TWI390017B - Phosphorous phosphor for use in light emitting diodes and its preparation method - Google Patents

Description

Fluoride-boring phosphor powder for light-emitting diode and preparation method thereof

The invention relates to a phosphor powder and a light-emitting diode, in particular to a boron fluoride fluorescent powder capable of creating high luminous efficiency and a light-emitting diode thereof, the phosphor powder and the light-emitting diode of the invention The polar body can be used in the nuclear physics of low- and medium-energy quantum fields, as a very good bright yellow paint in lacquers, detectors, and in the jewelry industry.

At present, semiconductor lighting technology is developing very rapidly. Japanese researcher S Nakamura. has developed this work and created very efficient technology (please refer to S.Nakamura.Blue laser, Springer Verlag, Berlin.1997). ). In this paper, an InGaN heterojunction (ie, PN junction) is used as a matrix, combined with a luminescence converter, to create a white light emitting diode by mixing blue light and ultraviolet light.

Similar to such a light-emitting diode, the first-time radiation excitation of the short-wavelength semiconductor heterojunction is combined with the luminescence converter.

This combination of light luminescence and partial luminescence that does not absorb heterojunction radiation produces a different hue of white light (according to Newton's complementary color law) and luminescence on the green visible spectrum sub-band. The structure of the luminescence converter is usually realized by a light-transmitting polymer and a phosphor powder filled in its range. This type of luminescence converter was used as a preparation of arsenide light-emitting diodes in 1972 (please Reference is made to US U.S. Patent No. 3,709,827 (10.02.1970) to Auzel F., and then to GaN in 1977 (see BC Abrabov, BP. Suskov, Soviet Publication, 12.09.1977). Finally, recently, a luminescence converter similar to an InGaN heterojunction has appeared (please refer to the Canadian CA 9000620 patent approved by Grodkiewicz and the Japanese JP 7183576 patent 21.07.1995 approved by S Nakamura, respectively).

The spectral conversions produced in inorganic phosphor particles may be of different chemical properties, such as fluoride or zinc sulfide, as well as the common yttrium aluminum garnet, with yttrium activator (YAG), which is widely used. Use in nuclear physics and electronic technology Medium (please refer to G.Blasse. Approved NP6706095 Patent 29.04.1967). For the first time, Nichia engineers on white light-emitting diodes (see US 5,998,992, 7.12.1997, approved by Shimizu S.). The present invention employs it as a patent reference object while noting its substantial drawbacks.

First, the efficacy of the LED is low, from 9 to 12 lumens per watt; second, the radiation color is not controllable; third, for the special low-output synthesis conditions for obtaining yttrium aluminum garnet, including the introduction of atmospheric and fluorine at high temperatures. Synthesis of hydrogen HF.

</ RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt; The data is as follows: for reducing the synthesis temperature of yttrium aluminum garnet and improving some special spectra, lumen-equivalent radiation, the composite material of the present invention incorporating aluminum fluoride AlF ₃ is used in the charge composition, and the aluminum salt is thermally processed. Sublimation during the charge process, the inventors of the present invention suggest that some of the fluoride ions may be introduced into the anion lattice of yttrium aluminum garnet, such as, for example, Y ₃ Al ₅ O ₁₁ F ₁ . The proposed method of the present invention achieves broad stretching and the use of this method to synthesize high quality products in the U.S. Patent No. 2,005,088, 770, filed to ss.

In order to solve the above disadvantages of the prior art, the main object of the present invention is to provide a light-emitting diode and a boron fluoride fluorescent powder thereof, which can improve the performance of the yttrium aluminum garnet of the light-emitting technique.

In order to solve the above-mentioned drawbacks of the prior art, another object of the present invention is to provide a light-emitting diode and a boron fluoride phosphor thereof which can reduce the reflectance of the first-order heterojunction nitride radiation.

In order to achieve the above object, a boron fluoride fluorescent powder of the present invention, which uses ruthenium as an activator, converts blue light emitted by a nitride heterojunction into bright yellow light, wherein the chemical formula is: Ln ₃ Al ⁺³ _2-x (AlO ₄ ) ^-5 _3-x (BF ₄ ) ^-1 _2x , wherein Ln=Y _1-yz Gd _y Ce _z , and a boron fluoride component is added to the phosphor powder (BF ₄ ) ^-1 to replace (AlO ₄ ) ^-5 in a part of the garnet lattice.

