阅读说明：本技术 增强磷光体稳健性和分散性的方法及所得的磷光体 (Method for enhancing phosphor robustness and dispersibility and resulting phosphors ) 是由 马修·戴维·巴茨 詹姆斯·爱德华·墨菲 马克·丹尼尔·多尔蒂 于 2020-04-20 设计创作，主要内容包括：本申请公开了一种生产呈固体形式的稳定的Mn～(4)掺杂磷光体和含有这种掺杂磷光体的组合物的方法。这种方法可以包括将a)包含至少一种选自以下的物质的溶液：K-(2)HPO-(4)、磷酸铝、草酸、磷酸、表面活性剂、螯合剂或它们的组合与b)呈固体形式的式I的Mn～(4+)掺杂磷光体组合,其中式I可以是：A-(x)[MF-(y)]:Mn～(4+)。该方法还可以包括分离该呈固体形式的稳定的Mn～(4+)掺杂磷光体。在式I中,A可以是Li、Na、K、Rb、Cs或它们的组合。在式I中,M可以是Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Y、La、Nb、Ta、Bi、Gd或它们的组合。在式I中,x是[MF-(y)]离子的电荷的绝对值,并且y是5、6或7。(The present application discloses a method for producing stable Mn in solid form 4 Doped phosphors and compositions containing such doped phosphors. Such a method may comprise contacting a) a solution comprising at least one substance selected from the group consisting of: k 2 HPO 4 Aluminum phosphate, oxalic acid, phosphoric acid, surfactants, chelating agents or combinations thereof with b) Mn of formula I in solid form 4+ Doped phosphor combinations, wherein formula I maySo that: a. the x [MF y ]:Mn 4+ . The method may further comprise isolating the stable Mn in solid form 4+ A doped phosphor. In formula I, a can be Li, Na, K, Rb, Cs, or a combination thereof. In formula I, M may be Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof. In formula I, x is [ MF ] y ]The absolute value of the charge of the ion, and y is 5, 6 or 7.)

1. A method comprising contacting a) a solution comprising at least one substance selected from the group consisting of: k₂HPO₄Aluminum phosphate, oxalic acid, phosphoric acid, surfactants, chelating agents or combinations thereof with b) Mn of formula I in solid form⁴A doped phosphor combination;

A_x[MF_y]:Mn⁴⁺

I

and isolating the stable Mn in solid form⁴⁺A doped phosphor; wherein

A is Li, Na, K, Rb, Cs or a combination thereof;

m is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof;

x is [ MF_y]The absolute value of the charge of the ion;

y is 5, 6 or 7.

2. The method of claim 1, further comprising, prior to combining with the at least one substance, allowing the Mn of formula I to react at an elevated temperature⁴⁺The doped phosphor is contacted with a fluorine-containing oxidizing agent in gaseous form to form a product phosphor.

3. The method of claim 1, wherein

M is Si, Ge, Ti or a combination thereof;

a is Na, K or a combination thereof.

4. The method of claim 1, wherein the phosphor of formula I is K₂SiF₆:Mn⁴⁺。

5. Root of herbaceous plantThe method of claim 1, wherein the at least one substance comprises K₂HPO₄。

6. The method of claim 1, wherein the at least one substance comprises the surfactant.

7. The method of claim 1, wherein the at least one substance comprises the surfactant and K₂HPO₄。

8. The method of claim 1, wherein the solution is aqueous and further comprises H₂O₂。

9. The method of claim 6, wherein the solution further comprises at least one solvent selected from the group consisting of: 1-octadecene, iso-norbornyl acrylate, water and propylene glycol monomethyl ether acetate.

10. The method of claim 1, wherein the at least one substance comprises the surfactant, and wherein the surfactant comprises at least one selected from the group consisting of: polyoxyethylene octyl phenyl ether, potassium oleate, polyoxyethylene-polyoxypropylene block copolymer; polyoxyethylene (20) sorbitan monolaurate, poly (acrylic acid sodium salt), and potassium sorbate.

11. The method of claim 1, wherein the Mn of formula I⁴⁺A doped phosphor comprises a core comprising a phosphor of formula I and a composite coating disposed on the core, the composite coating comprising a metal fluoride selected from the group consisting of: calcium fluoride, strontium fluoride, magnesium fluoride, yttrium fluoride, scandium fluoride, lanthanum fluoride, and combinations thereof.

12. A composition comprising a) at least one substance selected from the group consisting of: k₂HPO₄Aluminum phosphate, oxalic acid, phosphoric acid or combinations thereof, withAnd b) Mn of the formula I⁴⁺A doped phosphor;

A_x[MF_y]:Mn⁴⁺

I

wherein

A is Li, Na, K, Rb, Cs or a combination thereof;

m is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof;

x is [ MF_y]The absolute value of the charge of the ion;

y is 5, 6 or 7.

13. The composition of claim 12, wherein

M is Si, Ge, Ti or a combination thereof;

a is Na, K or a combination thereof.

14. The composition of claim 12, wherein the phosphor of formula I is K₂SiF₆:Mn⁴⁺。

15. The composition of claim 12, wherein the at least one substance comprises K₂HPO₄And magnesium fluoride.

16. The composition of claim 12, wherein the Mn of formula I⁴⁺A doped phosphor comprises a core comprising a phosphor of formula I and a manganese-free composite coating disposed on the core, the manganese-free composite coating comprising a compound of formula III and a metal fluoride selected from: calcium fluoride, strontium fluoride, magnesium fluoride, yttrium fluoride, scandium fluoride, lanthanum fluoride and combinations thereof,

A¹ _x[M¹F_y](III)

wherein A is¹Is H, Li, Na, K, Rb, Cs or combinations thereof; m¹Is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is [ M ]¹F_y]The absolute value of the charge of the ion;and y is 5, 6 or 7.

17. A display device comprising the stabilized Mn produced according to the method of claim 1⁴⁺A doped phosphor.

18. The display device of claim 17, wherein the display device comprises a television, a computer display, a cell phone or traditional phone, a digital photo frame, a tablet computer, an automotive display, an e-book reader, an electronic dictionary, a digital camera, an electronic keyboard, or a gaming device.

19. A lighting device comprising the stabilized Mn produced according to the method of claim 1⁴⁺A doped phosphor.

20. A phosphor composition comprising phosphor particles and at least one surface composition on the surface of the phosphor particles selected from the group consisting of: 1) a composition comprising a phosphorus-containing moiety and a carbon-containing moiety; 2) a composition comprising the phosphorus-containing moiety and a metal fluoride; 3) a composition comprising the phosphorus-containing moiety and the carbon-containing moiety and the metal fluoride; and 4) compositions comprising the phosphorus-containing moiety without an alkyl phosphate compound, wherein the phosphor particles comprise Mn of formula I⁴⁺A doped phosphor;

A_x[MF_y]:Mn⁴⁺

I

wherein

A is Li, Na, K, Rb, Cs or a combination thereof;

m is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof;

x is [ MF_y]The absolute value of the charge of the ion;

y is 5, 6 or 7.

21. The phosphor composition of claim 20, wherein the metal fluoride comprises magnesium fluoride.

22. The phosphor composition of claim 20, wherein the phosphorous-containing moiety comprises a phosphate moiety.

23. The phosphor composition of claim 20, wherein the carbon-containing moiety comprises at least one selected from the group consisting of: ethylenediaminetetraacetic acid, polyoxyethylene octylphenyl ether, potassium oleate, polyoxyethylene-polyoxypropylene block copolymers, polyoxyethylene (20) sorbitan monolaurate, poly (acrylic acid sodium salt), potassium sorbate, and derivatives or salts thereof.

24. The phosphor composition of claim 20, wherein the phosphor particles exhibit a) a quantum efficiency after one hour of exposure to liquid water at room temperature of 50% to 100% of the quantum efficiency exhibited prior to water exposure, or B) a loss of quantum efficiency of less than 40% after 100 hours of exposure to 85% relative humidity at 85 ℃.

25. The phosphor composition of claim 20, wherein the D of the phosphor particles is prior to sonicating a suspension containing the particles₅₀A particle size of not more than 30 μm, and D of the phosphor particles after the ultrasonic treatment₅₀The particle size is not more than 20 μm.

26. A display apparatus comprising the phosphor composition of claim 20.

27. A light emitting diode apparatus radiationally coupled to and/or comprising the phosphor composition of claim 20.

28. The light emitting diode device of claim 27, wherein the light emitting diode device is a mini LED or a micro LED.

29. The light emitting diode device of claim 27, wherein a) the light emitting diode device comprises an LED chip having the phosphor composition deposited thereon, and/or b) the composition is dispersed in a polymer resin in the form of a film.

Background

Based on Mn⁴⁺Red-emitting phosphors of activated complex fluoride materials (such as those described in US 7,358,542, US 7,497,973, and US 7,648,649) may be used in combination with yellow/green-emitting phosphors such as YAG: Ce to achieve warm white light from a blue Light Emitting Diode (LED) (CCT on black body locus)<5000K, Color Rendering Index (CRI)>80) Which is equivalent to the warm white light produced by current fluorescent, incandescent and halogen lamps. These materials strongly absorb blue light and emit light efficiently in the range between about 610nm and 658nm with little deep red/near infrared emission. Thus, the luminous efficiency is maximized compared to red phosphors having significant emission in deeper red light where eye sensitivity is poor. Under the excitation of blue light (440-460nm), the quantum efficiency can exceed 85%. Furthermore, the use of red phosphors for displays may result in high color gamut and efficiency.

The preparation of Mn with improved color stability is described in US 8,906724 and other patents and patent applications assigned to General Electric Company (General Electric Company) or Current⁴⁺A method of doping a complex fluoride phosphor. However, there remains a need to even further improve the stability and dispersibility of complex fluoride phosphors while maintaining excellent performance in lighting and display applications.

Disclosure of Invention

Briefly, in one aspect, the present invention relates to a method for producing stable Mn in solid form⁺⁴A method of doping a phosphor. Such a method may comprise contacting a) a composition comprising at least one member selected from the group consisting ofSolution of the substance: k₂HPO₄Aluminum phosphate, oxalic acid, phosphoric acid, surfactants, chelating agents or combinations thereof with b) Mn of formula I in solid form⁺⁴A doped phosphor combination, wherein formula I may be: a. the_x[MF_y]:Mn⁺⁴. The method may further comprise isolating the stable Mn in solid form⁴⁺A doped phosphor. In formula I, a can be Li, Na, K, Rb, Cs, or a combination thereof. In formula I, M may be Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof. In formula I, x is [ MF ]_y]The absolute value of the charge of the ion, and y is 5, 6 or 7.

Another aspect of the invention relates to a composition comprising a) at least one substance selected from the group consisting of: k₂HPO₄Aluminum phosphate, oxalic acid, phosphoric acid or combinations thereof, and b) Mn of formula I⁴⁺A doped phosphor, wherein formula I is: a. the_x[MF_y]:Mn⁴⁺. In formula I, a can be Li, Na, K, Rb, Cs, or a combination thereof. In formula I, M may be Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof. In formula I, x is [ MF ]_y]The absolute value of the charge of the ion, and y is 5, 6 or 7.

