame.Lead 14 provides electric current to LED chip 12, and therefore chip emission is promoted to radiate.

Lamp may include any semiconductor blue or UV light source, described when the radiation of its transmitting is directed on phosphor Light source can generate white light.In one embodiment, semiconductor light source is the blue-light-emitting LED doped with various impurity.Therefore, LED may include the transmitting for being based on any suitable III-V, II-VI or IV-IV semiconductor layer, and having about 250 to 550nm The semiconductor diode of wavelength.Particularly, LED contains at least one semiconductor layer comprising GaN, ZnSe or SiC.For example, LED may include by Formulas I n_iGa_jAl_kN (wherein 0≤i；0<j；0≤k and i+j+k=1) indicate nitride partly lead Body has greater than about 250nm and is less than about the launch wavelength of 550nm.In a particular embodiment, chip be have about 400 to The transmitting black light of the peak emission wavelength of about 500nm or the LED of blue light.For convenience's sake, radiation source is retouched herein It states as LED.However, radiation source can cover other semiconductor radiant sources including such as semiconductor laser diode.In addition, although The general discussion of the exemplary construction for the present subject matter being discussed herein is directed to the light source based on inorganic LED, it is to be understood that, unless It is otherwise noted, otherwise LED chip can be replaced another radiation source, and for semiconductor, semiconductor LED or LED chip Any refer to only represents any radiation source appropriate, including but not limited to Organic Light Emitting Diode.

In illumination instrument 10, phosphor material or the radiation of composition 22 are connected to LED chip 12.Phosphor material or group It closes object 22 and can be radiated with LED chip 12 and coupled, so that coming from the radiation quilt of one (for example, composition 22 and/or LED chip 12) It is transferred to another.Phosphor composition 22 is deposited on LED chip 12 by any method appropriate, for example, forming phosphorescence The suspension based on water of body, and LED surface is applied to as phosphor layer.It, will wherein phosphorus in a kind of such method The silicone slurry that body of light particle suspends at random is placed on around LED.This method is only phosphor composition 22 and LED chip 12 One example of possible position.Therefore, by the way that phosphor suspension is coated on LED chip 12 and is dried on it, phosphorus Body of light composition 22 can be coated on the light-emitting surface of LED chip 12 or directly over.The silicone base suspension the case where Under, suspension solidifies at moderate temperatures.Shell 18 and sealant 20 should be both it is transparent, with allow white light 24 transmit Pass through these elements.In one or more embodiments, the D50 particle size range of phosphor composition is about 1 to about 50 micron, special It is not about 10 to about 35 microns.

In other embodiments, phosphor composition 22 is dispersed in sealant material 20, rather than directly in LED chip It is formed on 12.Phosphor (in powder form) may be interspersed in the single region of sealant material 20 or in the whole of sealant material A volume is everywhere.The blue light issued by LED chip 12 is mixed with the light issued by phosphor composition 22, and mixed light is aobvious It is shown as white light.If phosphor will be dispersed in the material 20 of sealant, polymer or silicone can be added in phosphor powder In precursor, then mixture can be solidified with curable polymer or silicon after or before mixture is loaded to LED chip 12 Ketone material.The example of polymer precursor includes thermoplasticity or thermosetting polymer or resin, such as epoxy resin.It also can be used Its phosphor interspersion methods, such as transmitting load.

In some embodiments, sealant material 20 has refractive index R, and except phosphor (s) composition 22, also contains There are the diluent materials with absorbance and refractive index R ± 0.1 less than about 5%.Diluent materials are with≤1.7, especially ≤ 1.6, and refractive index more particularly≤1.5.In a particular embodiment, diluent materials have Formula II, A_x[MF_y], and have There is about 1.4 refractive index.Optics non-active material is added into phosphor/silicone mixture can produce through phosphor/sealing The more progressive light flux distribution of agent composition, and can lead to the relatively Small loss to phosphor.Suitable material for diluent Including fluoride compound such as MgF₂、CaF₂、SrF₂、AlF₃、K₂NaAlF₆、KMgF₃、CaLiAlF₆、K₂LiAlF₆And K₂SiF₆, It is about 1.38 (AlF that the fluoride compound, which has range,₃And K₂NaAlF₆) to about 1.43 (CaF₂) refractive index, and tool Having range is the polymer of the refractive index of about 1.254 to about 1.7.It is suitable as the non-limitative example packet of the polymer of diluent Polycarbonate, polyester, nylon, polyetherimide, polyether-ketone are included, and is derived from styrene, acrylate, methacrylic acid Ester, vinyl, vinyl acetate, ethylene, propylene oxide and oxirane monomers polymer and its copolymer, including it is halogenated With non-halogenated derivative.These polymer powders can be directly incorporated into silicone sealant before silicone cure.

