TW201022411A - Warm white light emitting diode using gadolinium lutetium cerium as substrate and phosphor powder thereof - Google Patents

Abstract

The present invention discloses a phosphor powder taking gadolinium lutetium cerium as substrates, the characterized in that: F.sup.-1 ions and N.sup.-3 ions are added into the phosphor powder to replace a portion of the oxygen ions in the garnet lattice, wherein the stoichiometric formula is: (Gd.sub.1-x-yLu.sub.xCe.sub.y).sub.3Al.sub.5O.sub.12-zF.sub.z/2N.sub.z/2. The phosphor powder can irradiate in the scope of orange-red spectrum after the phosphor powder is excited by an indium gallium nitride (InGaN) semiconductor heterostructure shortwave. Additionally, this invention also discloses a warm-white-light emitting diode that adopts the phosphor powder having gadolinium lutetium cerium as substrates. When the semiconductor heterostructure having the wavelength lambda that is equal to 420-500 nm is radiatively excited, the maximum emitting of the phosphor powder in the orange-red spectrum is that lambda is greater than 575 nm, the half wave width is greater than 135 nm, and the color rendering index Ra is equal to 80.

Description

201022411 IX. Description of the Invention: [Technical Field] The present invention relates to a warm white light emitting diode based on a milk transition and a fluorescent powder thereof, and more particularly to a novel solid state light source which can be combined with different #InGaN Nitride Heterojunction is a matrix and contains a large number of nano-structured heterojunctions. The warm white light-emitting diodes and their phosphors are based on the milk record. [Prior Art] Luminescent materials with Ja3d stone structure space group have been widely used in nuclear energy and laser physics in the 1960s; the first report of garnet synthesis was made by American engineers H Yooder and M. .Kettle (please refer to Amer. Mineralogist 1952 V36N6P15~98) for the first time to propose a single crystal artificial garnet containing Y3Al5〇i2, which is named as yttrium aluminum garnet (YAG). It has been pointed out in this work that the chemical composition lattice structure of YAG differs from the natural minerals Crossulara-Ca3Al2Si3012 and spessartine_Mn3Al2Si3〇i_.

For the first time, JooderH.J made it very clear that the spacer group belongs to the J1〇3d artificial garnet. The same lattice parameter a^l2.01±〇.2A is larger than the natural garnet a~1186A. Using large-size Y+3 and Mn+2, the metering of this material can be written as A3B2(B〇4)3 'where A-type ions (rare earth elements such as calcium, iron, etc.) have twelve sides The coordination of the body, its valence number κ υ = 8, B type ion (矽 and part of aluminum) has its valence KU = 4, part of the Α 1 + 3 ion has octahedron, the price κ υ = 6.

Mr. Yo^era pioneered the new synthetic possibilities, which are more than just traditional garnet crystals. The long-term concern is often the market's beautiful ruby. The development of new workmanship has become an important development direction. This technical concept has been produced in the 2G century, combining high technology with laser. It must be pointed out here that the solid-state laser produced in the 1960s is more effective than the ruby Al203.Cr, a YAG_ based on single crystal.

Applyphysicsl%2, Volume 33, page 8 2519, Tong-Mizhi 1963, V34, P3063, 201022411

The same - miscellaneous ^ Chenna ^ in this - year's first stone stone composition from (10) (four) patent was born (please refer to Charvat's British GB1055 〇99 patent, Niels〇n J W