For the purpose of the above, a light-emitting diode of the present invention is based on a nitride heterojunction (InGaN), comprising: a crystal holder, a conical accumulator, a lens cover, and at least one conductive input. And an illuminating converter, according to the heterojunction radiation contact of the surface, wherein the illuminating converter has the boron fluoride phosphor powder particles and the cerium-containing polymer as described above, and has its own chemical composition connecting O- Si-OC.

For the above purposes, a method for preparing a boron fluoride phosphor of the present invention comprises the steps of: weighing an oxide of a desired rare earth element and a desired fluoride and boride according to a chemical formula, and then all After the materials are fully mixed, they are fully compacted in the crucible; the crucible is placed in an electric furnace to start the hot processing, and the hot processing is divided into three stages, and the whole process is protected with reducing gases H ₂ and N ₂ during the thermal processing. The product after hot working is reused for pickling to form ZnO on the surface of the phosphor powder particles. The SiO ₂ film layer; and the obtained phosphor powder are sieved, and then the parameters are measured.

First, the object of the present invention is to eliminate the disadvantages of the above-described phosphor powder and light-emitting diode. In order to achieve this goal, the boron fluoride fluorescent powder of the present invention uses yttrium as an activator to convert blue light emitted by a nitride heterojunction into bright yellow light, which is characterized in that its chemical formula is: Ln ₃ Al ⁺³ _2-x (AlO ₄ ) ^-5 _3-x (BF ₄ ) ^-1 _2x , wherein Ln=Y _1-yz Gd _y Ce _z , and a boron fluoride component (BF) is added to the phosphor powder ₄ ) ^-1 to replace (AlO ₄ ) ^-5 in part of the garnet lattice.

The stoichiometric parameter of the chemical formula is x=0.001~1, y=0.04~0.2, and z=0.005~0.1.

The cubic lattice parameter of the phosphor powder particles is a>11.9 Å.

The blue light emitted by the nitride heterojunction has an excitation wavelength of λ=430-470 nm and a radiation of λ=530-580 nm, wherein the atomic ratio is 4=(Y/Gd)<20.

The reflectance of the first-order short-wave luminescence of the phosphor powder in the nitride heterojunction may be less than 20%, and the reflectance parameter decreases after increasing the (BF ₄ ) ^-1 content in the phosphor powder.

The phosphor particle has a color coordinate value of 0.80 Σ(x+y) 0.95.

When the main component (BF ₄ ) ^-1 is added to the phosphor component, the spectral half-wave width is from λ _0.5 = 115 to 121 nm.

The color temperature of the phosphor powder particles is T=3500~4500K.

Wherein, when the phosphor particles are heated to T=100° C., the light conversion efficiency is not more than 25%.

The particles of the phosphor powder are bright yellow particles and have high light transmittance.

It is pointed out first that the phosphor powder based on the aluminum garnet is mainly introduced into the Y, Gd, and Ce groups in its composition.

Other rare earth elements such as Lu, Yb, Sm, Eu, Pr, Dy, Er, Ho, La and Nd may be directly introduced into the mixture in the phosphor powder component of the present invention, and the atomic fraction is 1. 10 ^-4 ~1.10 ^-2 .

Second, the phosphor powder of the present invention has a lattice parameter a>11.9 Å.

In order to illustrate the characteristics and properties of the phosphor powder proposed in the present invention, the phosphor powder proposed in the present invention uses the professional measuring instrument of the "Sensing" company to analyze the spectrum of the phosphor powder and the like. The parameters were measured, and the phosphor powder was measured by an InGaN-based light-emitting diode having a radiation excitation wavelength of λ=465.5 nm. The spectrophotometer records the radiation spectral energy of the material, and then uses the computer to count its physical optical parameters and colorimetric parameters. The spectrum and other parameters are: 1. illuminating color coordinates x, y, z, and u, v , w; 2. color temperature; 3. luminous brightness (relative to the brightness of the bottom of the instrument); 4. listed in the standard radiation source (A, B, C, E, D ₆₅ ); 5. the maximum wavelength of the spectrum, nm; 6. Radiation main wavelength nm, used to determine the asymmetric spectral radiation curve; 7. Spectral half-wave width, nm; 8. Pure color radiation a, in the white light part; 9. Red, green and blue color ratio Must be a color that can be reproduced; and 10. The color rendering index is in Ra and other components, of which

Analyze the conductivity method to analyze the melting of the sample containing the Na ₂ CO ₃ phosphor powder, and decompose the obtained product, boil and cool in the flask, and determine the F ^-1 ion and the B ⁺³ ion in a special ionizing solution. The concentration, using a spectrophotometer, using experimental data compared to the method for determining the composition of the phosphor particles - Auger-spectrum and SIMS (second quality spectrum).

