TWI298348B - - Google Patents

Description

1298348 * ▲ IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a fluorescent powder of a self-photodiode and a method for producing the same, and a fluorescent powder of a white light diode, the color temperature thereof In Τ=12000~25〇(ρκ, ' Ά small angle is divergence 6-12 degree angle, the light intensity is very high, at this time heterogeneous 'W conductive contact is on the back of the heterojunction white light diode flash ride And its production ^ method. ', Lu [previous technology] Nowadays, due to the advancement of semiconductor technology, semiconductor lighting technology has been rapidly developed. It is mainly manifested in the invention of various fine and read to store all the electric vacuum light bulb 1 for lighting The main purpose is to produce white light diodes. In these luminescence = body, the heterogeneous society should be indium nitride or gallium nitride, and its wavelength is better than 475 (10). Blue or other short wave and phosphor powder inorganic _ grain side, the fluorescent powder is small The particles are distributed onto the polymeric film by a uniform sentence, and the polymeric film surrounds each of the light-emitting surfaces of the heterojunction. The short-wave light penetrates the transparent polymer coating to reach the layer of luminescent powder particles coated on the polymer surface. Physical phenomena: - Fluorescent powder particles cause short-wave scattering; - Fluorescent powder particles absorb light; - Re-radiate in the form of fluorescence. - Human-emitting wavelengths longer. Fluorescent powders are mixed with the original short-wave light to form Complete and uniform light, its color and hue are close to standard white light, and the color temperature is between Τ=2800 1298348 ^ nose-KKWK. The law of the above three resident phenomena is now widely recognized. Thus the initial light scattering and phosphor powder The distribution area is proportional to, that is, proportional to their size. At the same time, the light scattering is inversely proportional to the wavelength of the light emitted onto the phosphor particles, which causes the short waves emitted by the semiconductor heterojunction to be emitted compared to them. The long-wave scattering intensity is stronger. The second optical phenomenon - the absorption of light by the phosphor depends on the energy structure of the energy region of the material, and the energy region strongly absorbs the energy emitted for the first time, which is determined by the absorption coefficient value k >. The absorption coefficient is determined according to the residual radiation after passing through a specific thickness of material. This relationship is J=J0e-kd, where J and J0 are the last of the light passing through the thickness of d plating. Initial strength. The strong absorption of solid matter is related to the structure of the energy region of the phosphor material. If the material has a width of the forbidden zone Eg exceeding 2 electron volts, the similar material absorbs visible light radiation is not very strong. In the case where the absorption coefficients are the same, the particle size diameter of k = 5000 CM-1 phosphor powder is (1 = 10 μm = 1 χ 10 · 3 cm and absorbs more than 50% of the first > secondary radiation emitted onto the phosphor particles. The third optical phenomenon that occurs during the interaction between the initial short-wave radiation and the phosphor is the fluorescing phenomenon. The absorbed primary radiant energy excites the internal energy level of the catalyst at the center of the phosphor particle. After the level, the electrons in the initial state of the functions 3d and 4f are transferred to the position of the more energetic state 'At this time, the catalyst atoms are not ionized. The life cycle of the excited electrons in this state is not long, generally 1 X KT3 - 1 X 10-6 seconds, after which the excited electrons are recombined with the small holes in the lower layer of the 1298348 catalyst. At this time, the phosphorescence phenomenon of the catalyst center is characterized by exciting the "pool shift" between the chief ray of the phosphor powder and the light it emits, and a sub-output. If the initial value is "pool displacement", which is generally equal to δ = 12 〇 _15 〇 nm ′ then the quantum output generally rarely exceeds 〇 8. The quantitative relationship between the energy of the emitted light and the excitation light can be expressed as W-flow fW New λ 丝 / λ Wei · γ. In the case of wNEW = 1010 mw/mm2, for standard configuration of blue diode and long-wave yellow phosphor, the equation W (four) = 10 x 470 / 580 x 0.8 = 6.4 mW / mm ' This equation indicates that the fluorescence power density is about 6 4mW/mm2, which guarantees that the luminous one-pole luminous party exceeds 10,000 candelas/mm2. A similar white light-emitting diode is described in U.S. Patent No. 5,998,925, issued to Shimizu et al. In accordance with the patent, an aluminum bismuth phosphor is used in the binary radiation of the white light diode, and its composition is Y3Al5〇i2.Ce, which is applied as a fine powder on the surface of the gallium nitride indium nitride heterojunction. . According to the aforementioned patent data, the particle size of the phosphor powder is in the range of 〇 〇 〇 micrometers, for example, in the form of a suspension in the cerium oxide aerosol or epoxy resin to form a very thick coating on the light-emitting surface of the heterojunction. Under direct current, the light-emitting diode emits white light, and its color temperature is T=2800-10000 °K, the light intensity is 1〇15, and the light-emitting angle is 2Θ=6°. Although the intensity of the synthesized white light is quite high, this technical solution has a well-known defect that the white light is not uniform. This phenomenon reflects the formation of blue, blue-green and page-green concentric circles when the light-emitting diodes are projected onto the light-scattering screen by optical prisms. The maximum is that the scattering of this synthetic white light into several constituent colors 1298348 1 4 The phenomenon of 疋m is the initial blue filament of the heterojunction is actually rarely scattered by the glory powder. Therefore, the focus plane is not deviated from the center. Axis. At the same time, the glare beam is emitted from each of the phosphor particles in the form of self-illuminating lines, which have different angles of light at various angles that are very weakly focused on the output prism of the LED. Therefore, the proportional relationship between several constituent colors of the towel core and the initial blue and yellow radiance is immediately unbalanced. This produces a chromatographically dispersive color image when projected onto a white glory. A similar image is called the effect "rain" phenomenon. The aforementioned U.S. Patent No. 5,998,925 seeks to revise the technical solutions at various inventive levels. In addition, another U.S. Patent No. 6,351,69 B1 (2,2,2, issued to Lowery et al.) is incorporated herein by reference. According to this patent, in order to eliminate the dispersion of different light rays, these dispersing substances such as highly dispersed Si〇2 or Ti〇2 are added to the composition of the light-emitting diode phosphor conversion radiator. Since the presence of a large amount of the above-mentioned substance particles in the phosphor powder particles, the initial short-wave blue light emission causes multiple scattering. The part of the radiation excites the long-wavelength excitation light of the fluorescent powder particles. When radiating other parts with different directions in space, the optical prisms are combined to form a white light, and in this case, no "hot spots" (ie, brighter) are formed. Blue highlights. Light-emitting diodes synthesize white light in a variety of similar shades, which can be demonstrated by numerous US patents, such as U.S. Patent No. 6,340,824 B1, U.S. Patent No. 6,361,192 B1, No. 6,501,100 B1, and U.S. Patent Application No. 2002/0084745A1. Consistent with all of these patents, very finely dispersed phosphor particles are combined with optical dispersant particles such as Si〇2 or 1298348.