Yet another aspect of the invention relates to a phosphor composition comprising phosphor particles and at least one surface composition on the surface thereof, the surface composition being selected from the group consisting of: 1) a composition comprising a phosphorus-containing moiety and a carbon-containing moiety; 2) a composition comprising a phosphorus-containing moiety and a metal fluoride; 3) a composition comprising a phosphorus-containing moiety and a carbon-containing moiety and a metal fluoride; and 4) compositions comprising phosphorus-containing moieties that are free of alkyl phosphate compounds, wherein the phosphor particles comprise Mn of formula I⁴⁺A doped phosphor;

A_x[MF_y]:Mn⁴⁺

wherein A is Li, Na, K, Rb, Cs, or a combination thereof;

m is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof;

x is [ MF_y]The absolute value of the charge of the ion; y is 5, 6 or 7.

Drawings

These and other features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings in which like characters represent like parts throughout the drawings, wherein:

figure 1 is a schematic cross-sectional view of an LED package according to one embodiment of the present invention;

figure 2 is a schematic cross-sectional view of an LED package according to another embodiment of the present invention;

figure 3 is a schematic cross-sectional view of an LED package according to yet another embodiment of the present invention;

figure 4 is a cross-sectional side perspective view of an LED package according to one embodiment of the present invention;

fig. 5 is a schematic perspective view of a Surface Mount Device (SMD) backlight LED.

Fig. 6 shows a backlight unit or module.

Fig. 7 shows a backlight unit or module.

Detailed Description

In one aspect, the present invention relates to a method for producing stable Mn in solid form⁴A method of doping a phosphor. Such a method may comprise contacting a) a solution comprising at least one substance selected from the group consisting of: k₂HPO₄Aluminum phosphate, oxalic acid, phosphoric acid, surfactants, chelating agents or combinations thereof with b) Mn of formula I in solid form⁴A doped phosphor combination. In one embodiment, the amounts of the above are relative to the Mn of formula I⁴⁺The amount of doped phosphor is 0.01-20% by weight, such as 1% to 15%, and 2% to 10%.

In another aspect, the present invention relates to a composition comprising a) at least one substance selected from the group consisting of: k₂HPO₄Aluminum phosphate, oxalic acid, phosphoric acid, surfactants, chelating agents or combinations thereof and b) Mn of formula I⁴A doped phosphor.

Mn of the formula I⁴⁺Doped phosphors are complex fluoride materials or coordination compounds which contain at least one coordination center surrounded by fluoride ions as ligands and are charge-compensated, if necessary, by counter-ions. For example, at K₂SiF₆:Mn⁴⁺In (3), the coordination center is Si, and the counterion is K. Complex fluorides are occasionally written as combinations of simple binary fluorides, but such a representation does not indicate the coordination number of ligands around the coordination center. Brackets (occasionally omitted for simplicity) indicate that the complex ions they contain are a new chemical species, different from simple fluoride ions. Activating ion (Mn)⁴⁺) Also as coordination centers, replace some of the centers of the host lattice, such as Si. The host lattice (including the counter-ions) may further modify the excitation and emission characteristics of the active ions.

In particular embodiments, the coordination center of the phosphor (i.e., M in formula I) is Si, Ge, Sn, Ti, Zr, or a combination thereof. More particularly, the coordination center may be Si, Ge, Ti, or a combination thereof. The counterion or a in formula I can be Na, K, Rb, Cs, or a combination thereof, more particularly K. Examples of phosphors of formula I include K₂[SiF₆]:Mn⁴⁺、K₂[TiF₆]:Mn^{4 +}、K₂[SnF₆]:Mn⁴⁺、Cs₂[TiF₆]:Mn⁴⁺、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⁺、K₃[TaF₇]:Mn⁴⁺. In a particular embodiment, the phosphor of formula I is K₂SiF₆:Mn⁴⁺。

Mn of the formula I⁴⁺The amount of manganese in the doped phosphor may be in a range of about 1.2 mol% (about 0.3 wt% based on the total weight of the phosphor) to about 21 mol% (about 5.1 wt%), specifically about 1.2 mol% (about 0.3 wt%) to about 16.5 mol% (about 4 wt%), based on the total moles of Mn and M (such as Si). In particular embodiments, the amount of manganese may be in a range of from about 2 mol% (about 0.5 wt%) to 13.4 mol% (about 3.3 wt%), or from about 2 mol% to 12.2 mol% (about 3 wt%), or from about 2 mol% to 11.2 mol% (about 2.76 wt%), or from about 2 mol% to about 10 mol% (about 2.5 wt%), or from about 2 mol% to 5.5 mol% (about 1.4 wt%), or from about 2 mol% to about 3.0 mol% (about 0.75 wt%).

In combination K, as described in US 8,906,724₂HPO₄Before aluminum phosphate, oxalic acid, phosphoric acid, surfactants, chelating agents, or combinations thereof, can be applied to the Mn of formula I⁴⁺The doped phosphor is annealed to improve stability. In such embodiments, the product phosphor is maintained at an elevated temperature while in contact with an atmosphere comprising a fluorine-containing oxidizing agent. The fluorine-containing oxidizing agent may be F₂、HF、SF₆、BrF₅、NH₄HF₂、NH₄F、KF、AlF₃、SbF₅、ClF₃、BrF₃、KrF₂、XeF₂、XeF₄、XeF₆、NF₃、SiF₄、PbF₂、ZnF₂、SnF₂、CdF₂、C₁-C₄A fluorocarbon, or a combination thereof. Examples of suitable fluorocarbons include CF₄、C₂F₆、C₃F₈、CHF₃、CF₃CH₂F and CF₂CHF. In a particular embodiment, the fluorine-containing oxidizing agent is F₂. The amount of oxidizing agent in the atmosphere can be varied to obtain a color stable phosphor, especially with variations in binding time and temperature. When the fluorine-containing oxidizing agent is F₂In the case of (2), the atmosphere may contain at least 0.5% F₂Although lower concentrations may be effective in some embodiments. In particular, gasThe atmosphere may contain at least 5% F₂And more particularly at least 20% F₂. The atmosphere may additionally include nitrogen, helium, neon, argon, krypton, xenon, and any combination with fluorine-containing oxidizing agents. In particular embodiments, the atmosphere consists of about 20% F₂And about 80% nitrogen.

The temperature at which the phosphor is contacted with the fluorine-containing oxidizing agent at the elevated temperature may be a temperature in the range of about 200 ℃ to about 700 ℃, particularly about 350 ℃ to about 600 ℃, and in some embodiments about 500 ℃ to about 600 ℃ during the contacting. The phosphor is contacted with the oxidizing agent for a period of time sufficient to convert it to a color stable phosphor. Time and temperature are interrelated and may be adjusted together, for example, by decreasing the temperature while increasing the time, or decreasing the time while increasing the temperature. In particular embodiments, the time is at least one hour, specifically at least four hours, more specifically at least six hours, and most specifically at least eight hours. After holding at the elevated temperature for the desired period of time, the temperature in the furnace may be reduced at a controlled rate while maintaining an oxidizing atmosphere during the initial cooling. The temperature can be reduced to about 200 ℃ in the case of controlled cooling, and then the control can be stopped if necessary.

The manner in which the phosphor is contacted with the fluorine-containing oxidizing agent is not critical and can be accomplished in any manner sufficient to convert the phosphor to a color stable phosphor having the desired characteristics. In some embodiments, the chamber containing the phosphor may be metered and then sealed such that an overpressure is created as the chamber is heated, and in other embodiments, the mixture of fluorine and nitrogen flows throughout the annealing process, ensuring a more uniform pressure. In some embodiments, additional doses of fluorine-containing oxidizing agent may be introduced after a period of time.

The annealed phosphor may be treated with a saturated or near saturated solution of a composition of formula II in hydrofluoric acid

A_x[MF_y]

(II)

Wherein

A is Li, Na, K, Rb, Cs or a combination thereof;

m is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof;

x is [ MF_y]The absolute value of the charge of the ion; and is

y is 5, 6 or 7.

A nearly saturated solution containing about 1% -5% excess of aqueous HF is added to the saturated solution. The concentration of HF in the solution ranges from about 25% (weight/volume) to about 70% (weight/volume), specifically from about 40% (weight/volume) to about 50% (weight/volume). Lower concentrations of the solution may result in reduced performance of the phosphor. The amount of treatment solution used is in the range of about 2-30ml/g product, particularly about 5-20ml/g product, more particularly about 5-15ml/g product. The treated annealed phosphor can be isolated by filtration, washed with solvents such as acetic acid and acetone to remove contaminants and traces of water, and stored under nitrogen.

After treatment, the phosphor may optionally be contacted with a fluorine-containing oxidizing agent in gaseous form at a second, lower temperature. The second temperature may be the same as the first temperature, or may be lower than the first temperature, ranging up to and including 225 ℃, particularly up to and including 100 ℃, and more particularly up to and including 90 ℃. The time of contact with the oxidizing agent can be at least one hour, specifically at least four hours, more specifically at least six hours, and most specifically at least eight hours. In a specific embodiment, the phosphor is contacted with the oxidizing agent at a temperature of about 90 ℃ for at least eight hours. The oxidizing agent may be the same as or different from that used in the first annealing step. In a particular embodiment, the fluorine-containing oxidizing agent is F₂. More particularly, the atmosphere may comprise at least 20% F₂. The phosphor may be contained in a container having a non-metallic surface to reduce contamination of the phosphor by the metal.

Mn of the formula I⁴⁺The doped phosphor may have a core-shell structure consisting of a core comprising the phosphor of formula I and a manganese-free shell or composite coating disposed on the core. Manganese-freeThe composite coating comprises a compound of formula III and a metal fluoride

A¹ _x[M¹F_y]

(III)

Wherein A is¹Is H, Li, Na, K, Rb, Cs or combinations thereof;

M¹is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof;

x is [ M ]¹F_y]The absolute value of the charge of the ion; and is

y is 5, 6 or 7.