U.S. Patent No. 2,979,413 to Bell Laboratories and U.S. Patent No. 3,050,407 to Ballman A. It is derived from the garnet composition of YAG:Nd (refer to the US patent US 3,050,407 of the Baiiman), which differs in high efficiency, high light transmission and heat resistance, and is a reliable method for preparing larger-sized laser components. At the same time, the "synthetic" garnet (YAG: Nd) was realized according to the principles of physics and material analysis. According to the synthesis of different rare earth ions (〇6丨1^1〇^) garnet, the application of this unique material has been expanded. In 1966, detailed research applied to the paramagnetic resonance of YAG:Ce was published in H. .Lewis (please refer to Journal Apply physics Vol. 37N2, P739), the main conclusion is that helium is used as an activator in the single crystal form, and the same particles appear in the form of powder and yellow garnet powder containing yttrium (the topaz is in the jewelry market). Precious and rare). We have a technical solution for creating broadband garnet phosphors. The priority is the Dutch physicist G. Blasse in April 29, 1967 and ABRille in the patent on cathode ray tubes (please refer to the Netherlands N1 67〇6〇95 patent). A new type of phosphor powder (Y, Ce) 3Al5012 is used in the manufacture of fluorescent screens. These five patents are protected in different countries, pointing out the importance of G.Blass and A.Brill in this work. BlasseG of the Royal Phillips of the Netherlands has developed a new type of patented Cerium-Activated Yttrium Aluminate Phosphor (see US3,564,322, GB1174518, DE1764218 and Be714420) in the United States, United Kingdom, Germany and Belgium. The development of the color image screen has a wide-band phosphor powder (Y, Ce) 3Al5012 with a radiation of λ=470~720 nm, and the maximum radiation spectrum, shape = 55〇11111. Allows transparent multi-color enamels and slides to be built on electroluminescence to produce visible spectrum sub-bands showing blue, sky blue, yellow and red, for more 6 201022411 color balances and to establish the correct white light luminescence, Addition of garnet fluorescing powder' and the addition of the first well-known CaaA^SiO^Ce (Shiquanshi) fluorescing powder, combined with two materials to produce broadband radiation, color image quality is reproducible (Please refer to BlassGA.Brill JP Apply physics Lett 1967, Vol 11, P53) 〇YAG: Ce Fluorescent Powder is published by the founder GBlasse at the time published in the academic paper [Luminescent material] (please refer to GBlasse Uuminescentmaterial)