Ti〇2 or A!N, which makes the white light-free cross section very stable, and the color temperature T=2800-6000°K. The light intensity of a similar structure can reach κ 15_16 candle. Although similar instruments are used in large numbers, they have serious drawbacks: These structures have very low light intensity at small angles. Thus, even by using a special prism, it is possible to generate a white light of a strong candle from the surface of the heterojunction, which is not enough for the use of a structural fast on a special signal device such as the railway L number 4. The combination of such a light-emitting diode with a large φ angle optical structure does not allow the optical flow value to reach Φ^2-4 lumens, which is of course insufficient for economical illumination, and is a drawback. SUMMARY OF THE INVENTION In order to solve the above disadvantages of the prior art, the main object of the present invention is to provide a white light emitting diode phosphor powder, which is designed with a white light diode based on a GaN heterojunction. There is a very high or even very high white light small angle light intensity value 'specifically it will be public 4 turbid light. The other purpose of #P本月月 is to create a light-emitting structure that guarantees the reproduction of white light and the previously given light tones. (4) These shades may belong to warm white light, cool white light, and moonlight white. Table, > ^ Another purpose of the sun and the moon is to create a white light flow based on the secret __ heterojunction, such as (four) lumens. Similar illuminating elements can be used to produce special light sources. The pot is the glory powder of the white light-emitting diode of the present invention, which is formed by an indium-bonded indium nitride semiconductor, and the wavelength of the Wei-ray is less than (4) 1298348 nm, 'prepared by milk Prepared base, catalyzed multi-faceted large-grain dispersion glory powder, the general formula of the pupil converter is Gd3-xy-zYxLuyCezAlp〇q, wherein the chemical index changes as follows: · L〇 < x < 2.6, 0.0001 0.5, 〇〇 purchased into 5, 4^: 3曰-q=4.5+1.5*p, the difference is that the phosphor powder is a single crystal dispersed by a large particle, and the multi-edge is mainly: a hexahedron, a hexahedron has two The mutually parallel base faces are 12___, • these sides are 9〇-150 to each other. The radius of the inscribed circle of the fluorinated powder particles is between 6 _ 12 and the height of the two bases is between 4 and 10 microns, and the multi-edge particles are directly bonded to the front and four The end face is optically contacted and covers 20 - 85% of the area of the heterojunction light surface, and the light-emitting surface and the long-wavelength light of the wavelength λ exceeding 560 nm converted by the phosphor powder particles constitute a synthetic white light, and the color temperature thereof is between 12 and 2500 〇K. At a small angle of divergence of 6-12 degrees, the light intensity is high, and the conductive contacts of the heterojunction are at the back of the heterojunction. For the purpose of the above-mentioned 'the white light-emitting diode filament of the present invention', the method of the invention includes the following steps: first taking the following (10), ^^ and Αΐ2〇3 oxides 4; taking the dry concentration Ce_3)3 water miscellaneous; the number of oxides taken from the scale is added to the Ce(NG3)3 aqueous solution towel and mixed well; the well-mixed tolerant liquid is placed in the human) t, the box towel is dried 26' to obtain a mixed powder; Add a certain amount of NajO4, KsSO4 and Qiuqi 4 powder to the mixed powder, mix well, and then put the mixed powder into the Shiyang 坩 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; - Temperature, and spread the temperature at this temperature - _ after the private speed rise / strict to the first / set, the temperature is maintained for the second time and then warmed to the third at the same speed! 298348 1 other degrees, this temperature After the third time, the temperature is lowered to room temperature and taken out at a constant speed; the unreacted material is washed with nitric acid and phosphoric acid, and then washed repeatedly to neutral with a large amount of water; and the washed powder is placed in an oven. Dry, dry, and then get the fluorescent powder product. [Embodiment] The physical essence of the present invention will be briefly explained. First, two charts (see Table _1 and Preparation 2) are presented, which show how light is applied to the surface of the heterojunction through the phosphor powder. In this case, Table_1 gives a coating made of phosphor powder particles of standard dispersion distribution and size. From Table_1, it was concluded that the coating consisted of a single large particle size phosphor and its sinter and was uneven in fill thickness (10). The space between the counties is covered by very small fluorescent powder particles. In this case, since the small particles of the phosphor powder can be superimposed on the height, the thickness of the fresh coating layer is micrometer. A coating of similar thickness consisting of fine phosphor powder is located in a large particle size powder particle or particle sintered form having no regular shape. Due to the high degree of dispersion of the phosphor particles used in the prototype, it is not possible to precisely focus it during photographic or optical conversion. Obviously, the diffusivity of similar scattering is characteristic of the fluorescence emitted by fine particles. The free surface portion of the heterojunction covered by the standard phosphor does not exceed 5 or the position, which severely limits the initial short-wave radiation output of the heterojunction. Given initial blue and luminescent powder long-wavelength _ 互 〇 〇 · G5: 〇 · 95 - 0.1: 0.9 determines the color of synthetic white light, synthetic white light in the standard prototype design in the warm white light area, color coordinates in the ubiquitous 35 Yu 〇37 to commit