In the process of the invention of the present invention, it has been found that for F/B≒4, corresponding to the (BF ₄ ) ^-1 structure in the tetrahedral form F-B-F, four F ^-1 ions surrounding the boron ion are present, The structure proposed by the invention enters the aluminum garnet in its composition as (BF ₄ ) ^-1 , the corresponding component and the well-known boron salt structure type, NaBF ₄ and KBF ₄ .

B ⁺³ and the ion introduction F ^-1 garnet phosphor, there will be three phenomena: 1. The first is to replace part of Al ⁺³ ions with ion-B ^+3, careful observation of the spectrum of the sample obtained, this replacement is just Luminescence Brightness 5-6%, and has a special spectral composition for storage stability; 2. Ion F ^-1 is added to the synthetic yttrium aluminum garnet phosphor, such as AlF ₃ , YF ₃ and HF, all samples are in spectral radiation It shows that the spectral half-wave width changes △λ _0.5 =2~3nm, and the illuminance of the luminescent powder increases by △L=2~3%, and the radiation color coordinates of the fluorifiable powder occur △S(x+y) The change of 0.02; 3. When the phosphor powder is prepared, the ion B ⁺³ and the ion F ^-1 are simultaneously added to the charge, and the ratio is F/B≒4, and the finished product is as shown in Table 1.

Please refer to FIG. 1 to FIG. 3 together, wherein FIG. 1 is a schematic diagram showing the radiation spectrum of the fluorescent powder of the sample 1 in Table 1; FIG. 2 is a schematic diagram showing the radiation spectrum of the fluorescent powder of the sample 2 in Table 1; Schematic diagram of the fluorescence spectrum of the sample of sample 1 in 1.

As shown in Fig. 1, the phosphor powder of sample 1 in Table 1 was measured by the SPR-920D fluorescent powder color parameter comprehensive analysis system of Sensing Company, and the obtained radiation spectral parameters were: chromaticity Coordinate Chromaticity Coordinates: x=0.4363 y=0.4909 u=0.2176 v=0.3673 correlated color temperature Correlated Color Temperature: 3598 K Brightness: 29270.7 reference white light Reference White: C source peak wavelength Peak Wave length: 568.3 nm dominant wavelength Dominant Wavelength: 573 nm Linewidth Bandwidth: 119.5 nm Purity: 0.8109 Radiation Brightness Brightness: 72.508 Color Ratio: Kr=50.8% Kg=38.2% Kb=11.0% Color Rendering Index Rendering Index: Ra=61.2 R1=54 R2=69 R3=85 R4=51 R5 =49 R6=56 R7=83 R8=42 R9=-64 R10=29 R11=39 R12=11 R13=57 R14=92 R15=44

As shown in Fig. 2, the phosphor powder of sample 2 in Table 1 was measured by the SPR-920D fluorescent powder color parameter comprehensive analysis system of Sensing Company, and the obtained radiation spectral parameters were: chromaticity product Coordinate Chromaticity Coordinates: x=0.4395 y=0.4907 u=0.2195 v=0.3676 correlated color temperature Correlated Color Temperature: 3548 K brightness Brightness: 28923.9 reference white light Reference White: C source peak wavelength Peak Wave length: 565.8 nm dominant wavelength Dominant Wavelength: 573 nm Linewidth Bandwidth: 119.7 nm Color Purity: 0.8174 Radiant Brightness Brightness: 71.773 Color Ratio: Kr=51.5% Kg=38.0% Kb=10.5% Color Rendering Index Rendering Index: Ra=61.1 R1=54 R2=69 R3=85 R4=51 R5=49 R6=56 R7=83 R8=42 R9=-63 R10=28 R11=38 R12=10 R13=57 R14=91 R15=44