Amstepdam-.Berliu, 1994)' and also in the Fluorescent Powder Handbook in Japan (please refer to Phosphors Handbook, lst Edition, 1987). The emergence of the main YAG:Ce material is very effective for nuclear physics and scintillators, and its very short afterglow (t/lxHT7 sec) allows the detection of very high energy radiation. Such a sample 'light-emitting component (Y, Ce) 3A15〇i2 and similar analog components are like 'in the fluorescent powder manual' (please refer to Handb〇〇k〇f Phosphors) and teaching in various engineering schools. Reference books can be found. In this case, the composite (and two-group) device, with GaP GaAS as the main radiation in the infrared spectrum, uses anti-Stoke glory to convert the invisible radiation into visible red light. Or blue radiation. For a description of related patents, please refer to US Patent No. 3,882,215, Canadian CA9〇〇62〇 patent and CA900620A patent. A novel nitride material based on GaN is established to define the visible region (infrared light, ultraviolet light and blue light) of the light-emitting diode in the short-wavelength energy band. This material was obtained from the Soviet engineer BC Abramoff. She obtained the franchise of the Soviet CCCP 635, 813 patent (please refer to BC Ablam〇vCCCp635813 patent) ^Using Stoke Fluorescent Powder to Partial Primary Radiation of GaN Structure Converted to long-wave light shots 'white light that makes up different colors. In 1994, Japan's physics 豕 Nakamura proposed a heterojunction (ie, ρ·Ν junction) structure of indium and gallium nitride, which can improve performance (please refer to..., s. Naka Cong a) Blue laser. Springer Verlag, Beriin, and). After that, there was no 201022411. In 1995, the excellent physicist of "Nichia" company used the synthesis of white light emitting diodes. A wide-band phosphor powder Y3Al5012:Ce (refer to US Pat. No. 3,564,322, GB 1174518, DE1764218, and Be714420) and a composite structure of a light-emitting body (refer to US Pat. No. 3,564,322, GB 1174518, DE1764218, and Be714420). Patent) (CA 900620 patent of Grodriewicz W. Uitert W/Light, DE 2444107 patent of Pankove and CCCP 635813 patent of B. CAblamov). This concept combines two complementary colors to create white light radiation based on the 17th century Newton's complementary color principle. They applied for patents based on known materials, structures, and physical principles (see S. Nakamura. Blue laser Diode. Springer Verlag, Berlin, 1997). However, in the well-known N5988925 patent, the following disadvantages still exist: 1. The luminous efficiency of the instrument is not high, 1 〇 12 12 watts/watt for color int greater than 5000 K; 2. Blue light of the first partial heterojunction inN_GaN heterojunction Radiation has an adverse effect on vision; and 3. On a single material with a solid-state type (Y'Gd.CehAlsOu), it is impossible to replicate warm white light. In the establishment of a warm white light-emitting diode, due to the lack of a single component The garnet structure luminescent material has been limited for a long time, and it is inconclusive to try to establish a similar luminescent body with a single component (Gd, Ce) 3Al5 〇 12 (please refer to S. Nakamura. Blue laser Diode q SPringerVerlag, Berlin, 1997), in addition to the use of GdsAlsO^ in a series of research and development work, such a single fluorescent powder, in the article published by AedredF A (please refer to Aedred RATrans Brit Ceram Soc. 1959.vol 58N4p 199-210) Densification. In the use of YsAlsOhCe and CaAlSiN^Eu two-component structured phosphors to produce a light-emitting diode with warm red light (see US Patent Application No. US2008283801A, 2008/11/20, by Ryowat T). And the Chinese patent application of Soshchin N (CN 2008 1016492, 11.05.2008) and the various pomegranate structures proposed at the same time to obtain warm white light, Chinese patent application CN20081016492 relates to the invention, here, in the present invention Citing the relevant information, it is probably because of the complicated technology, the lack of illuminating technical parameters of 201022411, so far has not been used [invention content] Lin 缺点 shortcomings, the purpose of the present invention is to provide - a kind of 蟀 蟀 丞 丞 丞 先In the light-emitting diode, a region having a high luminescent material is formed in the junction structure region, and the region of the medium-mass x > 58 〇 nm has a red light shot. The 疋 in the reference φ is to solve the above-mentioned shortcomings of the prior art, the present invention == =, a polar body, which can establish a non-second solution for the purpose of the above, one of the inventions is a sputum cast sputum as a matrix filament f, and the hybrid 在于 杂 丝 丝 丝 丝 丝 丝 丝 丝 丝, replacing some of the oxygen ions in the garnet lattice, the stoichiometric formula 1 lyU^CeyhAlsO^-zFz^Nz^ 'The phosphor powder is excited by a short-wave excitation of a heterojunction of a gallium nitride gallium) Red spectral region In order to achieve the above object, a ruthenium-based warm white light-diode of the present invention is based on an indium gallium nitride (InGaN) heterojunction and has a = optical converter. The first stage of blue light luminescence conversion can be converted into warm white light, and =: the luminescent powder particle component of the luminescence converter is connected to the organic stone as described above, and distributed in the thickness uniformity The light-emitting surface of the knot and the radiant facet. In order to achieve the above object, the present invention relates to a preparation method of a fluorene-based phosphor powder for preparing a phosphor powder as described above, which comprises heat-treating a charge from an initial material, which is characterized by: The heat treatment is a heat treatment in a reducing temperature in three temperature stages, a first temperature stage and 11 Torr. 〇Second temperature stage T>1250°C, 201022411 The second temperature stage T>133Gt, the total time exceeds t=12 hours, and then the cold part of the product is used to carry out the Wei with the mineral solution, and the thinness of the surface is called. In order to enable the review committee to further understand the structure, features and objectives of the present invention, the detailed details of the attached and better specific implementations are as follows. [Embodiment] Firstly, the object of the present invention is to eliminate the lack of flit of the above-mentioned conventional garnet glory powder, and to achieve the goal of the present invention, the thief-based fluorescent powder of the present invention is decorated with I () (Lu) Ce) is a matrix, characterized in that the fluorescent powder ΟF曰-1 ion and N-3 ion replace the oxygen ion in a part of the garnet lattice, and the chemical formula is: sage private team-heart For example, the fluorescent powder can be radiated in the range of the red spectral region after being excited by a short-wavelength of an indium nitride (InGaN) semiconductor. The measurement parameter value of the stoichiometric formula is χ=〇〇〇〇1~〇3. y=0.001 ～0.08 ; ζ=〇.〇〇〇ι~〇5 Atomic fraction. The maximum spectral wavelength in the orange-red spectral region range is ^^=57511111, and its dominant wavelength is 〇58〇nm.