Between 11 1298348. In the case of _, it can be that the county has a warm color from the light, but the known light-emitting diode design made of the 鬲 dispersed fluorescent powder small particle coating has important defects. Based on the phosphor powder particles and the heterojunction of indium and gallium, the phosphor powder coating using the large-capacity prismatic particles suggesting the highly dispersed phosphor powder of the present invention appears to be completely different in the coating. Large, plate-tower-shaped particles can be seen covering the radiating surface of the heterojunction. The outer diameter of the phosphor particles is on average 6 to 12 microns or larger. The inventive towel uses large particles to disperse the fluorescing - most particles possess a prismatic, mostly hexahedral shape. The prismatic aura has no obvious roughness, so the radiation from the crystal is mainly small angles generally not exceeding 2 inches. According to the equation cp=arctg(ni/n2), it is concluded that ηι is the air refractive index, m is the refractive index of the glory powder material, and the young green money is formed by the flat (four) facet and the front surface of the particle. The optical enthalpy and reflection form of the scattering. Because of this, the fluorescent light emitted by the large particle phosphor is very close in the direction of the optical axis of the output prism. The axis extracts the radiation from the filament layer. In this case, the long-wave light is well separated. The surface of the polar body forms a blue (short wave) and yellow (long wave) level uniform light beam with a small divergence. Thus, in the ^ diode, there is not a large amount of scattered #jTi〇2 particles or random powdery glory, and scattered light h' eliminates the phenomenon of multiple diffusion of the diode. Under the multiple electron spectroscopy, the present invention produces a magnified circle-catalyzed image of the early large particle phosphor powder particles of the base 12 12298348. The image shows that the particles are hexahedral columns, and the sides of the facet are trapezoidal facets, and the trapezoidal facets are 9〇(10). The _ facets that are parallel to each other intersect with the trapezoidal facets to form a positive axis of the axis. The main money silk red is riding the wire, which is excited. The 丨 丨 heart « knot _ wave light is also emitted through this recording surface. Further, it can be seen from Table 2 that the back side of each regular single crystal particle =: light degree is directly in optical contact with the heterojunction emitting surface. In the formation of large particles B: layer ... between the surface of some of the surface may be very thin transparent polymer 2 under the early reading of the wire - shirt, (four) radiation and Sukh will not disappear. The part of β-Wei fluorescent powder covering the heterogeneous surface can be obtained from Table_2, which may be different. For example, 20-85% of the heterojunction radiation surface is covered by the phosphor powder: correspondingly 20-85% of the short wave The blue light only penetrates the loose layer of the regular crystal to form the mouth light. This short-wavelength optical power can be expressed by two equations: Wb=(w(6) ～γ)γΒ(ΐ Sy)fc, where the first added portion is the initial blue light through the loose hole, and the second is added. Indicates the portion of the blue light that is not absorbed by the regular phosphor. This kind of emotion = product αιγ) - dragon with mass balance = shot required to turn, γ Β _ heterojunction outer core light shot output, Sy-heterogeneous part covered by regular phosphor powder, fluorescent powder for initial blue light radiation absorption coefficient For RB. Each fluorescent powder carving converts the initial excitation blue light into yellow Wei, and successfully obtains the blue light equivalent of the big god 'WPKUy' YB (Bu &>λΒ/λ♦, (10) symbol conforms to 1298348 { ► Fluorescent powder light shot When the lumen value is equal, the index, sum, and the semiconductor heterojunction and the maximum spectral wavelength of the phosphor are added. The concentration of the synthesized white light of the diode is very large. This value is optically called For light intensity, generally denoted by J=d<D/d〇) and according to Kadella measurement • (candle light)' to reach the accurately measured light divergence angle (according to the light intensity at a specific radiation angle " half weak value) . In addition, this invention has been known to have a very high level of strength. ^ Table-1 lists the wire strength values corresponding to the corresponding color coordinates. It should be noted that the intensity of the diode used in the present invention exceeds the commercial standard light intensity by a factor of four to five. If the standard: = body = test diode is irradiated (four) degree digital comparison, then the difference in light intensity 疋 J / J3T = l 〇 9. 25 / 12. ο X 6Vi 〇 2 = 109 · 25 /12 X 36/100=3. 6. Table 1

1298348

28 598 4 92.75 0.25 0.2 99 286 5 105.27 0.30 0.3 63 051 6 89.43 0.25 0.2 37 141 7 81.83 0.29 0.2 01 758 8 89. 03 0.27 0.2 95 600 9 109. 25 0.25 0.2 48 169 10 95. 28 0.30 0.2 10 921 11 12.0 0.30 0.3 crystal current 40 mA 0 area of heterojunction 12 81.18 0. 32 0.3 S=0. 2x0. 3 mm2 69 395 radiation angle 13 84. 88 0. 35 0.3 2Θ=10° commercial gauge 48 799 grid

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After knowing that the fluorescent powder is used, the significant increase in the light intensity of the diode may be due to the new light-emitting diode design. The great advantage of the light intensity of the light-emitting diode of the present invention is that the heterojunction is a ratio of each surface of the rectangular parallelepiped is 1:1: 〇·i to 1:2: 〇·12, and the base surface and Heterojunction radiation © the ratio of the high-intensity projection inscribed radius of the granitic powder of Langda County is 1:3 -1:1, which guarantees the initial blue light in the case of the best height of 6-8 microns. And the second-launched yellow-orange-yellow towel is uniformly mixed due to the color coordinates x=0 ' 2548 y=0, 2169 to χ=〇, 363 y=0,351, so there is a jade between The light separates (selects) and forms a short-wave center region of the light. The structure of the light-emitting diode is mainly a heterojunction composed of indium nitride, gallium nitride based and single crystal SiC or sapphire substrate. In the plan view, the heterojunction is a rectangular side with a ratio of 1:2 to 1:1·5 and a thickness of the epitaxial film on the smallest side of the heterojunction rectangle 疋0·1 — 0·12 geometry. Heterojunction conductive leads can be found in several designs 1298348. In the present invention, a graded contact design is used, with the positive and negative electrodes on one side of the epitaxial sheet. In this case, there is a special face between the InN layer and the p-contact, from the n-layer