The metal fluoride may be one or more of the following: calcium fluoride, strontium fluoride, magnesium fluoride, yttrium fluoride, scandium fluoride, and lanthanum fluoride. In a particular embodiment, the phosphor of formula I is K₂[SiF₆]:Mn⁴⁺. In one embodiment, the metal fluoride may be MgF₂. Core-shell Mn of the formula I is described in WO2018/093832⁴⁺Doped phosphors and methods of making the same. Mn of formula I, as described above⁴⁺The doped phosphor may be combined with (or form part of) a solution or suspension comprising one or more of the following: k₂HPO₄Aluminum phosphate, oxalic acid, phosphoric acid, surfactants, chelating agents, or combinations thereof. K₂HPO₄Aluminum phosphate, oxalic acid, phosphoric acid, surfactants, chelating agents, or combinations thereof will be referred to herein as species. The weight ratio of phosphor to substance may be 200:1 to 1:1, more preferably 50:1 to 4: 1. Examples of suitable chelating agents include, but are not limited to, ammonium citrate, potassium citrate, iminodiacetic acid (IDA), and ethylenediaminetetraacetic acid (EDTA). The surfactant may be nonionic, anionic or cationic, or mixtures thereof. Examples of suitable surfactants include, but are not limited to, aliphatic amines, fluorocarbon surfactants, stearic acid and stearates, and oleic acid and oleates. Suitable nonionic surfactants include polyoxyethylene sorbitan fatty acid esters (obtainable fromCommercially available brands), fluorocarbon surfactants such as NOVEC^TMFluoroalkyl sulfonamide ammonium (available from 3M company) and polyoxyethylene nonylphenol ether. The surfactant (or other surfactant) may be one or more of the following: polyoxyethylene octyl phenyl ether, potassium oleate, polyoxyethylene-polyoxypropylene block copolymers (such as sold as Pluronic F-127); polyoxyethylene (20) sorbitan monolaurate (such as sold as Tween 20), poly (acrylic acid sodium salt), potassium sorbate, sorbitan monooleate (such as sold as Span 80(Span 80)), and sodium hexametaphosphate. Further examples of suitable surfactants are described in US 2015/0329770, US 7,985,723 and Kikuyama et al, IEEE Transactions on Semiconductor Manufacturing, volume 3, pages 99-108, 8/1990. In particular, the substance may comprise K₂HPO₄. As mentioned above, the substance may also include a surfactant. The substance may include a surfactant and K₂HPO₄。

The solution of which the surfactant forms a part may include one or more of the following solvents: 1-octadecene, iso-norbornyl acrylate, water and propylene glycol monomethyl ether acetate. Note that the organic solution of the present invention may contain a small amount of water. For example, water may be present in propylene glycol monomethyl ether acetate (less than 0.05% according to Karl Fischer) and small amounts of water may also be present in potassium oleate. If the surfactant is part of an aqueous solution, the aqueous solution may also contain H₂O₂. If H is used₂O₂Phosphor and H₂O₂May be in the range of 200:1 to 1:1, more preferably 50:1 to 3: 1.

An LED package or light emitting assembly or lamp 10 that may be used as part of a display or lighting device or apparatus is shown in fig. 1. LED package 10 includes a semiconductor radiation source, shown as an LED chip 12, and leads 14 electrically connected to the LED chip. The leads 14 may be thin wires supported by a thicker lead frame 16, or the leads may be self-supporting electrodes, and the lead frame may be omitted. The leads 14 provide current to the LED chip 12 and thus cause it to emit radiation.

The lamp may comprise any semiconductor blue or uv light source capable of producing white light when its emitted radiation is directed onto the phosphor. In one embodiment, the semiconductor light source is a blue emitting LED doped with various impurities. Thus, the LED may comprise a semiconductor diode based on any suitable group III-V, II-VI or IV-IV semiconductor layer and have an emission wavelength of about 250 to 550 nm. In particular, the LED may comprise at least one semiconductor layer comprising GaN, ZnSe or SiC. For example, the LED may comprise the formula In_iGa_jAl_kA nitride compound semiconductor represented by N (wherein 0 ≦ i; 0 ≦ j; 0 ≦ k and i + j + k ≦ 1), and having an emission wavelength of greater than about 250nm and less than about 550 nm. In particular embodiments, the chip is a near-uv or blue emitting LED having a peak emission wavelength of about 400 to about 500 nm. Such LED semiconductors are known in the art. For convenience, the radiation source is described herein as an LED. However, as used herein, the term is meant to encompass all semiconductor radiation sources, including, for example, semiconductor laser diodes. Furthermore, although the general discussion of the exemplary structures of the invention discussed herein is directed to inorganic LED-based light sources, it should be understood that, unless otherwise noted, the LED chip may be replaced by another radiation source, and any reference to a semiconductor, semiconductor LED, or LED chip is merely representative of any suitable radiation source, including but not limited to organic light emitting diodes.

In the LED package 10, the phosphor composition 22 is radiationally coupled to the LED chip 12. Radiation coupling means that the elements are associated with each other so that radiation passes from one element to another. The phosphor composition 22 is deposited onto the LED 12 by any suitable method. For example, a suspension of phosphor may be formed and applied to the LED surface as a phosphor layer. In one such method, a silicone slurry (silicone slurry) with phosphor particles randomly suspended therein is placed around the LED. The present method is merely exemplary of possible locations for the phosphor composition 22 and the LED 12. Thus, by coating and drying the phosphor suspension on the LED chip 12, the phosphor composition 22 can be coated over the light emitting surface of the LED chip 12 or directly on the light emitting surface of the LED chip 12. In the case of silicone-based suspensions, the suspension is cured at a suitable temperature. Both the housing 18 and the encapsulant 20 should be transparent to allow the white light 24 to be transmitted through those elements.

In other embodiments, the phosphor composition 22 is dispersed within the encapsulant material 20, rather than being formed directly on the LED chip 12. The phosphor (in powder form) may be dispersed within a single region of the encapsulant material 20 or throughout the entire volume of the encapsulant material. The blue light emitted by the LED chip 12 mixes with the light emitted by the phosphor composition 22, and the mixed light appears as white light. If the phosphor is to be dispersed in the material of the encapsulant 20, a phosphor powder may be added to the polymer or silicone precursor, loaded around the LED chip 12, and the polymer precursor may then be cured to solidify the polymer or silicone material. Other known phosphor dispensing methods, such as transfer loading, may also be used.

In yet another embodiment, the phosphor composition 22 is coated onto the surface of the shell 18, rather than being formed on the LED chip 12. The phosphor composition is preferably coated on the inner surface of the shell 18, but the phosphor may be coated on the outer surface of the shell if desired. The phosphor composition 22 may be coated on the entire surface of the shell or only on top of the shell surface. The uv/blue light emitted by the LED chip 12 mixes with the light emitted by the phosphor composition 22, and the mixed light appears as white light. Of course, the phosphor may be located in any two or all three locations, or in any other suitable location, such as separate from the housing, or integrated into the LED.

Fig. 2 shows a second configuration of the system according to the invention. Corresponding numerals in fig. 1-4 (e.g., 12 in fig. 1 and 112 in fig. 2) refer to corresponding structures in each of the figures unless otherwise specified. The structure of the embodiment of fig. 2 is similar to that of fig. 1, except that the phosphor composition 122 is interspersed within the encapsulant material 120, rather than being formed directly on the LED chip 112. The phosphor (in powder form) may be dispersed within a single region of the encapsulant material or throughout the entire volume of the encapsulant material. The radiation (indicated by arrows 124) emitted by the LED chip 112 mixes with the light emitted by the phosphor 122, and the mixed light appears as white light 124. If the phosphor is to be dispersed within the encapsulant material 120, a phosphor powder may be added to the polymer precursor and loaded around the LED chip 112. The polymer or silicone precursor may then be cured to solidify the polymer or silicone. Other known phosphor dispensing methods, such as transfer molding, may also be used.

Fig. 3 shows a third possible configuration of the system according to the invention. The structure of the embodiment shown in fig. 3 is similar to that of fig. 1, except that the phosphor composition 222 is coated onto the surface of the shell 218, rather than being formed on the LED chip 212. The phosphor composition 222 is optionally coated on the inner surface of the shell 218, but the phosphor may be coated on the outer surface of the outer shell if desired. The phosphor composition 222 may be coated on the entire surface of the shell or only on top of the surface of the shell. Radiation 226 emitted by the LED chip 212 mixes with the light emitted by the phosphor composition 222 and the mixed light appears as white light 224. Of course, the structures of fig. 1-3 may be combined, and the phosphor may be located in any two or all three locations, or in any other suitable location, such as separate from the housing, or integrated into the LED.

In any of the above structures, the lamp 10 may also include a plurality of scattering particles (not shown) embedded in the encapsulant material. The scattering particles may comprise, for example, silica, alumina, zirconia, titania, zinc oxide, or combinations thereof. The scattering particles effectively scatter the directed light emitted from the LED chip, preferably with a negligible amount of absorption.

As shown in the fourth structure in fig. 4, the LED chip 412 may be mounted in the reflective cup 430. The cup 430 may be made of or coated with a dielectric material, such as silicon dioxide, aluminum oxide, zirconium oxide, titanium dioxide, or other dielectric powders known in the art, or coated with a reflective metal, such as aluminum or silver. The remainder of the structure of the embodiment of fig. 4 is the same as that of any of the previous figures, and may include two leads 416, a wire 432, and an encapsulant material 420. The reflective cup 430 is supported by the first lead 416, and a wire 432 is used to electrically connect the LED chip 412 to the second lead 416.

Another structure is a Surface Mount Device (SMD) type light emitting diode 550, for example, as shown in FIG. 5. Such SMDs are "side emission type" and have a light emission window 552 on a protruding portion of the light guide member 554, and are particularly useful for backlight applications. The SMD package may contain an LED chip as defined above and a phosphor material excited by light emitted by the LED chip.

When used with an LED emitting light from 350nm to 550nm and one or more other suitable phosphors, the resulting illumination system will produce light having a white color.

In another embodiment, fig. 6 shows a backlight unit or module 600 according to the present invention, which includes a light source 602, a light guide plate 604, a remote phosphor portion 606 in the form of a sheet or film, an optical filter 660, and an LCD panel 616. Backlight unit 600 may also optionally include prisms 612 and brightness enhancement films 614. The light source 602 is an LED emitting blue light. To produce uniform illumination, blue light from the light source 602 first passes through the light guide panel 604, which diffuses the blue light. The LCD panel 616 also includes color filters, front polarizers, rear polarizers, and liquid crystals and electrodes arranged in the subpixels. Typically, an air space exists between the LCD panel 616 and the brightness enhancement film 614. The brightness enhancement film 614 is a reflective polarizer film that improves efficiency by repeatedly reflecting any unpolarized light back that would otherwise be absorbed by the rear polarizer of the LCD. The brightness enhancement film 614 is placed behind the liquid crystal display panel 616 without any other films in between. The brightness enhancement film 614 may be mounted with its transmission axis substantially parallel to the transmission axis of the rear polarizer. The brightness enhancement film 614 helps to recover the white light 622 that is typically absorbed by the rear polarizer (not shown) of the liquid crystal panel 616 and thereby increases the brightness of the liquid crystal panel 616.