Among them, the atomic ratio between this and the rotation is 3〇〇: 1~5:1, the best atomic ratio is 20:1~1〇: Bu activator composition...from 〇〇〇5~〇 〇 8 atomic fraction. , wherein, the oxygen ion, the rl ion, and the N.3 ion fraction in the anion lattice are βΜΝ-^ο.οοο^~〇.25. ' Among them, the tampering κι and the introduction of the atomic fraction [f-1mn-1]=0001~〇〇〇5' its maximum light spectrum is at λ=582ηιη, the introduced atomic fraction [卩-1]'1 ]:. When ^~0.1, the maximum radiation spectrum shifts to λ=585ηιη. Wherein the color coordinate value Sx+y> 0.82 of the phosphor powder has a radiation wavelength value of λ = 585 to 600 nm. Wherein, the luminescent excitation spectrum of the phosphor powder is located at a wavelength interval from λ=420 to 500 nm, mainly changing the content between lanthanum and cerium. 201022411 where 'the county's powder light touches the large radiation wave width ^ = 135~138nm. Wherein the phosphor powder is formed in the form of ultra-disperse particles, and the phosphor powder particles have an elliptical shape in shape, and the median diameter is d5 〇 = 2 μm. The solution proposed by the present invention will be briefly explained below. It is first pointed out that in the phosphor powder proposed by the present invention, the main material components are absent; the second, the glory powder has a stone = cubic lattice type. For Shiquanshi lattice material and its attached lc3d-0 η, and second, lack of antimony in the main components of the phosphor powder, it does not belong to YAG Rongguang, and fourth, the lattice parameter value of the phosphor powder. The method of production uses spring: species dropout structure: part of Gd+3 is replaced by the same valence state Lu+39Ce+3 such as ^(4), will, the divalent state $〇-2 is a monovalent fluoride ion F_1 and three f iiWi, the proposed filament_turn & +3 ion as the atomic fraction of worm λ ^ > 420 'chen 08, ensuring that the short-wave heterojunction InGaN material is absorbed in the yttrium, and the luminescent material is distributed in blue, The green, orange, and work colors are seen in the 7U area. The maximum spectrum has ^=582 lungs. ΐ ΐ ΐ 械 械 缺 植 γ γ γ γ + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + Half-wave width; 3. The afterglow time is very short, the small ❹ is mainly - the high quantum radiation output of the y = y > y = 0.90; and 5. The wavelength is mainly related to the main excitation band. The luminescence property of the county powder proposed by the present invention = the light of the agent is such that (10) _ linkage 4f-5d within the electric frequency band diffusion 'related transition range excitation ΪΪ root pair: two:: medium 'main c, 3 radiation Ce +3 miscellaneous; dip μ has a vertical curve with respect to vertical. And face with Cong and 2F7/2 (excitation level), 2D5/2 u this shape t) 'Raining the electrostatic field of the phosphor powder, Ce+3 short wavelength shop 11 201022411 Displacement' when reducing the electrostatic field force of the lattice The long wavelength shift of the Ce+3 radiation induced. In the process of the invention process, we have stated that for the mechanism of the Ce+3 in the radiation spectrum, first, the main maximum radiation spectrum is attached to the cationic lattice phosphor powder, with self-interesting ions Gd+3 and casting ions Lu+3. The relationship between the ratios. Secondly, among the structural components of the fluorescent powder radiation spectrum, the heterovalent substitution portion, the divalent 〇_2 is replaced by the valence-fluoride ion F1 and the trivalent Ν·3. The optical influence of the structure is explained in the present invention by a method of analyzing the h-picture. Spectral ❹ wavelength λ~ --二二

Spectral Half-wave width λ〇. 5, nm 136, 6 136, 1 136,4 136, 5 136, 7 583 Luminance Brightness