GaN is epitaxially 20-40 microns. The upper electrode is in direct contact with the gallium nitride layer. At this point, the phosphor particles cover the outer surface of the GaN heterojunction and are located at the level of contact around the plane of the heterojunction junction. In the present invention, the heterojunction radiation surface area of 2 〇〇χ 3 〇〇 micrometer may cover 300 - 750 single large particle fluoresce powder, the cross section (or granule inscribed circle) diameter is between 6 - 24 microns, then The height of each regular particle does not exceed 6 to 8 microns. It must be pointed out that the glare powder particles that are in direct contact with the heterojunction radiation surface do not form a multi-layer coating in all directions of the phosphor layer relative to the heterojunction light-emitting plane, which will certainly be reflected in the light structure output intensity. The synthetic white light spectrum consists of two main bands, the intensity of which depends on the heterojunction radiation surface (4) wire bonding _ coverage training. The color coordinate value calculated from the synthesized light varies between X and G.28 - 0.42, and varies with Q 3〇 - 0.44. It must be pointed out that there are known synthetic white light schemes within known variations, such as cold self-light, warm self-light, and energy white. Fluorescent powder is a three-dimensional crystal structure. With the known compound tablecloth data, the general molecule 'has been paid & in the private" 'we understand that all the phosphor powder particles have the domain crystal structure of the Pnm space group, which is related to the known compound table. Consistent: Ce, is a mineral compound. According to the information of the present invention, glory powder

17 1298348 The crystal grid parameter of a substance varies between a = 12.1A and 12.21Α. This variation depends on the amount of Gd ions in the phosphor component that partially replaces the fluorescent base ions. The replacement of the γ+3 ion in the cation node by the rare earth Gd+3 is a parity replacement, and there is no need to perform other compensation changes by introducing a compensation substance into the material crystal grid. Adding Gd ions to the crystal lattice of the phosphor powder material can increase the refractive index of the phosphor powder crystal, and increase the initial composition of the original YAROACe from η=ι·92 to the new composition (1^15〇12). The heart's 11=1.99-2.00. After a certain amount of ion in the phosphor component is replaced by the recorded ion without change, the refractive index of the phosphor powder material will reach a very south value. By adding 铛 to the phosphor component The ions can enhance the yellow-green color, which also enhances the large absorption of the primary radiation of the gallium nitride indium nitride heterojunction by the phosphor powder, such as the phosphor particles and the heterojunction plane filled with the nitrided Ga_In-N. The optical output angle is then close to 1 〇. The refractive index of the phosphor powder is from η=1·92 to η=2·0, which reduces the direct output angle of the outer surface of the heterojunction 'but at the same time The radiation output of the optical fine area between the money filaments increases. The phosphor powder radiates through the heterojunction, increasing the total light output of the light-emitting diode. This supplementary radiation is eliminated by using the Frenel prism, which makes the firefly Light can be focused. In order to be from Firefly The formation of the powder particles is finally formed by adding a special dispersion medium of the organic polymer, and the refractive index is V_45_155. The organic polymer coating can act as a light collecting enthalpy, so that the surface light output angle of the phosphor powder particles can be increased to φ- 45. 'This can increase the collection of fluorescent powder radiation to reach 8〇_9〇. And in fact

18 1298348 No optical loss. The number of the radiant light in the plane of the hair 同 ’ ‘ 所 钱 钱 钱 钱 钱 钱 钱 此时 此时 此时 此时 此时 此时 此时 此时 此时 所有 所有 所有 所有 所有 所有 所有 所有 所有Excitation of fluorescence: =?_ The sub-round is well absorbed by the blue light. According to the measurement of the present invention, it is clear that the higher quantum output is consistent with the phosphor powder, and a considerable portion of the phosphor powder is cast and cast. replace. For this material county characteristic S excitation optical wavelength reflection coefficient relationship curve has a smaller diterpene form of the silk material is optically transparent _, ridge yellow green as X month in the exhibition 7F sample is made of fluorescent powder The composition of the absorption band of the catalyst ion is determined. The change in the crystal field inside the phosphor powder matrix that occurs during the addition of IL ions and _ sub-processes not only increases the refractive index of the phosphor powder material, but also enhances its absorption. This is the absorption spectrum of the glory powder material. The best optical matching with a heterojunction light shot, with a half-width of the heterojunction light shot, 5=35 -45 !1111. The strontium ions added to the glory powder extend the absorption spectrum to the short-wavelength region, so a more suitable short-wavelength light-emitting diode is known for exciting the glory powder, compared with the wavelength λ=45 camphor. Thus, in the present invention, a short-wave Ga-InN light-emitting diode is used, and the combination of the wavelength of λ = 445 lungs or shorter and the phosphor of the present invention ensures a high optical flow value and light output. As described above, known industrial phosphor powders, such as a series of phosphor powders produced by companies in Japan and the United States, do not satisfy the needs of the present invention, so that the phosphor powder particles are broken.