In another embodiment, phosphor composition 22 is coated on the surface of shell 18, rather than in LED chip It is formed on 12.Phosphor composition is preferably coated on the inner surface of shell 18, although need, phosphor can be coated on shell Outer surface on.Phosphor composition 22 can be coated in the whole surface of shell or only be coated on the top of surface of shell Point.The UV/ blue light issued by LED chip 12 is mixed with the light issued by phosphor composition 22, and mixed light is shown as White light.Certainly, phosphor can be located in any two or all three positions or any other suitable position, for example, with shell It separates or is integrated into LED.

Fig. 2 shows second structures according to the system of invention described herein theme.Unless otherwise stated, coming From Fig. 1 to 4, the respective digital of (for example, 112 in 12 and Fig. 2 in Fig. 1) is associated with the corresponding construction in each figure.Fig. 2's The structure of embodiment is similar to that of Fig. 1, in addition to phosphor composition 122 is dispersed in sealant material 120, rather than Except being formed directly on LED chip 112.Phosphor (in powder form) may be interspersed in the single region of sealant material or Sealant material whole volume everywhere.The radiation (being indicated by arrow 126) that is emitted by LED chip 112 with by phosphor 122 The light of sending mixes, and mixed light is shown as white light 124.If phosphor interspersion is in sealant material 120, phosphorescence Body powder can be added in polymer precursor, be then loaded into around LED chip 112.Then polymer or silicone precursor can be made solid Change, so that polymer or silicone solidification.Other known phosphor interspersion methods, such as transfer modling can also be used.

Fig. 3 is shown may structure according to the third of the system of invention described herein theme.Implement shown in Fig. 3 The structure of example is similar to that of Fig. 1, in addition to phosphor composition 222 is applied on the surface of encapsulation object 218, rather than Except being formed on LED chip 212.Phosphor composition 222 is preferably coated on the inner surface of encapsulation object (envelope) 218, Although need, phosphor can be coated on the outer surface of encapsulation object.Phosphor composition 222 can be coated on the entire of encapsulation object On surface or only it is coated on the top section on encapsulation object surface.The radiation 226 that is emitted by LED chip 212 with by combination of phosphors The light mixing that object 222 issues, and mixed light is shown as white light 224.Certainly, can constitutional diagram 1-3 structure, and phosphor It can be located in any two or all three positions or any other suitable position, such as separate or be integrated into encapsulation object In LED.

In any above structure, lamp may also include multiple scattering particles (not shown) in embedding sealing agent material.It dissipates Penetrating particle may include such as aluminium oxide or titanium dioxide.Scattering particles effectively scatter the directional light issued from LED chip, preferably With negligible uptake.

As shown in the 4th structure in Fig. 4, LED chip 412 can be fixed in reflector 430.Cup 430 can be by dielectric material It is made or is coated with dielectric material, such as aluminium oxide, titanium dioxide or other dielectric powders known in the art, or by anti- Radioglold belongs to such as aluminium or silver coating.The rest part of the structure of the embodiment of Fig. 4 is identical as any of earlier figures, and can wrap Include two leads 416, conducting wire 432 and sealant material 420.Reflector 430 is supported by first lead 416, and conducting wire 432 is used In LED chip 412 is electrically connected with the second lead 416.

Another structure (being especially used for backlight application) is surface-mount devices (" SMD ") type light emitting diode 550, example Such as, as shown in Figure 5.The SMD is " side emission type ", and has luminescence window on the protrusion of light conducting member 554 552.SMD encapsulation may include LED chip as defined above, and the light activated phosphor material issued by LED chip. Other back lighting devices include but is not limited to TV, computer, monitor, smart phone, tablet computer and other hand-held devices, With the display including semiconductor light source；And Mn according to the inventive subject matter⁴⁺The phosphor of doping.

When being used together with the LED emitted under 350 to 550nm with one or more other phosphors appropriate, institute Obtained lighting system has the light of white by generating.The scattering particles that lamp 10 may also include in embedding sealing agent material (do not show Out).Scattering particles may include such as aluminium oxide or titanium dioxide.Scattering particles effectively scatter the orientation issued from LED chip Light preferably has negligible uptake.

Except Mn⁴⁺Except the phosphor of doping, phosphor composition 22 may also include one or more other phosphors.When When the blue or near ultraviolet LED of radiation in luminaire with transmitting within the scope of about 250 to 550nm are applied in combination, by component The gained light of sending will be white light.Other phosphors can be used in the blend, such as green, blue, yellow, red, orange Or the phosphor of other colors, to customize the white of gained light and generate specific spectral power distribution.Suitable for phosphor group The other materials closed in object 22 include electroluminescent polymer such as polyfluorene, preferably poly- (9,9- dioctyl fluorene) and its copolymer, Such as poly- (double-N of 9,9'- dioctyl fluorene -co-, N'- (4- butyl phenyl) diphenylamines) (F8-TFB)；Poly- (vinyl carbazole) and Polyphenylene vinylene and its derivative.In addition, luminescent layer may include blue, yellow, orange, green or red phosphorescent dye or gold Category complex compound, or combinations thereof.The material for being suitable as phosphorescent coloring includes but is not limited to three (1- phenyl isoquinolin quinoline) iridium (III) (orchil), three (2- phenylpyridine) iridium (green dye) and iridium (III) are bis- (2- (4,6- difluorophenyl) pyridine-N, C2) (blue dyes).The Commercial optical and phosphorescent metal complex of ADS (American Dyes Source, Inc.) can also be used. ADS green dye includes ADS060GE, ADS061GE, ADS063GE and ADS066GE, ADS078GE and ADS090GE.ADS Blue dyes includes ADS064BE, ADS065BE and ADS070BE.ADS orchil include ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE and ADS077RE.

