TW200835777A - Illumination system comprising radiation source and a luminescent material - Google Patents

Abstract

An illumination system comprising a radiation source and a luminescent material comprising at least one first phosphor capable of absorbing a part of the radiation emitted by the radiation source and emitting radiation of a wavelength different from that of the absorbed radiation, wherein said at least one phosphor is an europium(III)-activated hetero-polyoxometallate of general formula AaREb-zMmO3m+3/2b+a-1/2xFx:Euz, wherein A is as least one alkaline metal selected from the group of lithium, sodium, potassium, rubidium and cesium, RE is at least one rare earth metal selected from the group of yttrium, lanthanum and gadolinium, M is a metal selected from the group of molybdenum and tungsten or a combination thereof and wherein 0 ≤ a ≤ 1, 1 ≤ b ≤ 3, 2 ≤ ≤ m ≤ 6, 0 ≤ x < 2 and 0.002 < z <1.0 can provide light sources having high luminosity and color-rendering, especially in conjunction with a light emitting diode as a radiation source. The red-emitting europium(III)-activated hetero-polyoxometallate phosphor is efficiently excitable by primary radiation in the near UV-to-blue range of the electromagnetic spectrum.

Description

200835777 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention generally relates to an illumination system containing a radiation source and a luminescent material containing a phosphor. The invention also relates to a luminescent material for use in such a lighting system. [Prior Art]

In particular, the present invention relates to an illumination system and a luminescent material which are produced by cold-light down-conversion and color mixing based on a radiation source that is emitted in the near-UV or (four) circumference of the electromagnetic spectrum. Specific colored light of white light. In particular, a light-emitting diode is used as a source of radiation. Today's lighting systems that serve as a source of radiation are durable, compact, lightweight, and versatile applications that are single or in cluster lighting. See the use of colored red, green, and blue light-emitting diodes as a high-efficiency, long-acting, low-voltage source that requires white or color.

= one of the display products; Ming:: : 2 such as computer monitors, stereo receivers, players, VCI machines:: status indicators for such products. The indicator is also used for instrument panels such as flying, car, and boat 'cars. A plurality of visible and arrayable arrays of components can be visible =: hundred or thousands of leds are found in large-area two-color hair such as full-color video wall: colorful group of LEDs = outdoor_screen. I-wide from the special traffic lighting of the traffic signs or buildings. ^I know that the color hair is often inclined to low yield, and it is considered as 126865.doc 200835777 It is difficult to produce uniform emission characteristics in batches. Within a single batch, the LEDs can exhibit large wavelength variations across the wafer and can exhibit strong wavelength and emission variations in operation with operating conditions such as drive current and temperature. When the polar body is configured to produce white light, there is a problem that white light of a desired color cannot be produced due to changes in the hue, luminosity, and other factors of the visible color light-emitting diode. A known method is used in an illumination system in which the color of a light-emitting diode emitted in the range of 2UV to blue of the electromagnetic spectrum is converted by a luminescent material containing a phosphor. Phosphor conversion &quot;white&quot; The LED system is especially based on a two-color (Βγ) method, which mixes yellow and blue colors. In this case, the yellow secondary component of the output light can be provided by a yellow light body, and the blue color It can be provided by a light-filling body or by a blue LED: to be provided by emission. Similarly, the white lighting system is based on a three-color (rgb) method, that is, based on mixing three colors of red, green and blue, in this case, The red and green components may be provided by a phosphor, and the blue component is provided by the primary emission of a blue emitting LED. Because the latest advances in LED technology have been produced in the near UV to blue range of the electromagnetic spectrum. Very effective light-emitting diodes, nowadays a wide range of color and white-emitting phosphor-converted light-emitting diodes have been sold in the market, challenging traditional incandescent or fluorescent lighting. C exists in the near-blue range of the available electromagnetic spectrum One of the conventional luminescent materials for absorption spectroscopy, which can effectively convert the near uv/blue light shot into visible color or white light while maintaining long-term stability. 126865.doc 200835777 Developed and optimized conventional phosphors Used in two main applications: (丨) fluorescent lamps, which use 254 nm uv radiation from Hg discharge as excitation, and (2) CRT, RGB scale system excited by an electron beam. The luminescent material of the light-converting LED device proves to be a new challenge for phosphor research. For luminescent materials that emit yellow, amber or red light, it is known to contain phosphorescence as an activator in any kind of host crystal. The body satisfies the absorption criterion in the near-UV of the electromagnetic spectrum. Given the example, US 2006/0028117 揭示1 discloses a red phosphor which is (Li+y-xMxMAOOy.-Euz, a compound of the SmA table and a fluxing aid) Training" where K, M Na, Ca, Sr or Ba, A is Mo or W, 〇SxS2 ' 〇'5SyS5 ' 〇·〇κζη 5, and 〇"〇, its emission efficiency is transmitted through a long-wavelength UV excitation source It will be excellent and have a good and uniform particle size. It should also be noted that the market for phosphor converted LEDs is subject to a configuration in accordance with the configuration of the (ΒΥ) mode and in particular the combination of a blue emitting diode and a phosphor that emits in the amber to red range of the electromagnetic spectrum. In order to improve the efficiency of such illumination systems containing blue emitter diodes, a new amber to red emission luminescent material is generally required which has an improved excitation by emitting in the blue-violet range of the electromagnetic spectrum. A source of radiation. The life of the disc is another subject with respect to phosphor-converted light-emitting diodes. SUMMARY OF THE INVENTION The present invention provides an illumination system including a radiation source and a radiation containing a portion of the radiation emitted by the radiation source and emitting a wavelength different from the wavelength of the absorbed radiation. a luminescent material of at least one first phosphor, wherein the at least one phosphorescent system is a helium-P〇lyoxometallate having a general formula