The remote phosphor portion 606 includes particles 608A of a complex fluoride phosphor of formula I and particles 608B of a second luminescent material dispersed in a polymer resin. It is "remote" in the sense that the primary light source and the phosphor material are separate elements and the phosphor material is not integrated with the primary light source as a single element. Primary light is emitted from the primary light source and passes through one or more external media to radiationally couple the LED light source onto the phosphor material. Those skilled in the art will appreciate that the backlight unit according to the present invention may vary in configuration. For example, a direct lighting configuration may be used. In alternative embodiments, the prism 612 may also be removed or replaced with other brightness enhancement components. The brightness enhancement film 614 may be removed if desired.

In another embodiment, fig. 7 shows a backlight unit 700 comprising a back plate 702, a light guide panel 704 mounted in the back plate 702, LED light sources 706, a mounting bracket 708, and a remote phosphor package 710 in the form of a strip. The remote phosphor portion 710 is mounted between the light guide panel 704 and the LED light sources 706 via mounting brackets 708, whereby light emitted from the backlight 706 is transmitted through the portion 710 and then into the light guide panel 704. The backlight unit may further include a bottom reflection plate disposed between the light guide plate 704 and the back plate 702 and an optical film assembly disposed over the light guide plate 704.

With stable Mn⁴⁺The doped phosphor radiationally coupled LEDs may form part of a display device. The display device may comprise Mn radiatively coupled to the light emitting diode⁴⁺Doped phosphors, including mini light emitting diodes (mini LEDs) or micro light emitting diodes (micro LEDs) that emit light in the blue spectrum. Micro light emitting diodes (also known as micro LEDs, micro-LEDs, mleds and muleds) are one technology used for displays, where each pixel on the screen may have at least one small LED device, or each pixel may have at least more than one small LED device, and these LED devices may be coupled to red and green phosphors, respectively. Such a displayThe device may comprise a backlight unit, and a) a stable Mn being part of the backlight unit of the display device and being in direct or indirect contact with the LEDs or micro-LEDs⁴⁺Doped phosphor, or b) stable Mn as part of a backlight unit and remotely coupled to an LED or micro-LED and optionally in the form of a film⁴⁺A doped phosphor. Stabilized Mn⁴⁺The doped phosphor may be operatively connected to a backlight unit through at least one filter, and the backlight unit contains light emitting diodes or micro light emitting diodes. In display devices, Mn⁴⁺The doped phosphor may be operatively connected to a backlight unit of the display device or a portion thereof in any manner known in the art.

In some embodiments, Mn according to the present disclosure⁴⁺The doped phosphor is used in a direct emission display device comprising an array of micro LEDs having a size in the range of 1 μm to 300 μm, or more specifically 1 μm to 100 μm, and even 1 μm to 50 μm, 1 μm to 20 μm, or 1 μm to 10 μm. Exemplary methods of manufacturing a direct emission display device comprising phosphor particles coupled into a wavelength converting layer of a micro LED are described in US9,111,464 and US9,627,437, both of which are incorporated herein by reference in their entirety. Devices including a backlight unit or direct-emitting display according to the present invention include, but are not limited to, televisions, computers, smart phones, tablet computers, and devices having a display including a semiconductor light source and a Mn according to the present invention⁴⁺Other handheld devices for phosphor doped displays. In one embodiment, the phosphor particles of the present invention are part of a device comprising an LED, quantum dot, mini LED or micro LED. Mini LEDs are LEDs with dimensions between 50 μm and 300 μm. The display device according to the invention may be a television, a computer monitor, a mobile or traditional telephone, a digital photo frame, a tablet computer, an automotive display, an electronic book reader, an electronic dictionary, a digital camera, an electronic keyboard or gaming device, or any other electronic device with a screen.

Except for Mn⁴⁺Outside of the doped phosphorThe device according to the invention may comprise one or more further luminescent materials. When used in combination with a blue or near-ultraviolet LED emitting radiation in the range of about 250nm to 550nm in a lighting device or apparatus, the resultant light emitted by the assembly may be white light. Other phosphor or Quantum Dot (QD) materials, such as green, blue, yellow, red, orange or other colored phosphors or QD materials, may be used in the form of blends to tailor the color of the resultant light and produce a particular spectral power distribution. In other embodiments, the materials may be physically separated in the multilayer structure, or may be present in the multilayer structure as one or more blends. In fig. 1-5, the phosphor composition 22 may be a single layer blend or a multilayer structure containing one or more phosphor or QD materials in each layer. In a micro-LED direct-emitting display device, a single micro-LED may be individually coupled to Mn⁴⁺Phosphors and other phosphor or Quantum Dot (QD) materials are doped to produce light of a desired specification.

Suitable phosphors that may be used in the device according to the invention, together with Mn⁴⁺Doped phosphors, including but not limited to

((Sr_1-z(Ca,Ba,Mg,Zn)_z)_1-(x+w)(Li,Na,K,Rb)_wCe_x)₃(Al_1-ySi_y)O_4+y+3(x-w)F_1-y-3(x-w)，0<x≤0.10，0≤y≤0.5，0≤z≤0.5，0≤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(Cl,F,Br,OH):Eu²⁺,Mn²⁺；

(Ba,Sr,Ca)BPO₅:Eu²⁺,Mn²⁺；

(Sr,Ca)₁₀(PO₄)₆*nB₂O₃:Eu²⁺(wherein 0)<n≤1)；Sr₂Si₃O₈*2SrCl₂:Eu²⁺；(Ca,Sr,Ba)₃MgSi₂O₈:Eu²⁺,Mn²⁺；BaAl₈O₁₃:Eu²⁺；2SrO*0.84P₂O₅*0.16B₂O₃:Eu²⁺；(Ba,Sr,Ca)MgAl₁₀O₁₇:Eu^{2 +},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-nO_4-2n:Eu²⁺(wherein n is more than or equal to 0 and less than or equal to 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-aO_12-3/2a:Ce³⁺(wherein a is more than or equal to 0 and less than or equal to 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)_bSi_gN_m:Eu²⁺(wherein 2b +4g ═ 3 m); 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. ltoreq. u.ltoreq.1, 0<v is less than or equal to 0.1, and w is less than or equal to 0 and less than or equal to 0.2); (Y, Lu, Gd)_2-m(Y,Lu,Gd)Ca_mSi₄N_6+mC_1-m:Ce³⁺(wherein m is more than or equal to 0 and less than or equal to 0.5);

(Lu, Ca, Li, Mg, Y) doped with Eu²⁺And/or Ce³⁺alpha-SiAlON of (1); (Ca, Sr, Ba) SiO₂N₂:Eu²⁺,Ce^{3 +}；

β-SiAlON:Eu²⁺,Ba[Li₂(Al₂Si₂)N₆]:Eu²⁺,3.5MgO*0.5MgF₂*GeO₂:Mn⁴⁺；

(Ca,Sr)_1-c-fCe_cEu_fAl_1+cSi_1-cN₃(wherein c is more than or equal to 0 and less than or equal to 0.2, and f is more than or equal to 0 and less than or equal to 0.2);

Ca_1-h-rCe_hEu_rAl_1-h(Mg,Zn)_hSiN₃(wherein h is more than or equal to 0 and less than or equal to 0.2, and r is more than or equal to 0 and less than or equal to 0.2);

Ca_1-2s-tCe_s(Li,Na)_sEu_tAlSiN₃(wherein s is more than or equal to 0 and less than or equal to 0.2, t is more than or equal to 0 and less than or equal to 0.2, and s + t>0)；(Sr,Ca)AlSiN₃:Eu²⁺,Ce³⁺(CASN)；(Ba,Sr)₂Si₅N₈:Eu²⁺；Sr[LiAl₃N₄]:Eu²⁺(ii) a And Sr [ Mg)₃SiN₄]:Eu²⁺。

U may also be used⁶⁺-a doped phosphor; exemplary compositions include Ba₆Al₅P₅O₂₆:U⁶⁺、Ba₂P₂O:U⁶⁺、BaZn₂(PO₄)₂:U⁶⁺And BaBPO U⁶⁺. Other U's are disclosed in US 2019/0088827, USSN 15/915341, filed on 8.3.2018, and USSN16/124520, filed on 7.9.2018⁶⁺Doped phosphors, all assigned to General Electric Company (General Electric Company).

Can be used in the device according to the inventionThe Quantum Dot (QD) material of (A) may be a group II-VI compound, a group III-V compound, a group IV-IV compound, a group I-III-VI₂Family compounds or combinations thereof. Examples of group II-VI compounds include CdSe, CdTe, CdS, ZnSe, ZnTe, ZnS, HgTe, HgS, HgSe, CdSeTe, CdSeE, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSETe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, or combinations thereof. Examples of III-V compounds include GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaGaAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GalnNP, GalnNAs, GalnPAs, InAlNP, InAlNAs, InAlPAs, and combinations thereof. Examples of the group IV compound include Si, Ge, SiC and SiGe. I-III-VI₂Examples of group chalcopyrite (chalcopyrite) type compounds include CuInS₂、CuInSe₂、CuGaS₂、CuGaSe₂、AgInS₂、AgInSe₂、AgGaS₂、AgGaSe₂And combinations thereof.

The QD material may be a core/shell QD comprising a core, at least one shell coated on the core, and an outer coating comprising one or more ligands (preferably organic polymeric ligands). Exemplary materials for making the core-shell QDs include, but are not limited to, Si, Ge, Sn, Se, Te, B, C (including diamond), P, Co, Au, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, MnS, MnSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si₃N₄、Ge₃N₄、Al₂O₃、(Al,Ga,In)₂(S,Se,Te)₃、Al₂CO and suitable combinations of two or more such materials. Exemplary core-shell QDs include, but are not limited to, CdSe/ZnS, CdSe/CdS, CdSe @CdS/ZnS, CdSeZn/ZnS, InP/ZnS, PbSe/PbS, CdTe/CdS and CdTe/ZnS.

QD materials typically include ligands conjugated, coordinated, associated, or attached to their surfaces. In particular, the QDs may include a coating comprising a ligand to protect the QDs from environmental conditions, including elevated temperature, high intensity light, external gases and moisture. Such a coating may also help to control aggregation and allow the QDs to disperse in the matrix material.

Phosphor compositions useful in display or lighting devices may include one or more phosphors that produce a green spectral power distribution upon excitation with ultraviolet, violet, or blue light. In the context of the present invention, this is referred to as green phosphor or green phosphor material. The green phosphor may be a single composition or blend that emits light in the green to yellow-green to yellow range, for example cerium-doped yttrium aluminum garnet, more particularly (Y, Gd, Lu, Tb)₃(Al,Ga)₅O₁₂:Ce³⁺(YAG). In some embodiments, the color temperature of the LED package 10 is less than or equal to 4200K, and the only red phosphor present in the phosphor composition 22 is Mn⁴⁺A doped phosphor; in particular K₂SiF₆:Mn⁴⁺. The composition may additionally include a green phosphor. The green phosphor may be Ce-doped³⁺Of garnet or of a mixture of garnets, in particular doped with Ce³⁺And more particularly YAG. When the red phosphor is K₂SiF₆:Mn⁴⁺When the mass ratio of the red phosphor to the green phosphor material is less than 3.3, this may be significantly lower than a red phosphor of similar composition, but with a lower level of Mn dopant. Can react with Mn⁴⁺Other green emitting materials used with doped phosphors include green emitting QD materials and β -SiAlON.