Color temperature K 21281 21002 19691 1 9051 18397 3229 3310 3278 3203 3406 137, 〇138, 5 21729 3300 ^ί^^!Α15〇1,.5ι Light: C1~Fig. 8, in which Figure 1 shows the intention of Kenting, 2 is a schematic diagram showing the spectrum of the sample 2 glory in Table i; FIG. 3 138, 6 20227 20302 3127 3396 12 201022411 Schematic diagram of the sample 3 phosphor powder in Table 1; FIG. 4 shows the sample 4 in Table 1 = powder Schematic diagram of the spectrum; Figure 5 shows the spectral representation of the sample 5 phosphor in the surface = =, Figure 6 shows the table! Schematic diagram of the spectrum of the sample 6 phosphor powder; Figure 7 shows the schematic diagram of the sample 7 fluorescent powder; the diagram is called the spectrum of the sample 8 fluorescent powder. ... From the above Table 1, we found: 1. Replace the oxygen ions with Γ1 and Ν'3, the maximum radiation spectrum of fluorescein 2 is 2.9nm; 2. The maximum spectral radiance (four) wave width, the change is Δ=2ηΐη; 3. The illuminance of the luminescence is changed by the change of the concentration of Γ1 and N-3, and in the 19 Κ Κ ^ position, or more, 1 G% higher; and 4. The color of the phosphor powder is reduced by Δ Τ = 279 Κ. The invention has the advantages of (4) the highlight, which is characterized in that: when the atomic ratio of Gd ion and Lu = sub is suspected to be 1~5:1, the optimal ratio is 2Q: 1~1():1 and μμ The ratio of the agent is 0.005 to 0 08 atomic percentage. The glare powder proposed by the present invention includes a feature in which the oxygen ions are replaced by rl ions and ν_3 ions in an anion lattice, and the amount is from [FlMN-3] = 0.00005 to 0.25 atomic fraction. In the method of Table 1 of the domain data group, the method refers to & the invention = powder (sample) has the largest spectrum I, 9 atomic ratio of the earthquake when replacing a small amount of & ion, there is _« _ Lattice is an important reflection of the wavelength shift. When the atomic fraction is increased, the gamma atomic fraction is increased by the fluorescence of the phosphor. & Μ Μ 实质 实质 实质 实质 实质 实质 实质 实质 实质 实质 实质 实质 实质The internal ion and surface of the f_ orbit are mutually restricted, and the yin secret 5d----------------------------------------------------------------------------------------------------------------------------------------------- -2+ luminescence quantum-cf v〇-2_^e+3(4F5/2_5D). Contains strong absorption light 'ion excitation returns to the initial state of the touch, the quantum luminescence difference released is ~7〇nm, Therefore, the maximum light spectrum of Ce+3 is from 530~590mn in the sub-band of the pumice cubic lattice type. In the radiation transfer containing the whole Ce+3 ion, we found that the maximum radiation is in the cubic structure Gd3Al5〇i2 λ^=580~585nm, suitable for the orange-red visible spectrum region. I found in the process of invention, pointed out The color coordinate value is increased to (]x+y)>0.82 day^· 'The light wavelength of the dominant wavelength is different from the maximum value of the light-radiance spectrum and the dominant wavelength of the λ=58〇~595 legs. I also pointed out that Increasing the fluoride ion Fl and Ν-3 ions to replace the λ large-spectrum radiation half-wave width increase. 联 疋 疋 疋 疋 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要 主要: ί!? Also reveals a preparation of fluorinated powder based on enamel cast enamel. ί 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二, then 5 t / min temperature 5 « (Ν 2: Η 2 = ί: 5) holding temperature rate (10) position, powder: the light out of the dry disaster and grinding to the overnight acid wheel Si = medium pickling, and The surface of the camping powder powder is coated with ―, like this: with 14 201022411 blind holes, if the powder of the phosphor powder is very small, d5 〇 < 2 microns, then it will increase the scattering of light 'in the first semiconductor heterojunction When the radiation is excited, the luminance of the light is lowered. The above-mentioned average particle control is d5〇=2.00 soil 0.5 micrometer, which is proposed by the present invention. The firefly, the powder has a high luminous brightness, and the relationship standard of other chemical components of the fluorescent powder is calculated. This is because the material of the garnet luminescent phosphor is lacking in the literature, so the solid solution (YoaGdomCeo.oAAlAa fluorescent light is utilized). Powder is used as a benchmark to compare. ❹ ❹ According to its chemical composition (Gd/Lu correlation), and replacement in tetrahedral A1〇, the ion number of fluoride ion F1 and nitrogen ion Ν'3 introduced by oxygen ion, we have obtained ^ light The party level is 72~76.5% of the phosphor powder sample, with the largest radiation spectrum = 56lnm 'mainly in the yellow visible spectrum field, the proposed light powder brightness is higher than 75%, and the brightness is very high.实施 One of the preparations for the implementation of the seam of this (4) _ silk 贱 _ is preferred to weigh the following raw materials

Gd203: 48.95 g Al2〇3 : 25.5 g

Lu203 : 4.18 g A1F3.3H20 : 0.92 g

Ce02 : 1.55 g AIN : 〇.82 g The above raw materials are thoroughly mixed and placed in a 300ml Wengeng electric field, which is held for 4 hours by π theory and then heated to j 5 at a heating rate of 5〇C/min. At this time, add a weak reducing gas (n2:H2=95:5) to the temperature increase rate of 5 °C/min to Τ=ι42οχ:, with #4, €乳, then But to the room temperature. You stay for 4 hours' then naturally remove the hanging from the electric furnace, then the powder is powdered, pickled with 0.1M HN〇3 strong acid, and removed and ground to 50nm zinc ZnO. Si〇2 film. According to the above powder powder surface, the sample 1 in Table 1 was applied. The sample produced by Μ is 15 201022411 w ^ 卜田 ϊ ϊ 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 暖 暖 暖 暖 暖 暖 暖 暖 暖 暖 暖 暖 暖 暖 暖 暖 暖 暖 暖