AaREbMm〇3m+3&quot;b+ai/2xFx, wherein A is at least one alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium and cesium, and ER is in the group of the following Selecting at least one rare earth metal: 镧, 镧 and, the lanthanide is selected from the group consisting of molybdenum and tungsten or a combination thereof, and wherein OSaU, and 叱χ &lt; This lighting system provides an efficient and long-lasting way of lighting. The efficiency of a lighting system using a primary source of radiation and a lining that converts the primary light into a secondary light is particularly important to the efficiency of the light conversion process. A radiation conversion program can be characterized generally by a wavelength including an extinction coefficient, an excitation, and an emission spectrum, a Stokes displacement, a quantum efficiency, and a lumen efficiency - a wavelength of the absorbed power of the phosphor. Dependent measurement-excitation (4) is the dependence of the emission intensity of the excitation wavelength measured at the "single-odd" emission wavelength. - The emission spectrum is the wavelength distribution of the emission measured after excitation at a single constant excitation wavelength. The term "s" displacement is generally defined as shifting the spectral line or ▼ of luminescent radiation to a longer wavelength than the excitation line or band. The number of photons emitted by the quantum efficiency phosphor is not the number of photons absorbed. The light-emitting program consumes one part of the energy resulting in inefficient radiation transfer. 126865.doc 200835777 For 0 The illumination system according to the present invention exhibits luminescence with a lining efficiency that has been improved over prior art systems. This efficiency increase is due to the following facts. The inventive phosphor has an excitation band in the blue-green and blue range of the electromagnetic spectrum and extends into the UVA and UVB ranges. If the excitation spectrum is in the blue and blue-green range, if the wavelength of the excitation source is In contrast to the phosphor excitation wave length matching, the phosphor described in the present invention has a very small Stokes shift. • ΓΠ This minimizes the conversion of a major photon emitted by the light source into The quantum 敎 caused by the yellow to red photon at one time. The lower energy of the light to the lamp is consumed as heat, and the luminous efficiency is increased. The luminescence spectrum permits the phosphors to be effectively excited by, for example, ordinary laser and arc lamps and any wavelength-limiting source of inorganic or organic light-emitting diodes. In particular, a light-emitting diode is included to serve as one of the present invention. The source of radiation. • The narrow spectral half-width of the emission spectrum of the target. The emission produced by a light-emitting diode generally has excellent monochromaticity. In a particularly preferred embodiment of the invention, the source is An illuminating diode having a peak emission wavelength in the range of 370 to 480 nm is used as a source of radiation. In the case of Guangsang, the illumination system will provide white light. The photon is excited by the blue light emitted by (4) 'Let it emit yellow, lack

^ m n Amber or red light. The blue light emitted by the LED is transmitted through the phosphor, and the light is mixed with the yellow to amber or red light emitted by the phosphor. The viewer will mix the blue and the station or the red light. 126865.doc 200835777 The object is perceived as white light. The luminescent material may also contain at least one second phosphor. When the luminescent material contains a phosphor blend of a phosphor according to the present invention and at least a second phosphor, a high quality white light illumination system having a good color appearance at the desired color temperature will be obtained.

According to a particular embodiment of the invention, the second phosphorescent system emits a scale body from green to yellow. It is particularly useful when the green to yellow emitting phosphorescent system is selected from the group consisting of (Ba1-xSrx)2Si04:Eu, where 0SK1,

SrGa2S4: Eu, SrSi2N202: Eu, RE3Al5012: Ce, where RE contains and is all metal. According to another embodiment of the invention, the second phosphorescent system emits a blue to green phosphor. Phosphors selected from the group consisting of BaMgAl10017:Eu, Ba5Si04(C 1,Br)6:Eu, CaLn2S4:Ce, wherein Ln contains lanthanum and lanthanide metals and (Sr, Ba, Ca ) 5 (P〇4) 3ChEu. According to another embodiment of the invention, the second phosphorescent system emits a red fill light. Phosphors selected from the group of the following are particularly useful: Eu(II) active fillers containing (Cai xSrx)s:Eu, and (Sri-x-yBaxCay)2-zSl5-aAlaN8-aOa: Euz, where 〇&lt;a&lt;5, 〇&lt;xd, 0&lt;y&lt;lJL0&lt;z&lt;l. According to another aspect of the present invention, a luminescent material comprising at least a first phosphor capable of absorbing a portion of the light emitted by the source and emitting a different light from the absorbed light is provided Wavelength of light, wherein the at least one phosphorescent system is a ruthenium (111) active heteropolyoxymethylene resin 126865.doc -12- 200835777 salt having the general formula AaREb-zMm〇3m+3/2b~i/2xFx:Euz, Wherein A is at least one alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium and planer, and RE is at least one rare earth metal selected from the group consisting of lanthanum, cerium and lanthanum. M is a metal selected from the group consisting of: turned to town or a combination thereof, and wherein Mad, 0幺x&lt;2 and 〇·〇〇2&lt;ζ&lt;〇·8 〇new luminescent material Matches with each single ideal requirement for the lighting system, ie • Strong amber or red emission • High quantum efficiency • Sensitivity to long-wave UV and especially by visible violet/blue light • At high operating temperatures Efficiency • Very long operating life from head to tail stable • High flow Iso-based equivalents thereof vinylidene polyoxyethylene resinates The key feature of the host lattice of the phosphors of the present invention. The stable crystal structure of the host lattice has no non-stoichiometric defects and is therefore stable with respect to external influences such as heat and ultraviolet to blue radiation. Therefore, the phosphorescent system according to the present invention is highly resistant to photobleaching and photodegradation. The tolerance to thermal enhanced photodegradation is important because the illuminating diode under operation can become very hot and any material surrounding the LED will also heat up. This heat can damage a conventional phosphor around an LED, degrading its ability to downconvert the LED light. The phosphorescent system according to the invention is resistant to heat and is suitable for applications up to 500 DC. In these heteropolyoxymallate phosphates, the rare earth metal selected from the group of 126865.doc -13 - 200835777 yttrium, lanthanum and cerium may be replaced by indium or lanthanum, which may be phosphor, vanadium or铌 replaces another portion of the metal selected from the group consisting of ruthenium and tungsten or a combination thereof. [Embodiment] The luminescent material according to the present invention contains at least one phosphor capable of absorbing a portion of the light emitted by the radiation source and emitting light having a wavelength different from the absorbed light; wherein the at least the constituting body has a ' _铕(m) active heteropolymer