The ratio of each individual phosphor in the phosphor blend may vary depending on the characteristics of the desired light output. The relative proportions of the individual phosphors in the various embodiment phosphor blends may be adjusted so that when their emissions are blended and used in an LED illuminationWhen the device is illuminated, visible light of predetermined x and y values is produced on the CIE chromaticity diagram, and preferably white light is produced. For example, the white light may have an x value in the range of about 0.20 to about 0.55 and a y value in the range of about 0.20 to about 0.55. However, the exact identity and amount of each phosphor in the phosphor composition may vary according to the needs of the end user. For example, the material may be used for LEDs intended for backlighting Liquid Crystal Displays (LCDs). In this application, after passing through the LCD/color filter combination, the LED color point will be appropriately adjusted according to the desired white, red, green and blue colors. The list of potential phosphors given here for blending is not meant to be exhaustive, and these Mn's are not meant to be exhaustive⁴⁺The doped phosphor may be blended with various phosphors having different emissions to achieve a desired spectral power distribution.

Other materials suitable for use in the device according to the invention include electroluminescent polymers such as polyfluorenes, preferably poly (9, 9-dioctylfluorene) and copolymers thereof such as poly (9,9 '-dioctylfluorene-co-bis-N, N' -bis (4-butylphenyl) diphenylamine) (F8-TFB); poly (vinylcarbazole) and polystyrene and derivatives thereof. In addition, the light emitting layer may include blue, yellow, orange, green, or red phosphorescent dye or metal complex, or a combination thereof. Materials suitable for use as phosphorescent dyes include, but are not limited to, tris (1-phenylisoquinoline) iridium (III) (red dye), tris (2-phenylpyridine) iridium (green dye), and iridium (III) bis (2- (4, 6-difluorophenyl) pyrido-N, C2) (blue dye). Commercially available fluorescent and phosphorescent metal complexes from ADS (American Dyes Source, Inc.) may also be used. The ADS green dyes include ADS060GE, ADS061GE, ADS063GE and ADS066GE, ADS078GE and ADS090 GE. The ADS blue dyes include ADS064BE, ADS065BE and ADS070 BE. The ADS red dye comprises ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE and ADS077 RE.

Mn of the invention⁴⁺The doped phosphors may be used in applications other than those described above. For example, as explained above, the material may be used as a phosphor in a fluorescent lamp, in a cathode ray tube, in a plasma display device or in an LCD. The material can also be used as electromagnetic heatA scintillator in a gauge, in a gamma ray camera, in a computed tomography scanner or in a laser. These uses are exemplary only, and not limiting.

The invention also relates to certain inventive phosphor compositions. For example, the present invention may be directed to a phosphor composition comprising phosphor particles and comprising at least one surface composition on the surface of the phosphor particles selected from the group consisting of: 1) a composition comprising a phosphorus-containing moiety and a carbon-containing moiety; 2) a composition comprising a phosphorus-containing moiety and a metal fluoride; 3) a composition comprising a phosphorus-containing moiety and a carbon-containing moiety and a metal fluoride; and 4) compositions containing phosphorus-containing moieties that are free of alkyl phosphate compounds, wherein the phosphor particles comprise Mn of formula I⁴⁺A doped phosphor of A_x[MF_y]:Mn⁴⁺Wherein A is Li, Na, K, Rb, Cs, or a combination thereof;

m is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is [ MF_y]The absolute value of the charge of the ion; y is 5, 6 or 7.

Surface compositions containing phosphorus-containing moieties can be prepared by exposing phosphor particles to K₂HPO₄Is formed by the steps of (1). The surface composition containing carbon-containing moieties may be formed by exposing phosphor particles to one or more of polyoxyethylene octylphenyl ether, potassium oleate, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene (20) sorbitan monolaurate, poly (acrylic acid sodium salt), and potassium sorbate. Surface compositions containing phosphorus-containing moieties that are free of alkyl phosphate esters can be prepared by exposing phosphor particles to K₂HPO₄Is formed by the steps of (1).

In one such composition, in one embodiment, the metal fluoride comprises magnesium fluoride. In another embodiment, the phosphorus-containing compound comprises a phosphate moiety; in the context of the present invention, "phosphate ester" means a compound containing PO₄And comprises phosphate ion PO₄ ^3-HPO, hydrogen phosphate ion₄ ^2-And dihydrogen phosphate ion H₂PO₄ ^-. In yet another embodiment, the carbon-containing compound comprises at least one selected from the group consisting of: ethylenediaminetetraacetic acid, polyoxyethylene octylphenyl ether, potassium oleate, polyoxyethylene-polyoxypropylene block copolymers, polyoxyethylene (20) sorbitan monolaurate, poly (acrylic acid sodium salt), potassium sorbate, and derivatives or salts thereof.

The surface composition improves the quantum efficiency of the phosphor particles upon exposure to liquid water or water vapor. In one embodiment, the phosphor particles exhibit a) a quantum efficiency after one hour of exposure to liquid water at room temperature of 50% to 100% of the quantum efficiency exhibited prior to water exposure, or B) a loss of quantum efficiency of less than 40% after 100 hours of exposure to 85% relative humidity at 85 ℃.

One advantage of the present invention is that the phosphor particles agglomerate less than would otherwise be the case. In one embodiment, D of the phosphor particles is prior to sonicating the solution containing the phosphor particles₅₀D of phosphor particles having a particle diameter of not more than 30 μm and after the ultrasonic treatment₅₀The particle size is not more than 20 μm. In other words, the phosphor particles are not sufficiently agglomerated such that the use of sonication will result in less agglomeration than would occur for particles not treated in accordance with the present invention. Fluorescent powders containing substantially non-agglomerated particles may exhibit improved flowability and dispersibility during LED package fabrication.

A light emitting diode device is a structure containing a light emitting diode. In one embodiment, a light emitting diode device is radiationally coupled to and/or comprises a phosphor composition according to the present invention. In another embodiment, the light emitting diode device is a mini LED or a micro LED. In yet another embodiment, a light emitting diode device can include an LED chip having a phosphor composition deposited thereon. The phosphor composition is optionally dispersed in the form of a film in a polymeric resin.

Examples

In the examples mentioned below, the primary particle size was measured using a scanning electron microscope using procedures known in the art, and the secondary particle size was measured using a Horiba LA-950V2 laser scattering particle size distribution analyzer also using procedures known in the art. The primary particle size according to the present application is the particle size of each phosphor particle, whether in an agglomerated state or not. The secondary particle size according to the present application is the particle size of each discrete particle or particle unit. For example, if two 10 μm phosphor particles are agglomerated to each other, the primary particle size will be 10 μm, since this is the size of each elemental phosphor particle. In this scenario, the secondary particle size will exceed 10 μm. For example, it may be 20 μm due to agglomeration.

The span is a measure of the width of the particle size distribution curve of the particulate material or powder and is defined according to equation (1):

wherein

D₅₀Is the median particle diameter of the volume distribution;

D₉₀is the particle size of the volume distribution, which is greater than the particle size of 90% of the particles in the distribution; and is

D₁₀Is the particle size of the volume distribution, which is greater than the particle size of 10% of the particles in the distribution.

Quantum Efficiency (QE) measurements are known in the art and can be done, for example, with a spectrophotometer. QE is a measure of the absorption of blue photons/emission of red photons from the phosphor emission. If there is 100% QE, this means that each absorbed blue photon will result in the emission of a red photon. QE is measured relative to a reference sample, so in this application when comparing QE, those are QE relative to a reference sample. It is not important which reference sample is used, as the comparison is of two or more other samples relative to the reference sample, so that the other two or more samples can be compared to each other.

Determining robustness against contact with water

Example 1

This example is for a compound of formula K₂SiF₆:Mn⁴⁺Phosphor of (1). The average primary particle size of this phosphor powder was 10.5 μm as determined by scanning electron microscopy. This phosphor was not as stable as described in the present application, nor was it exposed to the water test.

Example 2

1g of the phosphor of example 1 was mixed with 3g of deionized water in a 15mL plastic bottle. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and washed 4 times with a total of 100mL acetone (i.e., 4 washes were done using 100mL acetone). The powder was dried under vacuum for at least 24 hours.

Example 3

1.2g of the phosphor of example 1 was mixed with 3.6g of 39mM phosphoric acid solution in a 15mL plastic bottle. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and washed 4 times with a total of 100mL acetone. The powder was dried under vacuum for at least 18 hours. The powder was added to a fresh bottle and mixed with deionized water at a powder to water ratio of 1g:3 g. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and washed 4 times with a total of 100mL acetone. The powder was dried under vacuum for at least 24 hours.

Example 4

The experiment of example 3 was repeated, replacing 39mM phosphoric acid with 390mM phosphoric acid.

Example 5

The experiment of example 3 was repeated, replacing 39mM phosphoric acid with 39mM oxalic acid.

Example 6

The experiment of example 3 was repeated, replacing 39mM phosphoric acid with 390mM oxalic acid.

Example 7

The experiment of example 3 was repeated, replacing 39mM phosphoric acid with 39mM potassium hydrogen phosphate (dibasic).

Example 8

The experiment of example 3 was repeated, replacing 39mM phosphoric acid with 390mM dipotassium hydrogen phosphate (dibasic, pH 9).

A cured film of a 2 part thermally cured polydimethylsiloxane elastomer (such as sold as Sylgard 184 from Dow Corning) containing dispersed phosphor particles was prepared at a concentration of 0.5g phosphor/1.5 g silicone. The phosphors used were those prepared in examples 1-8. The Quantum Efficiency (QE) of the phosphor particles was measured in these films.

The QE measurement results for phosphor-containing films are summarized in table 1 of examples 1-8.

TABLE 1 measurement QE values of phosphor-containing films of examples 1 to 8.

Data in Table 1 show, K₂SiF₆:Mn⁴⁺Robustness of the phosphor is achieved by including K₂SiF₆:Mn⁴⁺With several substances such as K₂HPO₄The method of mixing the aqueous solutions of (a) and then performing powder separation and drying is enhanced. Enhanced robustness is shown relative to the QE of the starting phosphor powder not mixed with water as a retention of the QE after 1 hour of mixing the treated phosphor powder with water and the QE of the untreated powder produced at 1 hour of mixing with water. The QE of example 1 was 105.6%, which was not treated with water. The QE of example 2 was 74.6%, which indicates that water may have a large adverse effect on the QE of the phosphor. Example 2 was not treated according to the invention. Example 3 was treated according to the invention and showed a QE of 86.2%, which is much higher than 74.6%. In phosphor technology, QE is significant even for small percentage variations, and phosphor manufacturers often try to add several percent of QE to their phosphors. Thus, a jump from 74.6% to 86.2% is significant and surprising. In the above examples, with K₂HPO₄The effect of treating the phosphor powder with the aqueous solution of (1) is most pronounced in maintaining QE becauseExamples 7 and 8 show QEs of 100.7% and 104.2%, respectively.