I am the applicant of the present invention in the Chinese patent (10) coffee side A

(Please refer to the specification and drawings of the above patents, and will not be described here.) The heat-conducting substrate on which the stone Al2〇3 or single crystal stone is placed is filled with a glory conversion layer J: 隼:ΓΖ:) usually located in a conical shape In the refractory device, the accumulator leads all the f-collected first to the illuminating diode lens cover and retracts outward. lie in

The surface or the facet of the bulk heterojunction luminescence conversion layer is composed of a self-recorded ruthenium matrix powder mixed with a polymer, and the refractive index of the luminescent acid compound Up to n=i65~H liter? The external radiant output of the converter. The above semiconductor development: Yan Zhao,,, t bottom, animal light luminescence converter and light-emitting diode lens cover, etc. (10) 011 () 4 exposure pepper _ book 峨, here is no longer proposed in the present invention (10) In the light-emitting diode of the substrate, the light-emitting surface and the side surface are covered with a luminescence conversion layer having a thickness of 16 〇 to 200 μm. The uniform thickness of the luminescence conversion layer ensures high uniformity of light and 10, which is seen in the process of the invention, for glory powder particles and polymerization ~. When the weight ratio of the filament particles is 6%, the white non-hanging color temperature τ> surface 0Κ, when increasing the weight ratio of the phosphor powder, the whole light color is orange-yellow, and the optimal weight ratio of the phosphor powder The luminance of the light-emitting diode and its high color rendering. k ensures the advantages of the light-emitting diode of the substrate as indicated by the present invention, characterized in that the UnGaN IU dopant heterojunction is a semiconductor-based luminescence conversion layer, and the first-order blue radiant luminescence Converting and reconstructing light, characterized in that: the illuminating converter is composed of the & component as described above, and is mixed with the organic stone polymer, and is fused to the radiation surface and the radiation facet of 16 201022411 in the form of thickness hooks. The weight ratio of the light powder particles is 6 to 70 〇 / 。. It should also be pointed out here that the light-emitting diode of the present invention proposed by the present invention uses a heterojunction radiation excitation displacement to be wider at a longer wavelength, compared with the standard (λ = 450 to 465 nm), the present invention The proposed light-emitting diode with ruthenium cast ruthenium has a heterojunction radiation region from λ=420~485nm, and it must be emphasized that the standard Shiquanshi phosphor powder (Yo.wGdo.^Ceo.oAAlsOi2 is not as wide as this) Excitation wavelength. Such a high-luminance luminance heterojunction requires a very high saturation color and a high quantum output. The color temperature of the light-emitting diode is 2500~4500K, and the color coordinates of the warm white light are

❿ χ=0·42, y=〇.44. The above-mentioned ruthenium-based light-emitting diode is characterized in that it further has a conical spherical lens cover (not shown) located above the luminescence converter, and the conical spherical lens cover is irradiated The observation angle is 2T=60. At the time, the self-power w=i watt to w=2 Watts, whose luminous flux is increased to f > 15 lumens, the luminous efficiency of the instrument is η 275 lumens / watt. Therefore, by using the ruthenium-based warm white light-emitting diode and/or phosphor powder of the present invention, the luminescent material is created in the short-wave semiconductor InGaN heterojunction structure region, which is the most important in the present month. It is in the area of WOnm that it has the advantages of red-shifting, which can establish the width and width of the widening (four) and has the S coloring 镰Ra, so as to improve the shortcomings of the conventional warm self-lighting diode and the stone weighting powder. 'It is a preferred embodiment. Anyone who changes or modifies the local source ====_(4) The person who knows the secret is easy to infer, and the case is not inconsistent with the purpose, the means and the levy, and the first The materials are also in the special + also in the "extraordinary review", and the analysis of the early patents, Yan Jiahui 17 201022411 society, real sense of virtue. [Simplified schematic] Figure 1 is a schematic diagram, showing this Inventive 矣] 音音图.. (4) Spectral indication of sample 1 fluorescent powder in 1 = is the schematic diagram 'The green spectrum of the sample 2 is the spectrum of the fluorescent powder in the sample i = _ schematic 'scale' shows the hair 1 The spectrum of the sample 3 phosphor powder is a schematic diagram showing the spectrum of the sample 4 phosphor powder in Table 1 of the present invention. Fig. 5 is a schematic view showing the invention. A _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The schematic diagram of the present invention shows that the spectrum of the sample 7 phosphor powder is not intended. Fig. 8 is a schematic view showing the sample 8 in the form of the present invention. Light is not intended to honor The main element symbol square DESCRIPTION no. 18