Milk partial resinate' has the general formula AaREb zMmQ3 (four) version of the heart H, where A is selected from at least the group of the following: metal, clock, sodium, potassium, strontium and strontium RE 'RE is a group of the following At least one rare earth metal selected from the group consisting of ruthenium, osmium and see 'M is a metal selected from the group consisting of indium and tungsten or a combination thereof, and wherein 叱ad, i 讣, 2(10) 6, 〇 Q &lt; 2 and 〇〇〇 2 &lt; z &lt; 〇 8. The disc system of this category is based on pin (ΠΙ) active luminescence, which has an iso-oxygen poly-n-tree n-salt structure. The molecular structure of the isomeric oxygen meta-resin can be derived from the basic isomeric oxygen meta-resin structure type, #中中金属原Π: The lanthanide is replaced by a heterometallic. In general, polyoxymethylene resin has an inorganic metal oxygen cluster that has been defined to recruit or polymerize structural units. The isomeric oxygen meta-resin acid salt can be described as: a meta-oxide oxide which can be miscellaneous [rxMm〇y]p• a heteropolyoxymoxy-alkali acid salt including: or a plurality of: original: such a hetero atom In other words, the non-metal, semi-metal or all-sub-substituent substitution of the MQy structure can be reduced by (4) the earthy gold bow into the solid-state host lattice of the hetero-oxygen meta-resin to become 126865.doc • 14- 200835777 Heteropolyoxymaleate has a crystal structure that typically includes one or more centers &quot;heteroatoms&quot; surrounded by a framework of metal atoms bonded to the milk atom. In a typical heteropolyoxymethylene salt, a suitable heteroatom (X") is typically bonded to the framework metal atom (&quot;M&quot;) by an oxygen atom (&quot;〇&quot;). The framework metal is typically bonded to a central X-ray through an oxygen atom and is further bonded to the other through the oxygen atom: the framework metal. The base metal may also have a non-bridged &quot;end&quot; oxygen atom. Beauty festival

: The oxidation state of atoms and base metals, a heteropolyacid cage body; 曰: f negative charge (-&quot;polyoxyanion)), which is balanced by a charge balance number of the appropriate metal cation. The frame bismuth metal is selected from the transition metal towel of !a and the combination of the crane and the combination thereof. A mixture of base metals can be used, however, the y ^ portion of the w atom is preferred. It can be replaced by indium lin or by phosphor, yttrium or yttrium. A portion of the metal selected from the group of combinations thereof. The hetero atomic lanthanide used in the polyoxygenate resin according to the present invention is a rare earth metal selected from the group of the following: 35, lanthanum. Preferred X heteroatoms of the invention, whether alone or in combination with ruthenium and osmium, may be substituted by indium or silk, or a portion of the rare earth metal of Group (4) &amp; (d) Oxygen partial resinate exhibits a substantial increase over the strength of polyoxymethylene metanates including other cationic forms, money 9. For specific embodiments La2m, eg, tungstic acid in polyoxymethylene resinate Salt substituted molybdate A substantial increase in excitation for the spectrum of the spectrum is shown in Figure 5. The dopant ion system is used alone or in combination with hydrazine to act as a total of 126865.doc -15-200835777 activator. The ratio Z of dopant ions, either alone or in combination with a coactivator, is in the range of 0·002 &lt; ζ &lt; 0·8. When the ratio z is low, the luminosity is lowered because of the excited emission of photoluminescence The number of centers is reduced, and density quenching occurs when the z is greater than 0.8. Density quenching refers to the decrease in the emission intensity that occurs when the concentration of the catalyst added to increase the luminosity of the luminescent material increases beyond the optimum level. According to a preferred embodiment of a series of the invention, one or more M〇 units of the heteropolyoxy cation [Mm〇y]P are replaced by a plurality of rare earth cations to produce a series of AXM2〇8:El ^ X2M3〇12:Eu, whose luminescent properties are studied by excitation, emission and reflection spectroscopy. LiLaW2O8 of the red-emitting phosphorescent composition according to the invention having particularly advantageous properties: 50% Eu, La2W3O12: 40% Eu,