Example 9

This example is for a compound of formula K₂SiF₆:Mn⁴⁺The phosphor of (1). This phosphor was not as stable as described in the present application, nor was it exposed to the water test. K for example 9 as determined by scanning Electron microscopy₂SiF₆:Mn^{4 +}The average primary particle size of the phosphor was 10.0. mu.m. In addition, the phosphor of example 9 did not use K after annealing₂SiF₆HF solution treatment.

Example 10

The phosphor used in example 10 was the same as that in example 1, and both were annealed with K₂SiF₆The saturated HF solution is treated. The embodiments are repeated with respect to each other. In fact, they gave similar results for QE, which means that this experiment was repeatable.

Example 11

Using K having a smaller average primary particle diameter than in examples 1 and 9₂SiF₆:Mn⁴⁺A phosphor. The phosphor powder of example 11 had an average primary particle size of 3.9 μm as determined by scanning electron microscopy and received no stabilization treatment according to the invention.

Example 12

Using K having a smaller average particle diameter than in examples 1 and 9₂SiF₆:Mn⁴⁺A phosphor. The phosphor of example 12 had an average primary particle size of 3.9 μm as determined by scanning electron microscopy and received no stabilization treatment according to the invention.

Examples 13 to 16

In four separate experiments, 1g of each phosphor sample from example 9, example 1, example 11, and example 12, respectively, was mixed with 3g of deionized water in a 15mL plastic bottle. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and washed 4 times with a total of 100mL each of acetone. The powder was dried under vacuum for at least 24 hours.

Examples 17 to 20

In four separate experiments, 1.2g of each phosphor sample from example 9, example 1, example 11 and example 12, respectively, was mixed with 3.6g of 390mM dipotassium hydrogen phosphate solution (dibasic, pH 9) in a 15mL plastic bottle. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and washed 4 times with a total of 100mL each of acetone. The powder was dried under vacuum for at least 18 hours. The powder was then added to a fresh bottle and mixed with deionized water at a ratio of 1g to 3g powder to deionized water. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and washed 4 times with a total of 100mL each of acetone. The powder was dried under vacuum for at least 24 hours.

Example 21

A1.2 g sample of phosphor from example 1 was mixed with 3.6g of 390mM dipotassium hydrogen phosphate solution (dibasic, pH 9) in a 15mL plastic bottle. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 15 minutes. The mixture was filtered on Whatman #4 filter paper and then washed 4 times with a total of 100mL acetone. The powder was dried under vacuum for 4 hours. The powder was then added to a fresh bottle and mixed with deionized water at a ratio of 1g to 3g powder to deionized water. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and then washed 4 times with a total of 100mL acetone. The powder was dried under vacuum for at least 24 hours.

Example 22

The experiment of example 21 was repeated except that 390mM K mixed with the phosphor of example 1 was used₂HPO₄The aqueous solution was rolled for 90 minutes instead of 15 minutes.

Example 23

1.2g of the phosphor from example 1 was mixed with 3.6g of 390mM potassium hydroxide solution (pH13.5) in a 15mL plastic bottle. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and then washed 4 times with a total of 100mL acetone. The powder was dried under vacuum for 4 hours. The powder was then added to a fresh bottle and mixed with deionized water at a ratio of 1g to 3g powder to deionized water. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and then washed 4 times with a total of 100mL acetone. The powder was dried under vacuum for at least 24 hours.

Example 24

The experiment of example 23 was repeated except that the 390mM KOH solution was replaced with a more dilute aqueous KOH solution adjusted to pH 9.

TABLE 2 measured QE values of phosphor-containing films of examples 9-24.

The data shown in Table 2 confirm that K is₂SiF₆:Mn⁴⁺Phosphor powder mixing with water has a significant adverse effect on the QE of the phosphor. Examples 17 and 18 clearly show that when the phosphor powder is mixed with K before mixing with pure water₂HPO₄The aqueous solution, when mixed, provides the phosphor powder with surprisingly more robust resistance to degradation upon subsequent exposure to water. A decrease in QE indicates degradation, and samples 13-16 are in the absence of K₂HPO₄In the case of exposure, the display shows a specific K₂HPO₄Processed examples 17-20 had much lower QE. Furthermore, without intending to be bound by any theory, this measure of stability or robustness is long-lasting, since even when the powder is transferred from aqueous K₂HPO₄The benefits remain after separation from the treatment solution, washing and drying. The data show that the stabilization of the powder is surprisingly fast, since with aqueous K₂HPO₄The QE of the powder mixed for only 15 minutes is essentially the same as when the mixing time was 1 hour or even 90 minutes. In examples 18, 21 and 22, exposure to aqueous K₂HPO₄QE generated in 15 minutes just and violentlyQE after 90 minutes of exposure was as high. Phosphor powder in K₂HPO₄Is substantially stable in the treatment solution over an extended period of time despite the fact that the aqueous K is₂HPO₄In general water, which is known to degrade the phosphor.

Examples 11, 12, 15 and 16 are not K-rich₂HPO₄Treated, and included samples having small particle sizes. Use of K for both examples 19 and 20₂HPO₄Treated, and included samples having small particle sizes. The results of examples 19 and 20 show that even when K is present₂SiF₆:Mn⁴⁺When the powder has a primary particle size of 3.9 μm, it is coated with aqueous K₂HPO₄The stability obtained by treating the phosphor powder is also surprisingly high.

In water using K₂HPO₄The surprising stability provided when dealing with phosphors is not merely a function of pH. As shown in example 24, the phosphor powder was pH adjusted to 390mM K₂HPO₄The pH matched (see examples 17-20) KOH aqueous solution mixing does not result in phosphor stabilization. In fact, example 24 has a QE of only 51%, which is even lower than example 14 (which is acidic, pH 3.28) which has a QE of 73.7% and is not mixed with a stabilizer. In other words, adjusting the pH to basic with KOH (example 24) results in much poorer results than without the addition of a stabilizer (example 14). When the phosphor powder was mixed with K in examples 17-22 with a minimum QE of 91.9%₂HPO₄A significant QE drop was also observed in example 23 (75.6% QE) when the concentration matched aqueous KOH (pH 13.48) of the solution (390mM) was mixed.

Reduction of agglomeration

To reduce agglomeration of the phosphor particles, several treatments were tested. The objective is to reduce agglomeration so that the dispersibility in the resin is improved so that the phosphor is uniformly distributed if the phosphor powder is dispersed in a film of, for example, photoresist or hydrophobic acrylate. Various combinations of solvents and surfactants are used. Typical solvents range from non-polar hydrocarbon solvents such as 1-Octadecene (ODE) to medium polar isobornyl acrylate to polar aprotic Propylene Glycol Monomethyl Ether Acetate (PGMEA). Surfactant/dispersant additives include nonionic (oleylamine, oleic acid, polyoxyethylene octylphenyl ether (sold as Triton X-100)), anionic (potassium oleate), and cationic (ammonium polyoxyethylene-derived fatty alcohol sulfate (sold as Hypermer KD25-LQ- (MV)). Examples 25-71 have a secondary particle size d50 measured using light scattering.

Example 25

Example 25 is a control and consists of 3g of K with a secondary particle size d50 of 15.0 μm₂SiF₆:Mn⁴⁺And (3) powder composition. No solvent or surfactant/dispersant was added. This control was used to determine the values in the second column of Table 3 (. DELTA.d 50-ODE + roller (. mu.m)).

Example 26

Example 26 with organic solvent and no surfactant and by taking 3g K from the same batch as example 25₂SiF₆:Mn⁴⁺And mixed with 20mL of ODE as an organic solvent to prepare a powder. The resulting composition was then briefly shaken for mixing and rolled at 80rpm for 20-30 minutes. The resulting mixture was then vacuum filtered to collect the powder and rinsed with 3x20mL acetone to remove traces of solvent. After acetone washing, the powder was dried on the filter for no more than five minutes before being collected and dried in a vacuum desiccator for at least 4 hours. The dried powders were then passed through a 170 mesh screen to improve flowability and then stored in a nitrogen purged bin until their Particle Size Distribution (PSD) and Quantum Efficiency (QE) could be analyzed. The secondary particle size d50 was then compared to the value measured in example 25 and the difference or "δ" was recorded in the second column of table 3.Δ d50 was-1.4 μm, so d50 of example 26 was 1.4 μm smaller than d50 of example 25. Thus, using ODE as a solvent reduced the secondary particle size of the sample.

Examples 27 to 31

Examples 27-31 were prepared by withdrawing 20mL of ODE and combining it with 0.3g of the corresponding surfactant as identified in the first column of Table 3, and then adding 3g of K from the same batch as example 25₂SiF₆:Mn⁴⁺Is prepared from powder. The resulting composition was then briefly shaken for mixing and rolled at 80rpm for 20-30 minutes. The resulting mixture was then vacuum filtered to collect the powder and rinsed with 3x20mL acetone to remove traces of solvent. After acetone washing, the powder was dried on the filter for no more than five minutes before being collected and dried in a vacuum desiccator for at least 4 hours. The dried powders were then passed through a 170 mesh screen to improve flowability and then stored in a nitrogen purged bin until their secondary particle size and QE could be analyzed. The secondary particle size d50 was then compared to example 25 and the difference or "δ" for each was recorded in the second column of table 3.

Example 32

Example 32 is a control and consists of 3g of K with a secondary particle size d50 of 33.4 μm₂SiF₆:Mn⁴⁺And (3) powder composition. No solvent or surfactant/dispersant was added. The QE for example 32 was 92.8%. This control was used to determine the values (Δ d 50-PGMEA + roller (. mu.m)) in the third column of Table 3.

Example 33

Example 33 with organic solvent and no surfactant and by taking 3g K from the same batch as example 32₂SiF₆:Mn⁴⁺And mixed with 20mL of Propylene Glycol Monomethyl Ether Acetate (PGMEA) as an organic solvent to prepare a powder. The resulting composition was then briefly shaken for mixing and rolled at 80rpm for 20-30 minutes. The resulting mixture was then vacuum filtered to collect the powder and rinsed with 3x20mL acetone to remove traces of solvent. After acetone washing, the powder was dried on the filter for no more than five minutes before being collected and dried in a vacuum desiccator for at least 4 hours. The dried powder was then passed through a 170 mesh screen to improve flowability and then stored in a nitrogen purged bin until its PSD and QE could be analyzed. The secondary particle size distribution d50 was then compared to example 32 and the difference or "δ" was recorded in Table 3 so that Δ d50 was-18.6 μm and so d50 for example 33 was 18.6 μm less than d50 for example 32.