Claims (1)

201022411 X. Applying for the patent garden: 乂-cultivating money _ is the fluorescent powder of the base f, the system (10) is still the substrate, and its special government adds F-1 ions and Ν'3 ions to the fluorescent powder material. Substituting the oxygen ions in the eight garnet lattice, the stoichiometric formula σ knife ff 0 is) full 〇 ^ bird 2 'the fluorescent powder has a specific The Ζ = 0,0001~G.5 atomic fraction. "· υΐ 0·08 ' 3. As stated in item 1 of the patent application, the orange red as f __ technical silk is ^=5751^; ^^ long λ=580ηπι. The ratio of the atomic ratio between the gadolinium (Gd) and the cast (Lu) in the pot of the chaotic cast brocade as described in the scope of the patent item is 3〇〇: 1~5:1, the fraction ratio is 2〇 :i~i〇:i, activator composition Ce+3 from 0 005~0 〇8 atomic fraction y, 5. According to the scope of application of the patent item! The anion is from the oxygen ion, F_i ion and N.3 material of the towel, '^=1^=0.00005~0.25. Knife 6. According to the scope of claim 1 The 釓 win 15:1 and the introduction of the atomic fraction [FiMn-i] = 〇〇〇 1 ~ 〇〇〇 5 & maximum radiation spectrum at λ = 582 ηηι, the introduced atomic fraction [Γι] gas π 〇〇 When 5~〇f, the maximum radiation spectrum shifts to λ=585ηηι. ., ' 7. As shown in the first paragraph of the patent application, the fluorescent pink coordinate value Sx+y> , the radiation wavelength value λ = 585 ~ 6001 ^., 8. If the patent application scope 1萤 釓镥钸 釓镥钸 之 之 , , , , 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 复 釓镥钸 釓镥钸 釓镥钸 釓镥钸 釓镥钸 釓镥钸 釓镥钸The thief is a matrix of phosphor powder, and the half-wave width of the maximum radiation of the spectrum is λ 〇 5 5 5 5 5 5 5 5 5 5 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如a phosphor powder, wherein the phosphor powder is formed in a form of ultra-dispersion, and the shape of the phosphor powder is rounded, and the diameter of the median line is d5 () = 2 μm. Warm white light emitting diode, which is based on an InGaN heterojunction and has a luminescence converter which can be the first The level of blue light is illuminating, and the characteristic is that the fluorescent powder of the luminescent converter is as described in the article 专, and is connected with the organic stone polymer. The form is distributed on the radiating surface of the heterojunction and the light-emitting facet. 12. The warm white light-emitting diode according to the invention of claim 5, wherein the weight ratio of the phosphor powder particles is 6 to 7% by weight. "13. A warm white light-emitting diode based on yttrium as described in the scope of claim 5, wherein the light-emitting diode is suitable for λ=420~50〇nm#blue different-junction radiation' The illuminating light|| has a warm white tone color radiation, the color thereof, T=2500~4500K, and the color coordinates are χ=〇42 and the corpse 44. 14. As stated in the claim The warm white light-emitting diode of the substrate is 'stepped with a spherical lens cover of a cone-shaped cone, which is located above the light-emitting converter'. The m-turned ball is covered by the mirror _ 2τ=^ 'Luminous intensity l> 50〇〇mcd, power W=1 watt, luminous flux F=8〇~如沪明. /JlL 15. A method for preparing phosphor powder based on (10) ruthenium, for preparing such as Shenzhu Zhili The sigh _ is a matrix of fluorescing powder according to the first item, which includes a heat stage at a temperature of two furnaces, and the most (four) oxidized material is characterized in that the reduction is a heat treatment at two temperature steps of the reducing gas, _temperature stage, 20th 201022411 T> 1250 ° C, third temperature stage T > 1330 ° C, total time exceeds t = 12 hours, then the product is cold And an acid solution with a mineral acid, to form a thin film on the surface thereof Zn0, Si02. twenty one