As shown in Fig. 3, the phosphor of sample 3 in Table 1 was measured by the SPR-920D fluorescent powder color parameter comprehensive analysis system of Sensing Company. The spectral parameters are: chrominance coordinates Chromaticity Coordinates: x=0.3894 y=0.4516 u=0.2039 v=0.3546 correlated color temperature Correlated Color Temperature: 4226 K brightness Brightness: 28061.6 reference white light Reference White: C source peak wavelength Peak Wave length: 561.5 nm Dominant Wavelength: 570 nm spectral bandwidth Bandwidth: 128.9 nm color purity Purity: 0.5788 radiance Radiant Brightness: 75.411 color ratio Color Ratio: Kr = 43.5% Kg = 34.7% Kb = 21.7% color rendering index Rendering Index: Ra = 68.5R1=62 R2=78 R3=94 R4=56 R5=69 R6=71 R7=81 R8=47 R9=-47 R10=50 R11=49 R12=33 R13=66 R14=96 R15=51

First, compared with the standard, all the maximum radiation spectral shifts are Δλ _max = 7.3 nm and 4.8 nm, the color coordinate values △ Σ (x + y) = 0.0872 and 0.0902, and the change of the spectral half-wave width △ λ _0.5 = 2.5 nm and 2.3 In nm, the relative luminance of the light is increased by ΔL = 3.8% and = 2.6%.

The most notable changes in Figures 1, 2 and 3 are the two radiation spectra, short wavelength and long wavelength, which are 0.6:1 for the highest short-wavelength and long-wavelength values of the standard sample. Obviously, the smaller the maximum value with respect to the short wavelength, that is, the lower the efficiency of the fluorescent powder for reflecting the first-stage InGaN heterojunction radiation. The second sample has a short wavelength of only 20% compared to the long wavelength value.

For the first sample, the short wavelength is only 18% compared to the long wavelength value. The phenomenon that the phosphor powder like this has a low reflection efficiency against the first-order InGaN heterojunction is in the literature. It has not been described in China.

As shown in Table 1, the addition of the composition (BF ₄ ) ^-1 , spectral changes and special color coordinates in the phosphor powder requires an in-depth theoretical analysis of this unusual result.

It is well known fluoride ion radius of τ F ^-1 _F-1 = _1.32Å, oxygen ions O ^-2 radius τ _o-2 = 1.4Å, boron ions B ⁺³ radius of τ _{B + 3} = 0.2Å, aluminum ion Al The radius τ of ⁺³ is _Al+3 = 0.57Å, which shows that the unit structure size of (BF ₄ ) ^-1 is smaller than the unit structure size of (AlO ₄ ) ^-5 , so it can be assumed that part of the four sides is replaced by (BF ₄ ) ^-1 (AlO ₄ ) ^-5 in the body is relatively easy to access the Y ⁺³钇 ion and the activated ion Ce ⁺³ . Such a replacement will produce two phenomena: 1. One is because the (BF ₄ ) ^-1 unit structure is small in size, so the distance from the Y ⁺³钇 ion is shortened to cause a greater force; 2. The other is because (BF ₄ ) ^{-1 is} smaller than the charge ratio (AlO ₄ ) ^-5 , so the force of the Y ⁺³钇 ion is small, and the activated ion Ce ⁺³ has the same phenomenon, thus causing the displacement and luminescence of the maximum spectral wavelength. The asymmetry of the spectrum, as well as the half-wave width of the reduced spectral curve and the overall radiation efficiency of the phosphor powder of the present invention, are shown in Table 1.

Explain that the apparent short-wavelength and long-wavelength ratios are low, and the maximum possible basis is that it is activated when (BF ₄ ) ^{-1 is} surrounded by the oscillation absorption capacity of the activated ion Ce ⁺³ in the standard yttrium aluminum garnet composition. The oscillation absorption capacity of the ion Ce ⁺³ is increased.

Applying the known concept, the absorption light of a substance is related to its forbidden broadband Eg. If the substance is banned from broadband Eg > 3.8 electron volts (eV), the absorption wavelength of the substance is less than 380 nm, and an activated ion is introduced into Y ₃ Al ₅ O ₁₂ . Ce ⁺³ , absorption in the visible region of 380 ~ 780nm is very important, the substance can obtain strong red luminescence, this phenomenon is due to the strong charge transfer band of F ^-1 -Ce ⁺³ -O ^-2 ions Absorption, when 1% cerium ion Ce ⁺³ is introduced, high enough light absorption can be achieved. However, the same amount of activated ion Ce ^{+3 is added to the} standard phosphor powder, and the ability to absorb light cannot be improved. The reason for this is that the observed strong absorption of light has increased substantially, and the ability of the cesium ion Ce ^{+3 to} absorb light for the first time has increased two to three times.