Include but is not limited to for the suitable phosphor in phosphor composition 22:

((Sr_1-z(Ca,Ba,Mg,Zn)_z)_1-(x+w)(Li,Na,K,Rb)_wCe_x)₃(Al₁-_ySi_y)O_4+y+3(x-w)F_1-y-3(x-w), Wherein 0 < x≤0.10,0≤y≤0.5,0≤z≤0.5 and 0≤w≤x；

(Ca,Ce)₃Sc₂Si₃O₁₂(CaSiG)；

(Sr,Ca,Ba)₃Al_1-xSi_xO_4+xF_1-x:Ce³⁺(SASOF))；

(Ba,Sr,Ca)₅(PO₄)₃(C_l,F,Br,OH):Eu²⁺,Mn²⁺；

(Ba,Sr,Ca)BPO₅:Eu²⁺,Mn²⁺；

(Sr,Ca)₁₀(PO₄)₆*νB₂O₃:Eu²⁺(wherein 0 < ν≤1)；

Sr₂Si₃O₈*2SrCl₂:Eu²⁺；

(Ca,Sr,Ba)₃MgSi₂O₈:Eu²⁺,Mn²⁺；

BaAl₈O₁₃:Eu²⁺；

2SrO*0.84P₂O₅*0.16B₂O₃:Eu²⁺；

(Ba,Sr,Ca)MgAl₁₀O₁₇:Eu²⁺,Mn²⁺；

(Ba,Sr,Ca)Al₂O₄:Eu²⁺；

(Y,Gd,Lu,Sc,La)BO₃:Ce³⁺,Tb³⁺；

ZnS:Cu⁺,Cl-；

ZnS:Cu⁺,Al³⁺；

ZnS:Ag⁺,Cl-；

ZnS:Ag⁺,Al³⁺；

(Ba,Sr,Ca)₂Si_1-ξO_4-2ξ:Eu²⁺(wherein 0.2≤ξ≤0.2)；

(Ba,Sr,Ca)₂(Mg,Zn)Si₂O₇:Eu²⁺；

(Sr,Ca,Ba)(Al,Ga,In)₂S₄:Eu²⁺；

(Y,Gd,Tb,La,Sm,Pr,Lu)₃(Al,Ga)_5-αO_12-3/_2α: Ce3+ (wherein 0≤α≤0.5)；

(Ca,Sr)₈(Mg,Zn)(SiO₄)₄Cl₂:Eu²⁺,Mn²⁺；

Na₂Gd₂B₂O₇:Ce³⁺,Tb³⁺；

(Sr,Ca,Ba,Mg,Zn)₂P₂O₇:Eu²⁺,Mn²⁺；

(Gd,Y,Lu,La)₂O₃:Eu³⁺,Bi³⁺；

(Gd,Y,Lu,La)₂O₂S:Eu³⁺,Bi³⁺；

(Gd,Y,Lu,La)VO₄:Eu³⁺,Bi³⁺；

(Ca,Sr)S:Eu²⁺,Ce³⁺；

SrY₂S₄:Eu²⁺；

CaLa₂S₄:Ce³⁺；

(Ba,Sr,Ca)MgP₂O₇:Eu²⁺,Mn²⁺；

(Y,Lu)₂WO₆:Eu³⁺,Mo⁶⁺；

(Ba,Sr,Ca)_βSi_γN_μ:Eu²⁺(wherein 2 β+4 γ=3 μ)；

(Ba,Sr,Ca)₂Si_5-xAl_xN_8-xO_x:Eu²⁺(wherein 0≤x≤2)；

Ca₃(SiO₄)Cl₂:Eu²⁺；

(Lu,Sc,Y,Tb)_2-u-vCe_vCa_1+uLi_wMg_2-wP_w(Si,Ge)_3-wO_12-u/2(wherein 0.5≤u≤1,0 < v≤0.1 and 0≤w≤0.2)；

(wherein)；

(Lu, Ca, Li, Mg, Y), doped with Eu²⁺And/or Ce³⁺α-SiAlON；

(Ca,Sr,Ba)SiO₂N₂:Eu²⁺,Ce³⁺；

β-SiAlON:Eu²⁺,3.5MgO*0.5MgF₂*GeO₂:Mn⁴⁺；

(Sr,Ca,Ba)AlSiN₃:Eu²⁺；

(Sr,Ca,Ba)₃SiO₅:Eu²⁺；

Ca_1-c-fCe_cEu_fAl_1+cSi_1-cN₃, (wherein 0≤c≤0.2,0≤f≤0.2)；

Ca_1-h-rCe_hEu_rAl_1-h(Mg,Zn)_hSiN₃, (wherein 0≤h≤0.2,0≤r≤0.2)；

Ca_1-2s-tCe_s(Li,Na)_sEu_tAlSiN₃, (wherein 0≤s≤0.2,0≤f≤0.2, s+t > 0)；And/or

Ca_1-σ-χ-ΦCe_σ(Li,Na)_χEu_Φ·Al_1+σ-χSi_1-σ+χN₃, (wherein 0≤σ≤0.2,0≤χ≤0.4,0≤Φ≤ 0.2)。