Examples 34 to 38

Examples 34-38 were prepared by taking 20mL of PGMEA and combining it with 0.3g of the particular surfactant identified in column 1 of Table 3, and then adding 3g of K from the same batch as example 32₂SiF₆:Mn⁴⁺Is prepared from powder. The resulting composition was then briefly shaken for mixing and rolled at 80rpm for 20-30 minutes. The resulting mixture was then vacuum filtered to collect the powder and rinsed with 3x20mL acetone to remove traces of solvent. After acetone washing, the powder was dried on the filter for no more than five minutes before being collected and dried in a vacuum desiccator for at least 4 hours. The dried powders were then passed through a 170 mesh screen to improve flowability and then stored in a nitrogen purged bin until their PSD and QE could be analyzed. The particle size d50 is then compared to example 32 and the difference or "δ" is recorded in column 3 of table 3.

Example 39

Example 39 is a control and consists of 3g of K with a secondary particle size d50 of 35.2 μm₂SiF₆:Mn⁴⁺And (3) powder composition. No solvent or surfactant/dispersant was added. The QE of this sample was determined to be 94.1%. Example 39 is a control used in conjunction with columns 4-6 of Table 3(Δ d 50-PGMEA + ultrasound (μm); Δ d 50-acrylate + roller (μm); Δ d 50-acrylate + ultrasound (μm), respectively).

Example 40

Example 40 with organic solvent and no surfactant and by taking 3g K from the same batch as example 39₂SiF₆:Mn⁴⁺And mixing the powder with 20mL of acrylic acid isoborneol ester serving as an organic solvent to prepare the acrylic acid-isoborneol ester. The resulting composition was then briefly shaken for mixing and rolled at 80rpm for 20-30 minutes. The resulting mixture was then vacuum filtered to collect the powder and rinsed with 3x20mL acetone to remove traces of solvent. After acetone washing, the powder was dried on the filter for no more than five minutes before being collected and dried in a vacuum desiccator for at least 4 hours. The dried powders were then passed through a 170 mesh screen to improve flowability and then stored in a nitrogen purged bin until their secondary PSD and QE could be analyzed. However, the device is not suitable for use in a kitchenThe secondary particle size d50 was then compared to example 39 and the difference or "δ" was recorded in column 5 of Table 3, so Δ d50 was-19.4 μm, so d50 of example 40 was 19.4um less than d50 of example 39.

Examples 41 to 47

Examples 41-47 were prepared by taking 20mL of PGMEA (for examples 41-43) or 20mL of isobornyl acrylate (examples 44-47) and mixing each with 0.3g of the surfactant as identified in the last three rows of column 1 of Table 3. Subsequently, 3g of K from the same batch as in example 39 were added₂SiF₆:Mn⁴⁺And (3) powder. The resulting composition was then briefly shaken to mix and subjected to ultrasonic bath treatment for 7 minutes (examples 41-43 and 47) or rolling at 80rpm for 20-30 minutes (examples 44-46). The resulting mixture was then vacuum filtered to collect the powder and rinsed with 3x20mL acetone to remove traces of solvent. After acetone washing, the powder was dried on the filter for no more than five minutes before being collected and dried in a vacuum desiccator for at least 4 hours. The dried powders were then passed through a 170 mesh screen to improve flowability and then stored in a nitrogen purged bin until their secondary PSD and QE could be analyzed. The secondary particle size d50 was then compared to example 39 and the difference or "δ" was recorded in table 3. Examples 41-43 are reported in column 4 of Table 3(Δ d 50-PGMEA + ultrasound (. mu.m)), examples 44-46 are reported in column 5 (Δ d 50-acrylate + roller (. mu.m)), and example 47 is reported in column 6 (Δ d 50-acrylate + ultrasound (. mu.m)). The absolute secondary particle size d50 (i.e., not relative to example 39) of sample 41 was 12.9 μm, and the QE was 88.4%. The absolute secondary particle size d50 (i.e., not relative to example 39) of sample 42 was 12.0 μm, and the QE was 94.3%. Sample 43 had an absolute secondary particle size d50 (i.e., not relative to example 39) d50 of 12.5 μm and a QE of 94.2%.

TABLE 3 surfactant/dispersant treatment K₂SiF₆:Mn⁴⁺The particle size distribution of the powder in the absence of sonication during the measurement was reduced.

As can be seen in table 3, the use of certain solvents may help to reduce agglomeration. Agglomeration can also be reduced using certain surfactants. Certain combinations of solvents and surfactants also exhibit advantages. Regardless of the degree of agglomeration in the starting powder, potassium oleate, polyoxyethylene octylphenyl ether, and polyoxyethylene-derived ammonium fatty alcohol sulfate (PODFAE) (such as is available as Hypermer KD25-LQ- (MV), as the primary anionic, nonionic, and cationic additive candidates, respectively) resulted in an absolute secondary d50 of secondary particle size of 12-14 μm (i.e., not relative to the other sample). Comparison with the control is shown in table 3.

The advantages of the invention are also demonstrated by the variants of the embodiment shown above. Examples 48-51 below illustrate this and the results are in table 4.

Example 48

This is as K without any surface treatment₂SiF₆:Mn⁴⁺Control (3). In other words, there is neither KEDTA nor K₂HPO₄Nor potassium oleate, nor PGMEA, nor MgF₂Coated phosphor, also without MgSiF₆·6H₂O, also has no H₂SiF₆。

Example 49

This sample was intended to be treated with ethylenediaminetetraacetic acid dipotassium salt dihydrate (KEDTA)₂SiF₆:Mn⁴⁺. By adding 16.3g K to a 1L polypropylene bottle₂HPO₄6.4g KEDTA, 22mL aqueous 30% H₂O₂And 480mL of distilled H₂O to prepare a solution such that the pH is between 7 and 8. On the basis of the above, 128g K is added₂SiF₆:Mn⁴⁺The bottle was rolled at 40RPM for 20 minutes. The material was then allowed to settle, the supernatant decanted, and the slurry vacuum filtered,using 100mL of H₂O+2mL 30％H₂O₂Washed once and then 5 times with 100mL acetone before drying under vacuum.

The sample may also optionally be rinsed with acetic acid and ethanol and dried under vacuum at elevated temperatures up to 200 ℃. Sonication may also optionally be used in place of/in conjunction with rolling the bottle.

Example 50

This sample was directed to K with potassium oleate in an organic medium₂SiF₆:Mn⁴⁺And (6) processing. Potassium oleate (7.5229g, 23.47mmol, 40% by weight paste in water from Sigma Aldrich, relative to K₂SiF₆:Mn⁴⁺5 wt.%) was dissolved in 250mL PGMEA. Adding the solution to a solution containing 150.14g K₂SiF₆:Mn⁴⁺Powder and 250mL PGMEA in a 1 gallon plastic bottle. An additional three 250mL portions of PGMEA were used to flush the potassium oleate container and added to one gallon of K-containing solution₂SiF₆:Mn⁴⁺In a bottle of surfactant mixture (total PGMEA ═ 1.25L). A gallon bottle was capped and rolled for 30 minutes. The resulting stable phosphor powder was transferred to a plastic Buchner funnel and isolated by vacuum filtration. 500mL of acetone was used to rinse a one gallon plastic bottle and transferred to a Buchner funnel to wash the solids. Another three 500mL portions of acetone were used to wash the solids, which were stirred (total 2L of acetone) before each wash and then air dried for 3 minutes. The slightly wet powder was collected and dried in a vacuum desiccator for three days and then sieved through a 170 mesh membrane to provide 146.77g of surfactant treated K₂SiF₆:Mn⁴⁺And (3) obtaining the product.

Example 51

This sample was directed to MgF coated₂The phosphor of (1). Weighing MgSiF₆·6H₂O (17.6992g, 64.48mmol) was charged into a 60mL plastic canister, to which was then added 40g of high purity deionized water. After mixing, the slightly turbid mixture was filtered through a 0.45 μm membrane. The filtered solution was taken up in 40mL of 35% aqueous H₂SiF₆(52.8g, density 1.32) dilution.This produced solution a. Separately, 125g K₂SiF₆:Mn⁴⁺Add to a 2L mL plastic beaker equipped with a large stir bar. Each of the two syringe pumps was set to deliver 37.5mL of solution a (75 mL total of solution a) directly into the reaction mixture over 30 minutes. Adding 1.425L K to a beaker containing phosphor powder₂SiF₆Saturated 49% aqueous HF. The mixture was stirred vigorously for 30 seconds (300rpm), after which the stirring was reduced to 120 rpm. Addition of solution a to the stirred reaction mixture by syringe pump was started. After the addition was complete, stirring was stopped, the stir bar was removed, and the reaction mixture was allowed to stand for 10 minutes. The supernatant was decanted and discarded. The wet slurry was mixed with 400mL K₂SiF₆And MgF₂Saturated 49% aqueous HF was mixed. The wash mixture was allowed to settle for 10 minutes and then the supernatant was decanted and discarded. The slurry was transferred to a plastic buchner funnel fitted with a 0.65 μm fluoropolymer membrane. The residual HF solution was filtered off and the phosphor cake was washed 4 times with acetone, using a total of 800mL acetone, and the solids were stirred before each wash. The product was dried under vacuum for 3 days and then sieved through a 170 mesh membrane to provide the final product. The test results for examples 48-51 are shown in Table 4.

TABLE 4

The D50 secondary particle size of samples 48-51 was measured as follows:

1. d50 measurement in table 4. This was done on Horiba 950 without sonication before measurement, but the cycle was set to 5 for 3 minutes. The solvent is isopropanol.

2. D50 US measurement in table 4. Similar measurements as described above were done, but with the exception that the cycle was set to 5, the sonication was set to 7.

The Horiba measurement gives the size of the agglomerates, which is the size of the agglomerated mass of the base particles. The US measurement gives the size of the smallest agglomerates, which means that it is the agglomerate quality of the primary particles that is reduced by the ultrasound treatment.

Examples 48 to 51 show surface treatment and MgF₂The coating surprisingly produces smaller agglomerate particle sizes with little decrease in quantum efficiency.

Examples 52-76 also show that good quantum efficiency is maintained with a reduction in particle agglomeration, as explained below.

Example 52

This is a batch of K used in all examples 53-76₂SiF₆:Mn⁴⁺。

Example 53

This is the control batch. 4g K from example 52₂SiF₆:Mn⁴⁺20mL H in a 30mL Nalgene bottle₂And (4) in O. It was rolled at 80RPM for 30 minutes. The sample was then allowed to settle for 20 minutes, subjected to a centrifugal pulse at 2500RPM (about 30 seconds), then decanted, vacuum filtered, washed 3 times with acetone, vacuum dried, and sieved through a 170 mesh membrane. Example 53 did not contain a surfactant of the present invention and was compared to a sample containing a surfactant.