La2M〇3〇12:4〇〇/〇Eu and La2M〇1 $Wi 5〇12:5%, phosphor. This composition phosphor has a quantum efficiency of 80 to 95% at 465 nm excitation. Since the hetero atom is introduced into the crystal structure, the ruthenium (111) active heteropolyoxymethylene resin salt has a different charge distribution and polarity than the corresponding non-replacement heteropolyoxymoxylate. The type of heteroatomic pattern present in the phosphor compound and the local bonding environment of 铕(π) in the lattice of the oxygen-donating host in the number, and determining the characteristics of the excitation and emission spectra. Such ruthenium (III) active isomeric oxygen meta-resin phosphates are particularly responsive to the broad energy portion of the electromagnetic spectrum within the UV and visible blue portions of the electromagnetic aperture. An essential factor is the excitation wavelength of the luminescent material in the long-wavelength UVA (370 to 400 nm) range, and especially in the range of blue visible light (45〇 to 126865.doc -16-200835777 480 nm), see Figure 2 To 6. These phosphors are therefore sufficiently excited by all of the blue to violet light-emitting diodes on the market. Since the excitation spectrum of the phosphor in the blue/violet range is concentrated at 45 5 to 465 nm, it is preferred to combine the blue LED emitted in the wavelength range with the phosphor according to the present invention. The strong absorption of UV-A light and/or blue light is attributed to the weak 4f-4f of Eu(III) at about 37〇 to 41〇-nm (F6-5d3) and 450 to 480 nm (7F6-5D2). The absorption line is enhanced. This is achieved by using a host lattice containing a tungstate or molybdate moiety molecule that is either ruthenium alone or combined with ruthenium and osmium. In such a host lattice with a lower crystal structure symmetry, the banned characters of the 4f_4f transition of Eu(In) are relaxed to some extent, resulting in an increase in these transition absorption intensities. The reflection spectrum of La2M〇2 4wq 6〇i2:Eu is shown in the following exemplary manner (Fig. 7): absorption at the 4f-4f transition at 395, 465 and 530 nm has been enhanced. When excited by the UVA or blue range of radiation of the electromagnetic spectrum, each phosphor of the φ 铕(III) active isomeric oxygen meta-acidate type emits a narrow band of amber, or red fluorescing. In Figure 2, in accordance with the drawings of this specification, the emission (and excitation) spectrum of a typical phosphor according to the present invention is given. The phosphor according to the present invention has an emission spectrum whose peak wavelength is usually from 61 620 to 620 nm. Therefore, the luminescent material has an ideal property of converting the main UVA/blue radiation of the nitride semiconductor light-emitting diode into white or colored yellow, amber and red light. Table 1 lists the emission maxima of the 126865.doc -17-200835777 exemplary phosphor containing the composition of the heteropolyoxymoxylate resin according to the present invention: Table 1:

Phosphor composition emission maximum [nm] Gd2M〇2〇9:Eu 615 Gd2Mo3〇i2:Eu 615 La2Mo2〇9:Eu 612 La2Mo3〇i2:Eu 615 La2M〇3.xWxO π :Eu3+ 615 LiLaMo2〇8:Eu 615 LiGdMo208:Eu 615 LiYMo2〇8:Eu 615 La2W3〇i2:Eu 615 Y2W3〇i2:Eu 612 Gd2W3〇i2:Eu 615 LiGdW2〇8:Eu 615 LiYW208:Eu 615 LiLaW208:Eu 615 LiEuW208-x/2Fx 615 LiGdW2 〇8-x/2Fx:Eu 615 LiYW208.x/2Fx:Eu 613 LiLaW2〇8-x/2Fx:Eu 615 KGdW2〇8:Eu 615 KYW2〇8:Eu 615 KLaW208:Eu 615 KEuW208.x/2Fx 615 KGdW2 〇8.x/2Fx:Eu 615 126865.doc -18- 200835777 KYW2〇8.x/2Fx:Eu 615 KLaW208-x/2Fx:Eu 615 NaGdW2〇8:Eu 615 NaYW208:Eu 615 NaLaW2〇8:Eu 615 NaEuW2〇8-x/2Fx 615 NaGdW2〇8-x/2Fx:Eu 615 NaYW208.x/2Fx:Eu 615 NaLaW2〇8-x/2Fx:Eu 615 Heteropolyoxymethylene resin is used in this technology Prepared by known techniques. In a typical procedure, the isomeric oxygen meta-resin is prepared by a process starting from a suitable amount of low pH (usually &lt;1) molybdate and ferrite. The adjustment of the pH determines the host lattice of the polyoxygen cations. In this preparation, a source of a metal such as molybdate and/or tungstate, such as a source of a soluble phosphate, is combined with a mineral acid such as sulfuric acid to form an acidified mixture. . A soluble metal test compound is added to the resulting product which forms a precipitate of the heteropolyoxymethylene resinate. The precipitate is filtered, dried and burned. After combustion, the powders are characterized by an X-ray diffraction of the powder (Cu, Κα line), which shows that all of the compounds have formed. Since lithium is replaced by lithium and tungsten is replaced by niobium and tantalum, the X-ray diffraction data of LiLaW208:Eu as shown in Fig. 10 is consistent with the structure of NaLaW208 with some small deviation in position and intensity. Similarly, since tungsten is replaced by tantalum and niobium, the X-ray diffraction data of La2W3012:Eu as shown in Fig. 11 is based on the position and intensity of some small deviations 126865.doc -19-200835777 difference and La2W3〇12 structure Consistent. According to a second aspect of the present invention, there is provided a 彡 彡 H H , , , , , 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及Wavelength I: two luminescent materials of at least one first scale, wherein the system has a 铕 (III) active 昱 polyoxan pepper Jiuzhuang /, like milk partial resinate, has a universal