The ratio of each phosphor in phosphor blends can change according to the characteristic of required light output.It is adjustable each The relative scale of various phosphors in the phosphor blend of kind embodiment, so that the transmitting when them is blended and is used for When LED light device, the visible light of scheduled x and y value is generated on CIE chromaticity diagram.As stated, white light is preferably generated. For example, the white light can have the x value in about 0.20 to about 0.55 range, and the y value in about 0.20 to about 0.55 range. However, as described, every kind of phosphor in phosphor composition personal part and amount can become according to the needs of end user really Change.For example, the material can be used for being intended for the LED of liquid crystal display (LCD) backlight.In this application, passing through LCD/ coloured silk After colo(u)r filter combination, LED color dot is suitably tuned white based on expectations, red, green and blue.It provides herein The list of potential phosphor for blending be not exhausted, and these Mn⁴⁺The phosphor of doping can be different from having The various phosphors of transmitting are blended, to realize required spectral power distribution.

The Mn of invention as described herein theme⁴⁺The phosphor of doping can be used in the application in addition to those described above.For example, The material can be used as the phosphor in fluorescent lamp, cathode-ray tube, plasma display device or liquid crystal display (LCD).It should Material also acts as the scintillator in electromagnetic calorimeter, gamma camera, computed tomographic scanner or laser.These Purposes is only example, and does not limit all embodiments of invention as described herein theme.

Example

Following examples is merely illustrative, and should not be construed as to all scope of embodiments that theme is claimed Any kind of limitation.

According to reference United States Patent (USP) 7, program described in 497,973, in HF solution, with about 70 degrees Celsius of drying Temperature synthesizes manganese (Mn⁴⁺) doping K₂SiF₆。

By the K of 72.6 microns of D50₂SiF₆:Mn₄₊Particle ball milling 20 minutes in acetone.The K of table 1 display and synthesis₂SiF₆: Mn⁴⁺It compares, in grinding 5 minutes and K after twenty minutes₂SiF₆:Mn⁴⁺Quantum efficiency decline.

Table 1

Sample grinds phase (minute)	D50 granularity (micron)	QE (opposite)	Abs
				0 (synthesis)	72.6	100%	90%
5	61.7	94%	89%
				20	22.3	86%	70%

Example 1: by potassium fluosilicate (PFS:Mn) precursor of 15g additive Mn, K₂SiF₆:Mn⁴⁺(it has 46 microns of D50 Granularity, and contain the Mn of the 0.76 weight % of total weight based on precursor material) 250 milliliters for containing dry grinding medium are added In NALGENE bottles, and sealed in bottle.Bottle is placed on roller mill 15 minutes.Ground precursor is taken out from bottle, is had There is 16 microns of D50 particle.Then ground precursor granules are placed in furnace chamber.Furnace chamber is vacuumized and is filled and is contained There is 20%F₂/ 80%N₂Atmosphere.Then chamber is heated until 540 DEG C.After precursor is annealed 8 hours, chamber is cooled to room Temperature.Fluorine nitrogen mixture is evacuated；Chamber is full of and is purged with nitrogen several times, to ensure to completely remove fluorine before opening chamber Gas.Then by being placed in powder (~10g) containing 100mL K₂SiF₆Saturated solution (initially by room temperature 40% Addition~5g K in HF₂SiF₆, stirring and it is prepared by filtering solution) Teflon beaker in, use K₂SiF₆Saturated solution processing Annealed PFS powder.Suspension is slowly stirred, is filtered, is washed 3-5 times in acetone, and filtrate is done under vacuum It is dry.

Example 2: by potassium fluosilicate (PFS:Mn) precursor of 15g additive Mn, K₂SiF₆:Mn⁴⁺(it has 46 microns of D50 Granularity, and contain the Mn of the 0.76 weight % of total weight based on precursor material) 250 milliliters for containing dry grinding medium are added In NALGENE bottles, and sealed in bottle.Bottle is placed on roller mill 15 minutes.Ground precursor is taken out from bottle, is had There is 24 microns to 30 microns of D50 particle.Table 2 shows that after grinding the QE of PFS:Mn precursor is reduced.Then before will be ground Body particle is placed in furnace chamber.Furnace chamber is vacuumized and is filled containing 20%F₂/ 80%N₂Atmosphere.Then chamber is added Heat is until 540 DEG C.After precursor is annealed 8 hours, chamber is cooled to room temperature.Fluorine nitrogen mixture is evacuated；Chamber is full of and Several times with nitrogen purging, to ensure to completely remove fluorine gas before opening chamber.Then by by powder (~10g) be placed in containing 100mL K₂SiF₆Saturated solution (initially by addition~5g K in 40%HF at room temperature₂SiF₆, stir and filter molten It is prepared by liquid) Teflon beaker in, use K₂SiF₆Saturated solution processing (wet process) annealed PFS powder.By suspension It is slowly stirred, filters, wash 3-5 times in acetone, and filtrate is dried under vacuum.