19 1298348, does not have a natural crystal polygon ‘which includes a large number of parallel planes, the heterojunction short-wave light from the surface should be absorbed through these planes, long-wave fluorescence from the other side. This electron microscopy study of industrial grade phosphor powders shows that they have a large number of craters, bends and traces on the surface, and the scales are flamboyant. The final process of Weiye production is the ball smashing and rolling H-ray. The surface product is detected based on the reflection coefficient value R. Fluorescent powder weighing (~ touch milligrams) exposes it to light source A until 8G% is applied to the table _light counter (four). If the glare powder of the present invention is similarly tested, its reflection coefficient is reduced to 55%. In a small amount of glory powder said:!: The difference in light response coefficient will be more obvious. What is important is that the quantum output of the phosphor powder is different due to the light scattering phenomenon on the silk surface. Thus, for the Xiangong# product, the fluorescence quantum output does not exceed 5咬%, and the quantum output value of the regular crystal polygonal surface of the present invention has a difference of - _ the possible reason is 'this The light-emitting diode used in the invention contains a ribbed (four) light powder, and the quantum output from the surface of itself 12_16 (general 14) exceeds 85%. (4) The chemical formula of the chemical composition of the powder is: u LuyCezAlpOq, wherein the chemical index changes as follows. 〇<χ<2 6, 〇.〇_scale 5, 0.0 tear (10)5, 4.7 sister 3, (four) 々, guarantees the strong long-wave yellow-orange luminescence of the light powder, the wavelength is on the average U=53()~595 The maximum half width λ〇, 5=110~130mn, increases with the increase of Gd ion content in the phosphor powder. In the present invention, the influence of the above cations on the properties of the phosphor powder is also noted. First 20 1298348 First, the cesium ion guarantees the main catalytic ion ce+3 octahedral form of the fluorescent powder crystal grid. The difference in geometry between the ruthenium and osmium cations is not very large (τ γ = 〇 · 97 Α Tc'l. 〇 4A) ‘the reason why the main crystallographic principle of forming a solid solution is followed. The introduction of the cesium ion TGd=0.95A increases the electric field gradient in the crystal, which can greatly improve the illumination in the Ce ion. The erbium ion is a very small (Tlu=〇85A) radius, which stabilizes the phosphor powder crystal grid and may reduce its mechanical strength during the introduction of catalytic large particle ions 钸Ce+3 into aluminum_钇_釓. . I. Fluorescent powder particles lack mechanical strength and are accompanied by their natural polygonal faces, as it is well known that the geometrical dimensions of the constituents of complex compounds are uncompensated with the same day π疋 with deep fractures of the crystal or microcrystal surface, fault protrusions or Notch. The crystal shape of the complex compound must be accompanied by brittleness, reduced microhardness, rapid dissolution in the pickling agent, and the like. In the present invention, the energy configuration of the catalytic ion Ce+3 has two main criteria, 2Fi/2 and 兮, which are the main electric field decomposition states of Ce+3 ions 、..., 6). The excited ionic sadness 5d (5s25p6) produces a % of deuteration, which is located at the bottom of the conductive region of the fluorescent powder dielectric Gd3-x-y-zYxLuyCezAlpOq, which is ~ 〇·9 eV. % can be used to release ice from the lowest energy level above 2·6 eV, and passivated in the conduction zone, so there is actually no electron displacement of the lower layer 4f in the Ce+3 state. Therefore, it does not produce Supplemental energy consumption for excitation.

The main energy conversion between the Ce ions 313⁄42 and 2d requires excitation of the energy consumption of the quantum hV = 2. 7 electron volts, which corresponds to the wavelength of the absorbed light λ = 457 ηιη. This 21 1298348 1 n time electron cell displacement is actually the least likely, because the wavelength of the emitted light is 2 5 5 displacement equal to 525 525. A 12% low-value cell shift similar to that due to the divergent wavelength is a luminescence. In the present invention, it is known that the absorbed light of the main wavelength of 457 is likely to be due to the short-wave displacement of the Lu+3 ion added to the glory composition, and the Lu+3 ion content in the Qiansi _ optimal value. The wavelength is λ, 譲. Adding Gd+3 Xuan to the phosphor powder matrix can increase the absorption and increase the length by λ=477ηη!. The level of ~ 〇. 4 electron volts has a large effect on the luminescence of the 2 〇 main stimuli. The width of this level is located at a distance of 电子.9 eV from the material conduction zone, causing a large difference in the quantum wavelength of the light shot. In this case, the short-wavelength wavelength is between λ=51〇—565, and the long wave can reach λ=680^700 nm, and the maximum wavelength of the luminescence can reach λ=59〇. As shown above, the energy diversity of the Ce ion illuminating state makes it practically necessary to reproduce the yellow, yellow, red, and even deep red regions in the visible spectrum. This is required for the fabrication of optimal white light combining optical structures using semiconductor heterojunctions and phosphors. Indeed, if the maximum value of the short-wavelength spectrum of the heterojunction is between 1445 nm __ 475 legs, ie Δ - 3 〇 nm, then the maximum radiance of the luminescent powder can reach 65 nm, which satisfies the goal of achieving balanced white light. Necessary conditions for yellow, orange and red radiation. The present invention notes that the concentration of the primary catalyst Ce+3 ions has an effect on the luminescence spectral properties of the phosphor. If the Ce+3 ion concentration is the lowest and is between the 〇2, then the _$ light luminescence spectrum half is ^11()11111. The amount of Ce+3 ion in the fluorochemical forming knife increases. When the content z=〇〇5, the half-width of the radiation spectrum increases by 22 1298348 and is added to Δ=120ηιη, such as ζ=0·1, then Δ=130ηιη. The present invention also notes the effect of the introduced ruthenium and osmium ions on the increase in the half-width of the emission spectrum of the phosphor powder, the radiation half-width Δλ〇, 5=135-141 nm, and the small-particle cation Gd+ in the phosphor powder grid. 3 and the highest concentration of Y+3. * The present invention also notes changes in the emission spectrum of the phosphor. In the addition of 1.5 atoms to the Y ion, the flesh-colored glory powder particles have a yellow-yellow yellow color. If the repair wave is increased to x=2·0, the phosphor particles will have a stable yellow light. The Y ion content in the phosphor powder continues to increase to: ^2.4 accompanied by a green color in the reflectance spectrum. From all the data, it can be concluded that the ratio of oxidized rare earth elements to oxidized in the phosphor powder composition is 2 different from the chemical equation component _. Class _ Improve oxidation (4) contains more perfect large-particle multi-angle phosphor particles. Eight copies of the miscellaneous can be found on the $, the riding light has a similar crystal fluorescein powder is completely non-like granules. In Table 2, the phosphor powder particles used for the recommended instrument are large. * The specifications are compared with the standard phosphor powder specifications on the market. For light-emitting diodes. Fluorescent powder dispersion indicators Table-2

23 1298348

It should be noted that the surface ratio of the phosphor powder used in the present invention is smaller than that of Japanese and American standard phosphor powder. The smaller surface area can undoubtedly greatly reduce the heterogeneous clock