AaREb.zMm〇3m + 3/2b + a.l/2xFx: Ell2 〇

The luminescent material is useful in any of the illumination systems that contain a primary light source. The &amp; source includes a preferred semiconductor optically illuminating emitter and other means for emitting optical light in response to electrical excitation. The semiconductor optical light emitter includes a light-emitting diode chip, a light-emitting polymer (LED), an organic light-emitting diode (Peer, a polymer light device (PLED), etc. Also included, for example, are found in discharge lamps and fluorescent lamps, such as mercury low and high pressure discharge lamps, sulfur discharge lamps, and discharge lamps based on Kyoko Koda, and radiation sources in x-ray tubes. As a radiation source having the luminescence converter of the present invention, in a preferred embodiment of the present invention, the radiation source is a light-emitting diode. Any configuration of the m system is encompassed by the present invention, and includes a light-emitting diode. Or an array of light-emitting diodes according to the present invention and a luminescent material 'as specified above, when a specific UV or blue light is emitted by an LED emitting a specific color or white light. Combining the luminescent material with a luminescence An array of diodes or light-emitting diodes may be useful to configure an epitaxial device and a flip-chip device. In one preferred embodiment of the present invention, the source has a peak value of I26865.doc -20- 20 0835777 A blue to violet light emitting diode emitting at one of the wavelengths in the range of 370 to 480 nm. A detailed architecture of one embodiment of such illumination is shown in Figure 1, and will now be described. Figure 1 shows a A schematic view of a ruthenium-type light-emitting diode comprising a coating 3 of the luminescent material. The device comprises a wafer-type light-emitting diode 1 as a radiation source. The light-emitting diode dies are positioned in a reflector cup. In the lead frame 2, the die 1 is connected to a first via a soldering wire 7.

Terminal 6, and directly connected to the "the: electrical terminal 6. The recess of the reflector cup is filled with a coating material 3 comprising a luminescent material according to the invention to form a coating embedded in the reflector cup. Phosphors 4, 5 are applied individually or in the form of a blend. The coating material typically contains a -polymeric encapsulated scale or scale composition. The phosphor or phosphor blend in these embodiments should exhibit properties that are resistant to the high stability of the encapsulate. Preferably, the polymer has optical clarity characteristics to avoid severe light scattering. In the LED industry, many different polymers are known to be used in the manufacture of led lamps. In a specific embodiment, the polymer is selected from the group consisting of epoxy resins and lithene resins. Encapsulation can be accomplished by adding the phosphor mixture to a liquid of a polymer precursor. For example, the phosphor mixture can be a granular powder. The illuminating body particles are introduced into the polymer precursor liquid to form a slurry (i.e., the particles are suspended). After polymerization, the disc mixture is firmly encapsulated in place. In a specific embodiment, the luminescent material and the LED dies are encapsulated in a polymer. The transparent coating material may advantageously have light-diffusing particles (so-called diffusers) 126865.doc • 21 · 200835777 Examples of such diffusers include mineral fillers, 丨τ will be rumored, CaF2

Ti02, Si〇2, CaC03 or BaS04 or other organic, m organic pigments. These materials can be added to the aforementioned resins in a simple manner. In operation, power is applied to the die to initiate the double action of the day. The main light, such as blue light, is emitted when the die is activated. The part that has been emitted and the first part of the heart is completely or partially absorbed by the luminescent material. Shovel ..., silly, the luminescent material emits secondary light, that is: has a longer peak wavelength, palpitations are converted first, to return to the main

To absorb light. The unexposed portion of the emitted primary light is transmitted through the luminescent layer together with the secondary light. The reflector directs the primary light and the secondary light that are not absorbed in the normal direction to 1 m, which is a composite light composed of primary light emitted from the crystal grains and secondary light emitted from the cold light layer. The color temperature or color point of the output light of the illumination system in accordance with the present invention will vary depending on the spectral distribution and intensity of the secondary light. First, the color temperature or color point of the main can be changed by appropriately selecting the light-emitting diode. Secondly, the color temperature or color point of the secondary light can be varied by the appropriate selection of the phosphor blend in the luminescent material. At the same time, the thickness of the luminescent material and the associated phosphor content can be configured to convert a desired percentage of the primary light incident on the luminescent material. Depending on the light-emitting wavelength of the light-emitting diode and the phosphors, one of the chromaticity diagrams of the two (plural) phosphors and the color triangles (polygons) formed by the color points of the light-emitting elements can be provided. The light of the point. According to one aspect of the present invention, the output light of the illumination system can have a spectral distribution of "white" light. The light represented by the term "white light" stimulates the red color in the naked eye. , green and blue sensors to produce - a look that ordinary observers would consider to be "white". This light can be referred to as a warm white light or a blue light (generally called a cool white light). In a particular embodiment of the white light illumination system according to the invention - the device can advantageously be produced by selecting the luminescent material, which contains red-emitting enthalpy (10) active heteropoly oxygen according to the invention Partial resinate' to convert the radiation emitted by the blue-emitting diode into mutual