Table 2 shows the PFS sample of example 1 and example 2, together with the K being obtained commercially₂SiF₆: the phosphor of Mn is (relatively more real Example) quantum efficiency (QE) and stability (being tested under conditions of high throughput).Ground and post-treated sample, which is shown, to be increased The quantum efficiency (QE) added and service life, and compared with the PFS of comparative example and the PFS sample of synthesis, experience is significant smaller Damage.Example 2 is also observed, annealing makes the QE of PFS powder improve 23%-28%, reduces the suction at 300nm Luminosity, and increase the service life.In addition, wet process improves HTHH stability.The damage or loss of HTHH changes from more than 45% It is apt to less than 10%.

Table 2

One or more embodiments of aforementioned present invention theme are related to the manufacturing method for PFS, are related to synthesizing phosphorescence Body powder or particle, subsequent abrasive flour or particle then make ground powder or particle annealing, then handle annealed The surface of powder or particle.Alternatively, this method can be changed as described below, can be preferably resistant to than the above method with providing The phosphor of HTHH or other environmental conditions, while same as mentioned above, more preferable or roughly the same QE being also provided.

For example, and being ground into particle as described above, can get (such as synthesizing, such as use Formulas I) phosphor precursors (for example, using together with or not together with the ball milling of liquid medium).It then can be by making ground particle and including the oxidation of fluorine Agent contacts at high temperature, and ground particle is made to anneal.Then it can be used solution (for example, saturated solution of Formula II) processing annealed Particle.The processing can reduce the surface defect on annealed particle.The one or more of invention as described herein theme Other embodiment changes the manufacturing method, with improve the phosphor formed by particle relative to preceding method durability with Performance.

Fig. 6 shows the flow chart of another embodiment of the method 600 for providing phosphor particles.Method 600 can For manufacturing phosphor particles, in the embeddable sealant of phosphor particles or it is otherwise used for generating phosphor, uses In one or more optical assemblies as described herein or lamp.At 602, phosphor precursors are synthesized.As described above, Formulas I can be used Generate the phosphor precursors of the phosphor for tetravalence additive Mn.It can be by mixing the solution comprising potassium resource, silicon source and manganese source, so K is precipitated from mixture afterwards₂SiF₆: Mn particle, to synthesize phosphor precursors particle.These particles and remaining mixture are filtered, Solid particle to be separated with liquid.Then these particles can be cleaned in acetone or other solvents, and dry to provide Phosphor precursors particle.Precursor can synthesize the powder or particle of various sizes.In one embodiment, phosphor precursors are extremely Few some particles have 30 microns or bigger of D50 (for example, the intermediate value of size distribution is equal to or more than 30 microns).

At 604, by particle wet-milling particle is reduced in size to specified size or specified size range.It can be used wet Ball milling or another grinding technique carry out abrasive grains.Wet ball mill can be related to phosphor precursors particle and solution include in HF solution In saturation K₂SiF₆Mixture is placed in the container with the mill ball inert to solution by mixing, and rotate container with By particulate abrasive or it is milled to specified smaller size.

Fig. 7 schematically shows an example of grinding phosphor precursors powder or particle.By phosphor precursors particle 700 mix with the solution being placed in rolling container 702, and the rolling container 702 is pre-filled with mill ball 704, the grinding Ball 704 occupies the about one third of overall vessel volume to half.In one embodiment, the K of saturation is prepared at room temperature₂SiF₆ Solution is (initially by the way that K is added in 40%HF at room temperature₂SiF₆, stirring and it is prepared by filtering solution), it is molten to form grinding Liquid.By a certain amount of phosphor precursors particle (for example, 80 milligrams or another amount) and mill ball 704 (for example, 60 grams of grindings Ball or another amount) and saturation abrasive solution (for example, the K of 240 milliliters of saturations₂SiF₆/ HF solution or another amount) in container Mixing in 702 (for example, the NALGENE bottle of 250 milliliters of capacity or another type of containers).Mill ball 704 can by not with precursor The material that particle 700 reacts is formed, such as polytetrafluoroethylene (PTFE) (PTFE) ball.Container 702 is rotated to promote ball 704 in container 702 Interior movement, and grind or abrasive grains 700.In one embodiment, container 702 is placed in by USStoneware Corp. On the laboratory roller of manufacture, wherein mill speed is set as 70% or another speed.The rotation of container 702 is by the ruler of particle 700 The very little specified size or within the specified range, such as D50 granularity changed into is less than 30 microns, such as 10 microns to 20 microns or 12 Micron is to 18 microns.In one embodiment, by 700 wet-milling of particle until particle is not more than 22 microns.Alternatively, by particle 700 are ground into another size.The rolling of container 702 is sustainable to be reduced to particle 700 no more than specified size or in specified model It encloses the interior required period, such as four hours or another time span.