The scattering of the initial light. At the same time, it is pointed out that the size distribution curve of the phosphor powder particles is very different. The dispersion value of the phosphor powder of the present invention is the same as that of the Japanese company's phosphor powder but much smaller than that of the American Am. Tech. 6. The phosphor of claim 2, wherein the specific wavelength of the long wave exceeds 560 nm. Further, the phosphor powder of the present invention has a heterojunction in which the ratio of each side of the rectangular parallelepiped is 1:1:0.1 - 1:2:0.12, and at this time, the polygonal surface intersecting the light-emitting surface of the heterojunction The ratio of the height of the phosphor powder particles to the radius of the inscribed circle of the particles is 1:3. 丨: 丨, the value of which is 6-8 μm, so that there is a primary blue light in the synthesized light and a yellow and yellow light that is radiated again. The existence of large-capacity uniform mixing when they are compared with the color coordinates (between x=〇28 y=〇3() x=Q 42 y=〇.44), avoiding the formation of light mixing due to excessive scattered light. Uniform phenomenon. In addition, the phosphor powder of the present invention has a three-dimensional crystal structure, and when the ratio of the refractive index of the main heterojunction to the refractive index of the phosphor powder is between 2·8·1·8 3.2:2.0' The crystal thumbgness parameter is & = 12.1. Between eight and a=i2 2°α, mainly along the plane direction (m), the illumination output angle is between 8 and Μ, and the Frenel prism may be used to supplement the total optical radiation. Which should

24 1298348 The first plane of the prism is 100 to 2 μm from the luminescent base of the phosphor powder, filled with a transparent polymer filler, and the refractive index is between n=142 and η=1·55. In addition, the phosphor powder of the present invention has large particle polyhedral particles emitting light from all 14 interconnected planes, and the quantum output is 6〇95%. When the chemical formula of the phosphor powder is Gd3_x_y_zYx LuyCezAlp〇c^, the The intense yellow-picked yellow long-wavelength of the phosphor powder, with a wavelength between Xmax=530-595nm and a maximum spectral half-width of between 11〇130 nm, with the Gd ion dose in the chemical composition of the phosphor powder The increase in growth. The chemical index changes as follows: · 10 < χ < 26, 〇〇〇〇 1 takes 〇 5, 0.0001 幺 ZS0.5, 4.7 幺Ζ幺 5.3, q = 4.5 + 1.5 * p varies. Further, the present invention also discloses a method for producing a phosphor of a white light diode. The production of the phosphor powder of the present invention is carried out by a so-called ceramic flow chart, and the following nine kinds of phosphor powder preparation methods are described. Referring to FIG. 1, a schematic flow chart of a method for fabricating a phosphor powder according to a first embodiment of the present invention is shown. As shown in the figure, the method for manufacturing a phosphor powder according to a first embodiment of the present invention comprises the steps of: first weighing the following Gd2〇3, LU2〇3 and Al2〇3 oxides (step i); taking a concentration Ce(N〇3)3 aqueous solution (step 2); add the scaled oxides to the Ce(N〇3)3 aqueous solution and mix them thoroughly (step 3); place the well mixed aqueous solution in the oven Drying, mixing powder (Step 4); adding a certain amount of Na2S〇4, Temple LUSO4: after the end of the mixed powder, thoroughly mixing ', then putting the mixed powder into the quartz hanging pin (Step 5); Placed in an atmosphere protection furnace of free elevation 3, and heated to a first temperature at a specific speed, and maintained at the same temperature for a first time and then heated to a second speed at a constant speed.

25 1298348, the degree is maintained for the second time and then warmed to the third temperature at the same speed, the temperature is maintained for the third time and then cooled to room temperature at the same speed (step 6); the powder to be taken out is nitric acid The unreacted material is washed with phosphoric acid, and then repeatedly washed with a large amount of water until neutral (step 7); and the washed powder is placed in an oven to be dried, and after drying, the phosphor powder product is obtained (step 8). In step 1, the Gd203 is 17.2g, the Y2〇3 is 271g, and the Lu2〇3 is 59.7g.

And gossip 2〇3 is 26〇g. In step 2, the Ce(N〇3)3 aqueous solution contains 〇·ι μ of Ce (N03>. In step 4, the well-mixed aqueous solution is placed in an oven of 12 〇〇c to be dried to obtain a mixture. Powder. In step 5, add 24 g of ΝΜ〇4, 12 g ΜΑ and 4 g of LijO4 powder to the mixed powder, mix well, and then put the mixed powder into a 5 〇〇 ml stone pin. In 6, the composition of the lining from NH3 is %112=3: and the temperature is raised to 5. The temperature of the 默 minute is increased to the temperature of 4 mils, and the temperature is maintained for one hour (ie, the first day). Minutes to hide the $ two temperature, the bribe temperature to keep three small days (ie the second time) and then heat up to 5. Lions. The third temperature of C, this temperature for four hours (ie the first After three times), take the speed drop at 50C/min = take it out at room temperature. In step 7, the towel's _ is 1: Bu and Juzhiguan is also 1:1 clean unreacted material, and the amount of water is repeated.丝261298348 In step 8, the temperature of the oven is i2 〇 ° C. Please refer to FIG. 2, which illustrates the production of luminescent powder according to the second embodiment of the present invention. Schematic diagram of the method. As shown in the figure, the method for producing a phosphor powder according to a second embodiment of the present invention comprises the following steps: first weighing an oxide such as TGd2〇3_34.4g 'Y2O3-249g, WO3-59.7g 'Al2〇3 - 260g (Step 1); take Ce(N03)3 aqueous solution, containing 0.1 M (mole) of Ce(N〇3)3 in the aqueous solution (step magic; add the full oxide of the scale) to Ce (N〇3)3 aqueous solution, and thoroughly mixed (step 3); the well-mixed aqueous solution is placed in an oven to dry, to obtain a mixed powder (step 4); add right dry 1 NajO4, KjO4 in the mixed powder After thoroughly mixing with Li2S04· powder, put the mixed powder into a quartz crucible (step 5); place 500 ml of quartz crucible in an atmosphere protection furnace with free NH3 (N2:H2=3:1) to The temperature was raised to 450 ° C at a rate of 5 ° C / min. After maintaining this temperature for one hour, the temperature was raised to 12 ° C at a rate of 5 ° C / min. The temperature was maintained for three hours and then increased to 5 c C / min. 15〇〇〇c, keep at this temperature • After four hours, cool down to room temperature at 5 ° C / min (step 6); remove the powder with nitric acid ( Example 1:1) Wash unreacted material with tannic acid (1:1), then repeat washing with neutral water to neutral (step 7); and place the washed powder in an oven at T-120 °C. After drying and drying, the most fluorescent powder product is obtained (step 8). The chemical formula of the phosphor powder manufactured according to the preferred embodiment of the present invention is shown in Table _3. The phosphor powder is listed in Table-3. Main spectrum and luminescence index. Table-3 Recommended composition of crystal powder Xmax, nanometer quantum phase j main η% bright, 27 1298348 small (micron), hx 1 xk ------ -- % Gd〇> 2^2' 4L110»3Ce〇»1AI5' 10x1 545 85 80 l〇12'15 2x12 Gd〇* 4Y2 * 2Lu〇* 3Ce〇* 1AI5 > 12x1 '----- 550 95 95 l〇12 Ί5 2x12 Gd〇,6丫2,2Lu〇,3Ce〇,1AI5, 10x1 '——---- 555 100 100 l〇12' 15 0x10 Gdi ' 〇Yi ' gLu. ,iCe〇,1AI5, 8x10 ~—____ 565 100 92 l〇12,15 xl2 Gdi ' 3Y1 ' 6Lu〇,〇5Ce〇,05AI5, 10x8 575 94 90 l〇12,15 xl2 Gdi ' 4Y1,5LU0,〇5Ce 〇' 05 AI5, 10x8 595 90 86 l〇12' 15 xl2 Gdi, 4Y1, 5L110 ' ogCe. , 02AI5, 10x1 592 88 84 2〇12'3 0x14 Gdi * 4Y1 · 3L110» 2Cg〇> 1AI5 > 10x1 590 86 87 2〇12'3 0x14 Gdi · 1Y1 * 5LU0 . 3sCe〇· 05 10x1 570 94 91 AI5 2〇12 3 0x12 Y3 Al5〇i2Ce (standard) lx6x 550 80 75~~ 3 ----