The red wavelength range is reddened to form warm white light. In this embodiment, (4) transmitting (unabsorbed) light that is emitted from the diode through the scale layer, and (b) (four) light absorption and light emission from the diode are down-converted. In the red light, the illumination device thus emits light having a plurality of wavelength components. This result is a illuminating device that emits warm white light. In another embodiment, a white light illumination system in accordance with the present invention can be advantageously produced by selecting a luminescent material comprising a phosphor according to the invention and one or more second phosphors. A phosphor blend is such that a blue radiation emitted by the blue light-emitting diode is converted to a complementary wavelength range to form a multi-color, and in particular three-color (RGB) white light. A second phosphorescent system Eu(II) active phosphor suitable for use in the phosphor blend, such as (Cai-xSrx)S:Eu, wherein 0 1 and (Sri-x_yBaxCay) 2 wherein 0Sa&lt;5,0&lt;xSl , Ogysi and 〇&lt;ζ&lt;ι, and srs:Eu2+,· CaS:Eu2+; CaS:Eu2+^ Mn2+ , and (Zn,Cd)S:Ag+ ; 126865.doc 200835777

Mg4Ge05_5F: Mn4+; Y202S: Eu2+' ZnS: Mn2+ (for red emission), and additional phosphor material having an emission spectrum in the red region of the visible spectrum upon excitation as described herein. For green emission, a typical phosphor contains a material selected from the following: (BahSi^ Si04:Eu, where oun, SrGa2S4:Eu, SrSi2N202:Eii, RE3Al5〇i2:Ce, where RE contains the genus, and all lanthanide metals, And other phosphor materials having an emission spectrum in the green region of the visible spectrum upon excitation as described herein. In some specific embodiments, in addition to the specific red and green emission light, the can The light body blend contains blue or blue-green emitting phosphor particles; suitable emitting phosphors may contain, for example, BaMgAl1()〇17:Eu, Ba5Si04(Cl,Br)6:Eu, CaLn2S4:Ce^ wherein Ln contains yttrium and Lanthanide metal, and (Sr,Ba,Ca)5(P〇4)3Cl:Eu or other disc material having an emission spectrum in the blue region of the visible spectrum upon excitation as described herein. In a specific embodiment, the phosphor composition contains a type of phosphor particles selected to produce yellow light upon excitation. For yellow emission, a typical phosphor suitable for use in the phosphor blend contains (Y, Gd 3Al5〇12:Ce,Pr and as described herein upon excitation Visible emission spectrum of phosphor materials other of the yellow region of the spectrum displayed in the Table 2 Examples of useful compositions of the blends in the luminescent material LED and phosphor 126865.doc -24 · 200835777 Table 2:

^led 395 BaMgAli〇017:Eu (Sr1.xBax)2Si04 : Eu LiLaW208:Eu 395 BaMgAI10O17:Eu (Sri.xBax)2Si04 : Eu La2W3-xMox012:Eu 395 BaMgAli〇017:Eu (Sr1.xBax)Si2N2〇2 :Eu LiLaW208:Eu 395 BaMgAIi〇017:Eu (STi.xBax)Si2N2〇2:Eu La2W3.xMox012:Eu 395 BaMgAl10O17:Eu (Sri.xBax)2Si04 : Eu (Sr].xCax)2Si〇4 · Eu LiLaW208 :Eu 395 BaMgAli〇017:Eu (Sr1.xBax)2Si04 ^ Eu (Sri.xCax)2Si〇4 : Eu La2 W3.xMoxO 12: Eu 395 BaMgAI10O17:Eu Sr4Al14025:Eu (Sri.xCax)2Si〇4 : Eu LiLaW208:Eu 395 BaMgAl10On:Eu Sr4Al14〇25:Eu (Sri.xCax)2Si〇4 · Eu La2W3-xMox012:Eu 395 Ca5(P〇4)3Cl:Eu (Sr1.xBax)2Si〇4 ^ Eu LiLaW208:Eu 395 Ca5(P〇4)3 Cl: Eu (Sri.xBax)2Si〇4 * Eu La2W3_xMox012: Eu 395 Ca5(P〇4)3Cl:Eu (Sri.xBax)Si2N2〇2:Eu LiLaW208:Eii 395 Ca5( P04)3Cl:Eu (Sr1.xBax)Si2N2〇2:Eu La2W3.xMox012:Eu 395 Ca5(P〇4)3Cl:Eu (Sri.xBax)2Si04 : Em (Sr1.xCax)2Si04 ^ Eu LiLaW2〇s: Eu 395 Ca5(P〇4)3Cl:Eu (Sr1.xBax)2Si04 : Eu (Sri.xCax)2Si〇4 ^ Eu La2 W 3.xMoxO 12 : Eu 3 95 Ca5(P〇4)3Cl:Eu Sr4Ali4〇25:Eu (Sri_xCax)2Si〇4 : Eu LiLaW208:Eu 395 Ca5(P〇4)3Cl:Eu Sr4Ali4〇25:Ell (Sr1.xCax)2Si〇4 : Eu La2W3.xMox〇i2:Eu 465 (Y 1.xGdx)3Al5〇i2:Ce LiLaW208:Eu 465 (Y i.xGdx)3Al5〇i2:Ce La2 W3.xMoxO ! 2: Eu 465 (STi.xBax)Si2N2 〇2Eu (Y 1.xGdx)3Al5〇12*Ce LiLaW208:Eu 465 (Sr!.xBax)Si2N2〇2Eu i-xGdx)3Al5〇12:Ce La2 W 3.xMoxO 12: Eu 465 (Y UxLux)3A\ 5On: Co (Y 1.xGdx)3Al5〇i2:Ce LiLaW208:Eu 465 (Yi.xLux)3Al5012:Ce (Yi-xGdx)3Al5012:Ce La2W3.xMox〇i2:Eu 465 (Y (Sr1.xCax)2Si04 : Eu LiLaW2〇8:Eu 465 (Yj.xLUxisAlsOniCe (Sr1.xCax)2Si04 : Eu La2W3.xMox〇i2:Eu 465 (Y i-xLUx)3Al5〇!2:Ce (SrI.xCax)2Si04 : Eu (Sr1 .xBax)2Si5N8 : Eu LiLaW2Og:Eu 465 (Yi-JLi^AlsOeCe (Sr1.xCax)2Si04 * Eu (Sr^xBa^SisNg: Eu 1 La2W3.xMox012:Eu According to a specific embodiment of the invention, a white light emission The illumination system can be implemented by blending an inorganic luminescent material containing a mixture of one of the two phosphors to produce a luminescent conversion layer. When selecting a first phosphor (4) red emission -25- 126865.doc 200835777