At 606, ground particle is made to anneal.By the way that particle to be placed in the fluorine-containing oxidation with gaseous form at high temperature Agent contact, can make particle anneal.It can be F containing fluorine oxidiser₂、AlF₃、SbF₅、ClF₃、BrF₃、KrF、XeF₂、XeF₄、NF₃、SiF₄、 PbF₂、ZnF₂、SnF₂、CdF₂Or combinations thereof.At at least 200 degrees Celsius to 700 degrees Celsius of temperature or another temperature, it can incite somebody to action Particle is placed in be contacted with containing fluorine oxidiser.Alternatively, at least 350 degrees Celsius to 600 degrees Celsius of temperature or another temperature Under (for example, at least 100 degrees Celsius, at least 225 degrees Celsius or at least 350 degrees Celsius), particle can be placed in and contain fluorine oxidiser Contact.Particle is placed in the period contacted with containing fluorine oxidiser at high temperature to be changed based on temperature.For example, for hotter Temperature, annealing time can reduce, and for colder temperature, and annealing time can increase.

Relative to the particle by differently grinding phosphor precursors particle formation, by the above method in saturation K₂SiF₆Wet-milling particle can increase the durability of the phosphor generated by the particle that application method 600 obtains in/HF solution.The following table 3 Show before being exposed to HTHH, the phosphor precursors particle after being exposed to HTHH 47 hours it is several not same The difference in standardization QE before standardization QE and the HTHH exposure of product and after HTHH exposure.From same batch Synthesis precursor starts, and two samples are ground to 22 microns of identical D50 granularity using distinct methods.Labeled as JH-BM-A5 The sample of (control) passes through formed below: synthesis particle (such as 602), particle of then dry grinding, then make particle annealing (such as 606) surface of particle, is then handled.By by K₂SiF₆: Mn phosphor precursors powder and the stable ZrO of caesium₂Grinding stone is with 90 The mixing of gram precursor powder/tetra- hectogram grinding stones ratio, and the mixture is covered in 250 milliliters NALGENE bottles, to hold The dry grinding of row control sample.Then it places the bottle on the laboratory roller manufactured by U.S.Stoneware Corp., wherein speed Dial is set as 70%.Application method 600 prepares remaining sample (JH-BM-C2 (test) in table 3), i.e., in capping Use PTFE ball in the K of saturation in NALGENE bottles₂SiF₆Wet-milling in/HF solution.

The HTHH exposure of sample is related in the particles of different samples incorporation bi-component silicone, can for from The RTV615 of Momentive Performance Materials Inc., with 50 to 75% phosphor loaded, to generate Silicone/phosphor particles composite sample.Then these samples are poured into the Al patch bracket (plaque with small dent Holder in).For each sample measurement 450nm excitation under transmitting and reflection (relative to BaSO₄Standard).Retain Patch, and be stored under drying nitrogen as control sample.The aging under about 80 DEG C and about 80% relative humidity of other patches, And after a fixed time, re-measure the spectrum of the patch being exposed through and control patch intensity.Calculate QE and and standard sample Compare, wherein reporting relative value.The comparison of QE before aging and after aging is the measurement of sample degradation, is indicated in product The HTHH reliability of phosphor during.QE reduction is fewer, and HTHH reliability is better.

Table 3:

HTHH (80 DEG C/85%RH)	0hr	47hr	, reduce
				Powder	QE	QE	QE
JH-BM-A5 (control))	100.00%	86.00%	14.00%
				JH-BM-A5 (control)	100.00%	86.80%	13.20%
JH-BM-C2 (test)	100.00%	90.90%	9.10%
				JH-BM-C2 (test)	100.00%	92.00%	8.00%

Fig. 9 is scanning electron microscope (SEM) image of JH-BM-A5 (control) sample.Figure 10 is JH-MN-C2 (test) The SEM image of sample.As shown in table 3, the standardization QE of all samples is reduced after powder is exposed to HTHH 47 hours, but wet The sample (such as JH-BM-C2) of mill is substantially reduced less.QE by all powder prepared according to 600 wet-milling powder of method In maximum be reduced to 9.10%, and the minimum in the QE of powder prepared by application method 600 is reduced to 8.00%.However, not Experienced 13.2% or 14.0% in QE using powder prepared by wet-milling reduces.

Optionally, longer period (for example, ten hours rather than four hours) can be performed in 604 wet grinding operation, with into The size of one step reduction phosphor precursors particle.It executes wet-milling and the granularity of phosphor precursors can be reduced to for more time and is not more than 15 microns.Relative to other methods for manufacturing phosphor precursors, longer wet-milling process also further increases phosphorescence The reliability of body precursor.