The phosphor powder used in the present invention is aluminum-niobium-tantalum-niobium, and the phosphor powder particles have a large particle-shaped prism face shape, and a modification process of the glory powder polymer layer is required for self-use. First, fine mechanical agitation must be used to configure the phosphor suspension; a preferred method is to use an ultrasonic bath for the mixing operation. Second, reasonably improve the particles of the two filaments of the suspension. According to the information of the present invention, the optimum content of the fluorescent powder particles is 750/0, which is 0·001-〇·002 ml. 28 1298348 In the present invention, the working life of the produced white light diode is also measured in series. The 4 ° test includes the luminous intensity I (mCd) measurement of the LED for 1000 hours of continuous operation.

The 1° LED is stable at 20 mA and the supply voltage is U 〜3·20-3.28 V. Twenty-five light-emitting diodes using large-particle phosphor powder were produced, and as a comparison standard, 25 light-emitting diodes of Japanese company N phosphor powder were used. Test results See Table ~4. Table ~4 Blue Light Emitting Diode Sample ι〇τη mCd Average Ιδ〇〇, mCd Average I loooJ mCd Average 11000/ Io, °/o Large Particle Fluorescent Powder 320 324.1 332· 2 103.76 Nichia Standard Fluorescence Powder 320 291.2 259.2 81.0 Since U can work continuously for 1 hour, it is assumed that the light intensity of the instrument may change due to the reduced operating voltage of the LED. The physical fact that the brightness of white light-emitting diodes made of large-particle polygonal phosphors has increased is not previously noted, and requires deep research. It is undoubted that the phosphor particles have unusual characteristics that are distinctive. In summary, each of the GafHnN crystal heterojunctions 29 1298348 with a size of 〇·2x0·3 microns has an optical flow of 4-6 lumens from a suspension of large particles of polycrystalline microcrystals covered by each radiation surface. The operating current of the heterojunction is j=2〇mA. 16 LEDs connected in series on the emission matrix, the required current J = 800 mA, the optical flow is F = 98-120 lumens, which ensures that the light output reaches η = 22-28 lumens / volt, so it is true Improve the shortcomings of the conventional white light diode and its fluorescent powder manufacturing method. Although the present invention has been disclosed above in the preferred embodiments, it is not intended to limit the present invention.

The invention is to be understood as being limited by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the flow of a method for producing a phosphor according to a first embodiment of the present invention. Fig. 2 is a schematic view showing the flow of a method for producing a glazing powder according to a second embodiment of the present invention. Table-1 shows the coatings made from phoenix powder particles of standard dispersion distribution and size. Table-2 + is the comparison of the specifications of the fluorescent powder in the market. Table-3 shows the chemical formulas of the nine kinds of phosphors of the present invention. The surface standard _4 is the comparison standard is _ 曰 曰 N N N N N N N N [Main component symbol description] 30 1298348 Step 1: First weigh the following Gd2〇3 ' ΙΟ3, ΜΑ and a certain amount of 〇3 oxide; Step 2: Take several concentrations of Ce(N03)3 aqueous solution; Step 3: The weighed compound is added to the Ce(N〇3)3 aqueous solution and mixed thoroughly; Step 4: The well-mixed aqueous solution is placed in an oven to be dried to obtain a mixed powder; Step 5: Adding a certain amount to the mixed powder After the powder 4,]^〇4 and Li2S04· powder, mix well, then put the mixed powder into the quartz steel; Step 6 · Place the quartz steel in a free atmosphere protection furnace to raise the fox at a specific speed To $ / dish degree, and to maintain the first time at this temperature, then increase the temperature to the second temperature at the same speed, and then maintain the temperature for the second time and then increase the temperature to the third / dish degree at the same speed. After the third time, the temperature is further reduced to room temperature and taken out; Step 7: The unreacted material is washed with nitric acid and phosphoric acid, and then washed with a large amount of water to the towel; and step 8 · after cleaning The powder is placed in a box for drying and drying Powder product is obtained after glory. ’

Claims (1)