When LiLaW2 〇 8: Eu, the second phosphor (5) yellow emission (Y'Gd) 3Al5012: Ce is selected. A portion of the blue radiation emitted by a 465 nm InGaN light-emitting diode is by the inorganic luminescent material ULaW2 〇 8: as displaced into the amber to red spectral region, and the result is complementary to the color blue In the wavelength range. Another portion of the blue radiation emitted by a 465 nm InGaN light-emitting diode is displaced into the yellow spectral region by the inorganic luminescent material (Y, Gd) 3Al5 〇 i2: Ce. In this embodiment, (a) passing (unabsorbed) blue light passing through the luminescent material, (b) amber to red light due to down-conversion of light absorbed by the first phosphor, and c) The yellow light caused by the down-conversion of the light absorbed by the second phosphor, the light-emitting device thus emits light having a plurality of wavelength components. The human observer perceives the combination of the blue primary light and the multicolor secondary light of the phosphor blend into white light. In this case, the color tone (color point in the CIE chromaticity diagram) of the generated white light can be changed by appropriately selecting the phosphor according to the mixture and the concentration. Figure 8 shows the emission spectrum of a pcLED having a luminescent material containing LiLaW208.Eu and (Y, Gd)3Al5012:Ce in combination with a blue emitting LED having a maximum emission at 465 nm. The correlated color temperature CCT, color rendering rate, associated color point, and lumen efficiency of this non-parallel pcLED have been measured. Table 3 below shows the lumen efficiency (LE), color appearance ((Ra8), and color point of a white LED with various combinations of blue-emitting InGaN LED (465 nm), LiLaW2〇8:Eu, and (Y,Gd)3Al5012:Ce. (x, y) is aggregated into a function of the correlated color temperature CCT. 126865.doc -26- 200835777 Table 3: CCTIK1 ^00 〇ζ υ, rotten 4 〇, 36 〇 6 3: 83 〇, 3594 〇, 3687

One alternative embodiment of light provides that the emission has money. For color [e.g., _ to red illumination of the output light ..., m applications of specific embodiments include security lighting for automobiles and traffic: and single-illumination. - The yellow to red light emitting illumination system can convert a blue radiation emitted by the blue light emitting diode by selecting a luminescent material containing a sulphur to red emitting yttrium (m) active heteropolyoxyl metaphosphate phosphor It is advantageously produced by forming a two-color yellow to red light in the complementary wavelength range. The color output of the LED phosphor (4) is very sensitive to the thickness of the scale layer. If the phosphor layer is thick and contains an excess of one-to-red (铕) active heteropolyoxygenate-phosphate phosphor, A smaller amount of blue LED light passes through the thick phosphor layer. The combined led phosphor system will then exhibit yellow to red light as the result is dominated by the yellow to red secondary light of the phosphor. Therefore, the thickness of the phosphor layer is a key variable affecting the color output of the system. Thus, in this embodiment, the colored yellow to red light is produced by a luminescent material comprising a ruthenium (III) active heteropolyoxymethylene phosphate phosphor. A portion of the blue radiation emitted by a 465 nm InGaN light-emitting diode is displaced into the amber to red spectral region by the luminescent material and results in a wavelength range complementary to coloration relative to the color blue. In this case, 126865.doc -27-200835777 'can change the color and the color of the color light (color point in the CIE chromaticity diagram) generated by the phosphor change according to the mixture and the concentration. A human observer perceives the combination of the amber and the secondary light of the red-emitting scale body into a yellow to red light.