The following table 4 is shown before being exposed to HTHH, the phosphor precursors after being exposed to HTHH 47 hours The difference in standardization QE before standardization QE and the HTHH exposure of several different samples of grain and after HTHH exposure It is different.Application method 600 prepares sample BM test pond F, but with by particle wet-milling ten hours, with cause D50 be 15 microns compared with Small grain size.

Table 4:

HTHH (80 DEG C/85%RH)	0hr	47hr	It reduces
				Powder	QE	QE	QE
BM test pond F	100.00%	95.37%	4.63%
				BM test pond F	100.00%	95.39%	4.61%

Figure 11 is the SEM image of BM test pond F sample.As shown in table 4, it is prepared according to method 600 by wet-milling powder, but Maximum reduce in the QE of the sample of a longer period of time is about 4.6% on an average.As described above, without using wet-milling or using wet Grind the larger reduction in the powder experience QE of shorter time period preparation.

Due to removing demanganization from the outer surface of particle, the wet-milling of phosphor precursors particle can increase particle as time go by Reliability and performance.Manganese for adulterating phosphor particles may be present in inside the particle of synthesis and both outer surfaces of particle On.During phosphor particles are exposed to moisture, manganese is degradable and reduces the QE of particle.In the K of saturation₂SiF₆In/HF solution Wet-milling can remove external manganese and reduce the size of particle, and manganese inside particle can be protected from moisture.As a result, such as this Wet milling process described in text can manufacture the phosphor of small grain size, remove demanganization from outer pellet surface, leave inside granular core Manganese allows particle as phosphor operation and to improve its HTHH reliability.

Fig. 8 shows the flow chart of another embodiment of the method 800 for providing phosphor particles.Method 800 can For manufacturing phosphor particles, in the embeddable sealant of phosphor particles or it is otherwise used for generating phosphor, uses In one or more optical assemblies as described herein or lamp.At 802, phosphor precursors are synthesized.As described above, Formulas I can be used Generate the phosphor precursors of the phosphor for tetravalence additive Mn.It can be by mixing the solution comprising potassium resource, silicon source and manganese source, so K is precipitated from mixture afterwards₂SiF₆: Mn particle, to synthesize phosphor precursors particle.These particles and remaining mixture are filtered, Solid particle to be separated with liquid.Then these particles can be cleaned in acetone or other solvents, and dry to provide Phosphor precursors particle.Precursor can synthesize the powder or particle of various sizes.In one embodiment, phosphor precursors are extremely Few some particles have 30 microns or bigger (for example, the intermediate value of size distribution is equal to or more than 30 microns).

At 804, by particle wet-milling particle is reduced in size to specified size or specified size range.It can be used wet Ball milling or another grinding technique carry out abrasive grains.Wet ball mill can be related to the K by phosphor precursors particle and saturation₂SiF₆/ HF is molten Liquid mixing, mixture is placed in the container with the mill ball inert to solution, and rotates container with by particulate abrasive Or it is milled to smaller size.It, can be by particle wet-milling as above with method 600 in conjunction with described in.

At 806, ground particle is made to anneal.By the way that particle to be placed in the fluorine-containing oxidation with gaseous form at high temperature Agent contact, can make particle anneal.It can be F containing fluorine oxidiser₂、AlF₃、SbF₅、ClF₃、BrF₃、KrF、XeF₂、XeF₄、NF₃、SiF₄、 PbF₂、ZnF₂、SnF₂、CdF₂Or combinations thereof.At at least 200 degrees Celsius to 700 degrees Celsius of temperature or another temperature, it can incite somebody to action Particle is placed in be contacted with containing fluorine oxidiser.Alternatively, at least 350 degrees Celsius to 600 degrees Celsius of temperature or another temperature Under (for example, at least 100 degrees Celsius, at least 225 degrees Celsius or at least 350 degrees Celsius), particle can be placed in and contain fluorine oxidiser Contact.Particle is placed in the period contacted with containing fluorine oxidiser at high temperature to be changed based on temperature.For example, for hotter Temperature, annealing time can reduce, and for colder temperature, and annealing time can increase.

At 808, particle is set to anneal again.It is connect with gaseous form containing fluorine oxidiser by being at high temperature placed in particle Touching, can make particle anneal again.Reagent and temperature for annealing can be identical as what is used at 806, or can be used different Reagent and/or temperature.

The particle that is formed relative to not wet-milling phosphor precursors particle or relative to without using wet-milling and being moved back using other The particle that fire operation is formed, wet-milling particle and can increase the particle obtained by application method 800 using other annealing operation and produce The durability of raw phosphor.The following table 5 is shown before being exposed to HTHH, the phosphorus after being exposed to HTHH 47 hours Standardization before standardization QE and the HTHH exposure of several different samples of body of light precursor granules and after HTHH exposure Difference in QE.Labeled as JH-BM-A5 (control) sample pass through it is formed below: synthesis particle (such as 602) is then dry grinded Particle (as above with table 3 in conjunction with described in) then anneals particle (such as 606) primary.Application method 800 prepares remaining sample Product (JH-BM-C5 (test) in table 5).Since the synthesis precursor of same batch, it is 22 micro- that two samples, which are ground to D50, The same particle sizes of rice.