Examples 54 to 76

Examples 54-76 were carried out as follows: 4g K from example 52₂SiF₆:Mn⁴⁺20mL H in a 30mL Nalgene bottle₂O or 20mL of 0.78M K₂HPO₄(aqueous solution) +0.3g or 0.6g (or 0.3mL) of surfactant. The bottle was rolled at 80RPM for 30 minutes. The sample was then allowed to settle for 20 minutes, subjected to a centrifugal pulse at 2500RPM (about 30 seconds), then decanted, vacuum filtered, washed 3 times with acetone, vacuum dried, and sieved through 170 mesh. Information on the details of each example is found in table 5 below. The ammonium polyacrylate polymer in examples 73 and 74 can be sold as Dispex AA 4040.

Table 5 below shows the "examples" number in column 1 and the surfactant or other "surfactant" used in column 2. In column 3, whether K is used₂HPO₄(this column is labeled "0.78M K₂HPO₄"). If that column writes Y, then 20mL of 0.78M K was used₂HPO₄If it writes N, then only 20mL of water is used. Column 3 may also be noted with K₂HPO₄Or other additives added with water, such as 1mL of 30% H₂O₂An aqueous solution. In column 4, labeled "amount", it is listed whether the amount of "surfactant" used is 0.3 grams or 0.3 mL. QE is shown in column 5. Column 6 shows Δ QE, which is QE with and without K₂HPO₄The difference between the samples.

TABLE 5

By using K, as shown above in the Δ QE column₂HPO₄The average QE improvement of (a) was surprisingly 24.2%. Another observation is that, as shown in example 58, H₂O₂Make QE increase>25 percent. Furthermore, as shown in table 5, many surfactants also increased QE by a significant amount.

Examples 77 to 86

For examples 77-84, 3.5g K₂SiF₆:Mn⁴⁺Added to a solution at 15mL of 0.39M K₂HPO₄(aqueous solution) containing the surfactant listed in Table 6. The surfactants are also provided in the amounts listed in table 6. The sample was roll milled for 30 minutes. The material was then allowed to settle, the supernatant decanted, and the slurry vacuum filtered with 30mL H₂O+2mL 30％H₂O₂Washed once and then 5 times with 40mL acetone before drying under vacuum. The dried sample was then sieved through a 120 mesh nylon screen. Example 86 was the master batch used for examples 77-85 and was not treated with water. Example 85 was treated with water, but not with a surfactant. The test results are shown in table 6, the first column gives the example number, the second column identifies the surfactant used, the third column quantifies the amount of surfactant ("SA") used, and the fourth column provides the QE of such samples. As shown in the table 6 below, the results,the effect of water treatment on example 85 significantly reduced QE. However, surfactants and K₂HPO₄The addition of (c) largely reversed the detrimental effects of QE shown in example 85.

TABLE 6

Additional test results for samples 77-86 are provided in Table 7 below.

TABLE 7

In table 7, the first column is the example number. The second column shows the secondary particle size measured without sonication. The third column shows the span without sonication. Span measures the width of the particle size distribution. In the third column, examples 85 and 86, which were not treated with surfactant, show a relatively large span. In addition to example 80, the examples with surfactants show a reduction in span relative to examples 85 and 86, which means they show better dispersion and less agglomeration due to a narrower distribution of particle sizes. The fourth column is information on the secondary particle size under sonication. The fifth column is information about the span of the sample under sonication. Even with sonication, which improves dispersion and reduces agglomeration, the samples with surfactant have a reduced span relative to samples 85 and 86, which shows improved dispersion and reduced agglomeration. Column 6 shows the change in D50(Δ D50) between non-sonication and sonication. Δ D50 also correlates with the degree of dispersion and agglomeration, since a greater Δ D50 means a greater effect of sonication on dispersion and agglomeration. Examples 85 and 86 have a greater Δ D50 than all samples that received surfactant treatment, meaning that the examples that were surface treated improved dispersion and reduced agglomeration.

Examples 87 to 95

Example 87

Example 87 contains K₂SiF₆:Mn⁴⁺Without any stabilization treatment and also without exposure to water tests. This is a control used in conjunction with examples 88-95.

Examples 88 to 95

Examples 88-95 were conducted to determine the presence of AlPO₄In the presence of K₂SiF₆:Mn⁴⁺Of the liquid water exposure. 1.2g K₂SiF₆:Mn⁴⁺The sample was mixed with 3.6mL of high purity deionized water and 0.39M K₂HPO₄、0.39M AlPO₄、0.39M AlPO₄0.3mL of 30% H₂O₂、0.1M AlPO₄、0.1M AlPO₄0.3mL of 30% H₂O₂、0.6M AlPO₄And 0.6M AlPO₄0.3mL of 30% H was added₂O₂And (4) combining. All samples were briefly shaken for mixing and rolled at 40rpm for 1 hour. The pH of each sample was recorded, and then each sample was filtered and washed three times with acetone (50 mL total). The filter cake was collected and dried in a desiccator under vacuum overnight. High purity deionized water was then added to the separated powder in a new plastic bottle at a ratio of 1g powder to 3g water. The samples were briefly shaken for mixing and rolled at 40rpm for 1 hour. Each sample was filtered and washed three times with acetone (50 mL total), and the filter cake was collected and dried in a desiccator under vacuum overnight. The results are shown in Table 8 below.

TABLE 8

The above results and the treatment with water K therein₂SiF₆:Mn⁴⁺Resulting in a large drop in QE and using K₂HPO₄Other embodiments handling significantly improved QEAnd (5) the consistency is achieved. Δ QE is the difference between the control (example 87) and the remaining examples (examples 88-95). From the above data it is clear that the QE drop using water alone (example 88) is 63.1%. Surprisingly, all other examples had much smaller QE reduction. The maximum reduction was 38.0%, which is still much less than the QE loss observed in example 88. This further demonstrates the utility of the present invention in stabilizing phosphors to adversely affect water resistance. Although exposed to K₂HPO₄Result in a specific AlPO₄Better QE value, but AlPO₄And H₂O₂Treatment of both results in K alone₂HPO₄Similar behavior. However, AlPO at 0.39M and 0.6M₄Even in the absence of H₂O₂Also in the case of (3) very good QE values.

Examples 96 to 100

Examples 96-100 are directed to the use of MgF₂Improved robustness of the phosphor to liquid water and water vapor when treated and without potassium hydrogen phosphate treatment. Starting of K₂SiF₆:Mn⁴⁺The phosphor powder had an average secondary d50 particle size of 12.3 μm as determined by light scattering.

Example 96

1g of starting K₂SiF₆:Mn⁴⁺The phosphor was mixed with 3g of deionized water in a 15mL plastic bottle. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and washed 4 times with a total of 100mL acetone. The powder was dried under vacuum for 3 days.

Example 97

MgF was produced in an amount of 1 wt.% relative to the starting phosphor according to the procedure defined in example 51₂MgSiF of₆·6H₂Amount of O precursor, with MgF₂5g of the starting phosphor of example 96 was coated. 1g of the coated phosphor was mixed with 3g of deionized water in a 15mL plastic bottle. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and washed 4 times with a total of 100mL acetone. Drying the powder under vacuum for 3 days。

Example 98

MgF was produced in an amount of 1 wt.% relative to the starting phosphor according to the procedure defined in example 51₂MgSiF of₆·6H₂Amount of O precursor, with MgF₂5g of the starting phosphor of example 96 was coated. After filtering the residual HF solution from the product and rinsing 2 times with acetone, the semi-dry filter cake was transferred back to the reaction beaker. To this solid was added 30mL of 0.39M K₂HPO₄An aqueous solution. The mixture was mixed at 140rpm for 2 minutes. The slurry was transferred to a fresh plastic buchner funnel fitted with a 0.7 μm paper membrane. The aqueous solution was filtered off. The solid was washed 4 times with acetone and then dried under vacuum. 1g of this is subsequently treated with K₂HPO₄The treated coated phosphor was mixed with 3g of deionized water in a 15mL plastic bottle. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and washed 4 times with a total of 100mL acetone. The powder was dried under vacuum for 3 days.

Example 99

MgF was produced in an amount of 5 wt.% relative to the starting phosphor according to the procedure defined in example 51₂MgSiF of₆·6H₂Amount of O precursor, with MgF₂5g of the starting phosphor of example 96 was coated. 1g of starting phosphor was mixed with 3g of deionized water in a 15mL plastic bottle. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and washed 4 times with a total of 100mL acetone. The powder was dried under vacuum for 3 days.

Example 100

MgF was produced in an amount of 5 wt.% relative to the starting phosphor according to the procedure defined in example 51₂MgSiF of₆·6H₂Amount of O precursor, with MgF₂5g of the starting phosphor of example 96 was coated. After filtering the residual HF solution from the product and rinsing 2 times with acetone, the semi-dry filter cake was transferred back to the reaction beaker. To this solid was added 30mL of 0.39M K₂HPO₄An aqueous solution. Mixing the mixture withMix at 140rpm for 2 minutes. The slurry was transferred to a fresh plastic buchner funnel fitted with a 0.7 μm paper membrane. The aqueous solution was filtered off. The solid was washed 4 times with acetone and then dried under vacuum. 1g of this is subsequently treated with K₂HPO₄The treated coated phosphor was mixed with 3g of deionized water in a 15mL plastic bottle. The mixture was shaken by hand for 15 seconds and then rolled at 40rpm for 1 hour. The mixture was filtered on Whatman #4 filter paper and washed 4 times with a total of 100mL acetone. The powder was dried under vacuum for 3 days.

After mixing the starting phosphor in water for 1 hour, the QE dropped from 99.9% to 16.8% as shown in table 9 (example 96). In contrast, at 1% MgF₂The coated phosphor dropped only to 77.6% at the level (example 97) and at 5% MgF₂The phosphor coated at the level dropped only to 93.3% (example 99). By simply mixing MgF₂Coated product with 0.39M K₂HPO₄The aqueous solution was mixed for 2 minutes and the bond was made with aqueous K₂HPO₄Treating MgF₂The coated phosphor resulted in an even more significant preservation of QE upon exposure to liquid water. When the phosphor is applied at a 1% level with MgF₂Coated and then reacted with aqueous K₂HPO₄Upon mixing, the QE decreased only 1.3% after one hour of mixing with pure water. The data in table 9 also indicate the following facts: MgF compared to the primary phosphor₂The coated phosphor particles had a much smaller QE drop associated with exposure to 85% relative humidity for 100 hours at 85 ℃. When MgF is mixed₂Aqueous K for coated phosphors₂HPO₄Upon treatment, the QE drop after exposure to humidity was even further reduced.

TABLE 9

As shown in Table 9, with and without aqueous K₂HPO₄With MgF in the case of subsequent treatment₂Coating the phosphor has three benefits: it enhances dispersibility, it enhances robustness against liquid waterAnd it enhances robustness against humidity at elevated temperatures. These effects are still further enhanced in the compositions of the present invention, which will be coated with MgF₂The phosphor of (A) is then coated with aqueous K₂HPO₄And (6) processing.