1298348 X. Patent application Fan Park····· A kind of white light diode filament, which is made of heterojunction of gallium nitride and indium nitride semiconductor, which has several radiation wavelengths and is equipped with milk. The base is decorated with a catalyzed polyhedral filament dispersing county powder, and its light_cutting code is Gd3_x_y_zYxLuyCezAlp〇q 'where the chemical of the general equation of the spectral converter is: 1.0<χ<2.6, 0.0001<y< 〇.5 , 〇.〇〇〇ι<ζ<〇5,4 ?<z<5 3 , q=4.5+1.5V The powder is a large-surface dispersed single crystal, and the multi-edge is mainly 1 • body shape 'The hexahedron has two mutually parallel bases, consisting of 12 trapezoidal edges, which are at an angle to each other, and the polygonal particles are in direct optical contact with the front side and the four end faces of the heterojunction. And covering a certain area of the surface of the heterojunction light, the light-emitting surface is combined with the long-wavelength light of a specific wavelength converted by the phosphor powder particles to form a high-fibre high-- and the viewpoint of the different ceramic guide is in different β r two = please patent fine 1 The material of Si (4) 2 (4), wherein the wavelength of the radiation is less than 470 nm. 3. If the application is in contact with the second grade of the county, ^ 150. . H claims the glory powder described in the first item of the patent scope, wherein the multi-edge particles are directly related to the bismuth, . The front side of the wheel is in optical contact with the four end faces and covers 20 to 85% of the area of the heterogeneous surface. 5) If you apply for a special _ blue _, the length is more than 560nm. The fluorinated powder according to claim 1, wherein the radius of the inscribed circle of the phosphor powder is between 6 and 12 microns, and the height of the two bases is 4 to 1〇. Between microns. 7. The phosphor powder according to claim 1, wherein the color temperature of the synthetic white light is between Τ=12000-2500οΚ and has a high light intensity at a divergence angle of 6-12 degrees. _ / 8. The phosphor powder according to claim 1, wherein the heterojunction is a ratio of each side of a rectangular parallelepiped of 1:1: 〇1 to 1:2: 〇12, at this time, The ratio of the height of the polygonal prism powder and the radius of the inscribed circle of the granules of the base surface and the shells, and Ό are 1:3 - 1:1, and the height value is 6-8 μm, so that the synthesis In the light, there is the presence of yellow and orange light that emits blue light for the first time and re-radiation. When they are mixed with the color coordinates, between χ=〇·28 y=a30 xKU2 y=0 44), large-volume uniform mixing is avoided. Excessive light mixing results in uneven light mixing.鳙9·If the fluorescent powder described in Item 8 of the patented seam, the single crystal glory powder particles have a three-dimensional crystal structure 'when the main heterogeneous f-fold (four) number and the refractive index of the fluttering surface material are in the ratio of 2.8:1.8 - 3.2 Between 2.0, the crystal grid parameters are between a=121〇A •2 A, mainly along the plane direction (in), so that the illumination output angle is between 8 and 16 degrees, and may be used in (4) The mirror is used to supplement the total light radiation. The phosphor powder according to claim 9, wherein the first plane of the prism is 1 〇〇-200 μm from the hairline surface of the phosphor powder, and the intermediate filled transparent 33 1298348 m compound filler 'refracting The coefficient is between η=1·42 and n=:i M . 11. The phosphor powder according to claim 8, wherein the large particle polygonal particles emit light from all 14 interconnected planes, and the quantum output is 6〇95%, when the chemical formula of the fluorescent powder is Gd3. .x.y_zYx LuyCezAlpCMf, which can make the fluorescent powder have strong orange-colored long-wavelength light with a wavelength between _=53〇-595 nm and a maximum spectral half-width of between 'HO-130'. The amount of ion in the chemical composition of glory powder increases. %12·If the glory powder described in claim 11 of the patent scope, the chemical index changes as follows: 1·0<χ<2·6,0._奶〇.5, 〇·_(5)〇5,4 7 3, q=4.5+1.5*p changes. 13· a method for producing a white light diode phosphor powder, comprising the following steps: first weighing the following Gd203, γ2〇3, lU2〇3 and 八12〇3 oxide; taking a certain concentration of Ce (N03)3 aqueous solution; the meter will add the whole amount of oxide to the Ce(N〇3)3 aqueous solution and mix it thoroughly; the fully mixed water will be placed in the reading box to obtain the mixed powder, ·, Add a certain amount of the powder to the mixed powder and mix it thoroughly, then mix the powder into the quartz crucible, and put the quartz 放 _ _ _ 3 3 3 3 3 3 3 3 3 3 3 3 3 This temperature is maintained at the same time and then warmed up at the same speed. ^: Temperature, the temperature is kept at the second _ and then the temperature is tempered to the first degree, two 34 1298348. This / dish is kept at the third time and then cooled at the same speed. The mixture is taken out at room temperature; the removed powder is washed with nitric acid and phosphoric acid, and the washing is repeated until neutral, and the reacted material is then sprayed with a large amount of the powder after washing, and the dried cake is dried. R is the production method described in claim 13 of the patent application, wherein the (10) is • 2g YA is 271g ‘Lu2〇3 is 59.78 and 八12〇3 is 2 qing. 15. The method according to claim 13, wherein the Ce (N〇^ aqueous solution contains Ce(N03)3 of 〇·1M. 16. The well-mixed aqueous solution is placed in a 120V oven to be dried to obtain a mixed powder. m 17·If the preparation method of the patent item 13 is applied, the mixed powder is added with 24 g of the wind and 12 g of the crucible. 4 and 4 g of Li2S〇4 powder are thoroughly mixed, and then the mixed powder is placed in a 500 ml quartz crucible. 18. The production method according to claim 13, wherein the free Nh3 component is Ν2: Η2=3··1; the specific speed is ^c/min speed; the first temperature is 400 ° C; the first time is one hour; the second temperature is 12 〇〇〇c; the second time is Three hours; the third temperature is 15 〇〇〇c; and the third time is four hours. 19. The method according to claim 13, wherein the ratio of nitric acid is 1:1, and The acid ratio is also 1:1. 35