Although the present invention has been described in connection with specific embodiments for the purpose of illustration, the invention is not limited to the specific embodiments. Various adaptations and modifications can be made to the invention without departing from the scope of the invention. For example, an 'I synthetic luminescence converter can be fabricated from a phosphor material other than the disc. These phosphors can be replaced with any conventional phosphor material. Therefore, the spirit and scope of the attached patent application should not be limited to the above description. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram of a two-color white scale light conversion led lamp comprising one of the luminescent materials according to the present invention, which is oriented in the path direction of the radiation emitted by an LED wafer. Figure 2 shows the excitation and emission spectra of a luminescent material in accordance with the present invention. Figure 3 shows the excitation spectrum of LiLaW208:E\i which is dependent on the concentration of Eu(III). Figure 4 shows the excitation spectrum of La2W3012:Eu which is dependent on the concentration of Eu(III). Fig. 5 shows the excitation spectrum of La2(Mo,W)3012:Eii which is dependent on the concentration of W(VI). Fig. 6 shows the excitation spectrum of La2Mo3012:Eu which is dependent on the concentration of Eu(III). 0 126865.doc -28 - 200835777 Fig. 7 shows the reflection spectrum of 1^21^1〇2.4^〇.6〇12: £11. Figure 8 shows an emission spectrum of three versions of a warm white light-emitting LED with Tc = 5200 K, Tc = 4570 K, and Tc 3920 K, containing a blue (465 nm) emitting LED wafer as a yellow emitting phosphor ( Y, Gd) 3Al5012: Ce and LiLaW208: Eu as a red emitting phosphor. Figure 9 shows the effect of different metal tests on the emission intensity of A LaMo2〇8:Eu, where A = Li, Na, K, Rb, Cs. Figure 10 shows the x-ray diffraction ® pattern of NaLaW208 compared to LiLaW2〇8:Eu. Figure 11 shows an X-ray diffraction pattern of La2W3〇i2 compared to La2W3012:Eu. [Main component symbol description] 1 2 3 4 6 7 Light-emitting diode Reflector cup lead frame Coating (material) Phosphor Electrical terminal Solder wire 126865.doc -29-

Claims (1)

200835777 X. Patent application scope ···, the monthly system 'which contains-radiation source and luminescent material, the luminescent material contains a part capable of absorbing radiation emitted by the radiation source and: the shot has a different absorption At least one first-phosphorus wire of the radiation of the wavelength of radiation, wherein the at least-scale system - 铕(4) active heteropolyoxygen ^ ^ M ^ ^ ^ AaRE, zMm 〇 3m + 3/2b + a. 1/2 x Fx; Eu2 , Wherein A is at least one alkali metal selected from the group consisting of lithium, sodium, potassium, cesium and samarium, and RE is selected from the group of the following: to a rare earth metal: lanthanum, cerium and釓, M is a metal selected from the group consisting of molybdenum and tungsten or a combination thereof, and wherein 叱ad, , 2Sm$6, 〇&lt;χ&lt;2 and 〇·〇〇2&lt;ζ&lt; Ϊ́.〇. 2. The illumination system of claim 1, wherein the source of radiation is a light emitting diode. 3. The illumination system of claim 2, wherein the source of radiation is a light emitting diode having a peak emission wavelength in the range of 370 to 480 nm. 4. The illumination system of claim 1 which also contains at least a second optical body. 5. The illumination system of claim 4, wherein the second phosphorescent system emits a phosphor from green to yellow. 6. The illumination system of claim 5, wherein the second fill system is a green to yellow emitting phosphor selected from the group consisting of: (BaNxSrx)2Si04:Eu, wherein OSxSl, SrGa2S4: Eu, SrSi2N202: Eu, RE3Al5012: Ce, where RE contains the genus, and all lanthanide metals. 7. The illumination system of claim 4, wherein the second phosphorescent system emits a phosphor from blue to green. The illumination system of claim 7, wherein the blue to green emission phosphorescent system is selected from the group consisting of: BaMgAllD〇17.; Eu, Ba5Si〇4(ci, Br)6: Eu, CaLn2S4: Ce, wherein Ln contains ruthenium and the lanthanide metals and (Sr,Ba,Ca) 5(P〇4)3C1:Eu. 9. The illumination system of claim 4, wherein the second phosphorescent system emits a luminescent body. 10. The illumination system of claim 9, wherein the red-emitting phosphorescent system is selected from the group consisting of Eu(III) active phosphors, which contain (Cai_xSrj S: Eu, and (Sri x yBaxCay) 2 zSi5 aAlaN "〇 a: E\, where 0Sa&lt;5,0&lt;xsi,osyy and 〇&lt;zsi. 11 · A luminescent material containing a portion capable of absorbing light emitted by the radiation source and having a different emission than the absorbed At least one first phosphor of light of a wavelength of light, wherein the at least one phosphorescent system is a bismuth (ΠΙ) active isomeric oxygen meta-alloyate having the general formula AaKEb_zMm〇3m+3/2b+ai/2xFx:EUz, Wherein a is at least one alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium and planer, and the rule is at least one rare earth metal selected from the group consisting of ruthenium, osmium and釓' Μ is a metal selected from the group consisting of molybdenum and tungsten or a combination thereof, and wherein, isbu, 2SmS6, 〇&lt;χ&lt;2 and 0.002&lt;ζ&lt;1·〇〇六丁釓The part of the group selected from the rare earth metal. 13 · If the eye is good, the cold light is good. A coffin, in which a part of a metal selected from the group consisting of molybdenum and niobium or a combination thereof is replaced by a phosphor, vanadium or niobium. 126865.doc