Table 5:

HTHH (80 DEG C/85%RH)	0hr	47hr	It reduces
				Powder	QE	QE	QE
JH-BM-A5 (control)	100.00%	86.00%	14.00%
				JH-BM-A5 (control)	100.00%	86.80%	13.20%
JH-BM-C5 (test)	100.00%	91.40%	8.60%
				JH-BM-C5 (test)	100.00%	90.30%	9.70%

Figure 12 is the SEM image of JH-BM-C5 (test) sample.As shown in table 5, the standardization QE of all samples is in powder It is reduced after being exposed to HTHH 47 hours, but wet-milling and the multiple sample (such as JH-BM-C5) of annealing are substantially reduced less.Pass through 9.70% is reduced to according to 800 wet-milling particle of method and by the maximum in the QE of all powder that particle annealing is repeatedly prepared, and Minimum in the QE of particle prepared by application method 800 is reduced to 8.60%.However, prepared without using wet-milling and repeatedly annealing Powder experienced 13.2% or 14.0% reduction in QE.

Granularity as described herein is measured using laser diffraction particle size analyzer Horiba LA-960, wherein refractive index is set For 1.4 and ultrasound applies 30 seconds under the power setting of grade 7.

Although only showing herein and describing certain features of present subject matter, those of ordinary skill in the art will expect Many modifications and variations.Thus, it will be appreciated that the expected covering of appended claims falls into the true of invention as described herein theme All such modifications and variations in spirit.

Claims (18)

1. a kind of method comprising:

Acquisition formula A_x[MF_y]:Mn⁴⁺Phosphor precursors particle, wherein A include lithium (Li), sodium (Na), potassium (K), rubidium (Rb) or One of caesium (Cs) is a variety of, and wherein M includes silicon (Si), germanium (Ge), tin (Sn), titanium (Ti), zirconium (Zr), aluminium (Al), gallium (Ga), one of indium (In), scandium (Sc), hafnium (Hf), yttrium (Y), lanthanum (La), niobium (Nb), tantalum (Ta), bismuth (Bi) or gadolinium (Gd) or A variety of, wherein x has [MF_y] ion charge absolute value value, and wherein y have at least five and be not more than seven value；

Reduce the size of the phosphor precursors particle by particle described in wet-milling；With

The particle through wet-milling is set to anneal by making the particle and contact containing fluorine oxidiser, to provide the compound fluorine of additive Mn Compound phosphor.

2. according to the method described in claim 1, the size for wherein reducing the particle is included in comprising A_x[MF_y] solution in Grind the particle.

3. according to the method described in claim 1, the size for wherein reducing the particle includes grinding in the solution comprising HF The particle.

4. according to the method described in claim 1, the size for wherein reducing the particle is included in comprising A_x[MF_y] and HF's is molten The particle is ground in liquid.

5. according to the method described in claim 1, wherein make the particle through wet-milling at least 100 degrees Celsius at a temperature of move back Fire.

6. will be in being reduced in size to of the phosphor precursors according to the method described in claim 1, wherein grinding the particle Value is not greater than about 22 microns of size distribution.

7. will be in being reduced in size to of the phosphor precursors according to the method described in claim 1, wherein grinding the particle Value is not greater than about 15 microns of size distribution.

8. the composite fluoride phosphor of a kind of additive Mn, by preparing according to the method for claim 1.

9. a kind of illumination instrument comprising:

Semiconductor light source；With

The composite fluoride phosphor of additive Mn, by preparing according to the method for claim 1.

10. a kind of back lighting device comprising:

Semiconductor light source；With

The composite fluoride phosphor of additive Mn, by preparing according to the method for claim 1.

11. a kind of method comprising:

Obtain K₂SiF₆:Mn⁴⁺The particle of phosphor precursors；

Reduce the size of the phosphor precursors particle by particle described in wet-milling；With

The particle through wet-milling is set to anneal by making the particle and contact containing fluorine oxidiser, to provide the compound fluorine of additive Mn Compound phosphor.

12. according to the method for claim 11, wherein the size for reducing the particle is included in comprising K₂SiF₆It is molten with HF The particle is ground in liquid.

13. according to the method for claim 11, wherein obtaining the particle includes that the particle is synthesized by the following way: mixing Solution comprising potassium resource, silicon source and manganese source precipitates the particle from mixed solution, and filters the particle and described molten The remainder of liquid.

14. according to the method for claim 11, wherein make the particle through wet-milling at least 100 degrees Celsius at a temperature of Annealing.

15. according to the method for claim 11, wherein grinding the particle being reduced in size to the phosphor precursors Intermediate value is not greater than about 22 microns of size distribution.

16. the composite fluoride phosphor of a kind of additive Mn, by preparing according to the method for claim 11.

17. a kind of illumination instrument comprising:

Semiconductor light source；With

The composite fluoride phosphor of additive Mn, by preparing according to the method for claim 11.

18. a kind of back lighting device comprising:

Semiconductor light source；With

The composite fluoride phosphor of additive Mn, by preparing according to the method for claim 11.