According to the present invention, by substituting a tetrahedral (BF ₄ ) ^-1 moiety (AlO ₄ ) ^-5 in the Y ₃ Al ₅ O ₁₂ structure, the following results can be obtained: 1. Ce ^{+ 3} maximum spectral radiation wavelength shift; 2. half Wave width curve changes; 3. color coordinate value Σ (x + y) change; 4. asymmetric change of spectral radiation curve; 5. increase fluorescent powder radiation color purity; and 6. long wavelength luminescent color and short wave wavelength radiation excitation intensity Change.

The composition (BF ₄ ) ^-1 is retained in the garnet-structured phosphor, and the temperature conditions for the synthesis must be greater than 1300 °C. The bonding energy for B-F is E=757 kJ/mol, while the bonding energy of Ce-O is E=749 kJ/mol, and the bonding energy of small functional C-N is close to E=1004 kJ. /mol, it is known that the bonding of B-F has a very high durability. The (BF ₄ ) ^-1 component is composed of a fluoride ion F ^-1 and a BF ₂ atomic group, and its decomposition formula is BF ₂ →BF+F, and the required decomposition energy is 466 kJ/mol, which is also very important. The energy required for molecular decomposition of CeF ₃ →CeF ₂ +F is 686 kJ/mol (the highest value in the energy table for the decomposition of the entire polyatomic molecule or atomic group is ΔH° ₂₉₈ = 686 kJ/mol). Analysis of thermodynamic properties reveals that (BF ₄ ) ^-1 does not decompose at high temperatures.

Therefore, it can be asserted that boron fluoride (BF ₄ ) ^-1 can be fused in Y ₃ Al ₅ O ₁₂ and does not decompose at high temperatures. The main stoichiometric formula for the phosphor powder proposed by the present invention is: Ln ₃ Al ⁺³ _2-x (AlO ₄ ) ^-5 _3-x (BF ₄ ) ^-1 _2x .

The following is a description of the excitation spectrum of the phosphor powder proposed by the present invention. It has been determined that the maximum excitation spectrum has a short-wave displacement phenomenon compared with the standard phosphor powder, and is usually shifted from λ=450 to 475 nm to λ=435 to 470 nm. . This is an important advantage of the phosphors proposed in the present invention compared to standard phosphors. This advantage will be explained below. The maximum excitation spectrum of the standard phosphor powder is only 25 nm, and the maximum excitation spectrum of the phosphor powder proposed by the present invention is 35 nm, so that the phosphor powder proposed by the present invention can be more effectively utilized. The light energy radiated by the InGaN nitride heterogeneity enhances the overall brightness of the light-emitting diode. Expanding the first nitride heterojunction InGaN radiation excitation wavelength absorption interval is the main advantage of the phosphor powder proposed by the present invention, which is characterized in that the material is excited by radiation in a nitride heterojunction blue light with a wavelength from λ = 435 to 470 nm. And the maximum radiation spectrum from λ = 535 ~ 580nm, depending on the concentration between the ions, 5 = Y / Gd = 30 and the component (BF ₄ ) ^-1 replacement part of (AlO ₄ ) ^-5 . Please refer to Table 1 and Figure 1 to Figure 3 for the above description.

In the phosphor powder proposed by the present invention, the atomic fraction of Y changes from [Y]=0.94 to 0.85, and the ratio of Gd changes from Y/Gd=31 to 7, and the maximum spectral wavelength changes only 2.5~3 nm, which is related to The standard phosphor powder is very small compared to this, which is the first time we have observed this phenomenon.

We have noticed that the fluorescent powder proposed by the present invention has a new characteristic which substantially reduces the first reflected light and adds the component (BF ₄ ) ^{-1 to the} fluorescent powder. The establishment of a high-brightness white light-emitting diode can substantially reduce the thickness layer (or concentration) necessary for the phosphor particles. The first-order blue-radiation light may undergo several reflections at a high reflection coefficient without entering the active absorption of the phosphor powder, thus not only increasing the optical loss, but also reducing the overall brightness of the white light-emitting diode.

The main advantage of the phosphor powder proposed by the invention is that it has bright yellow luminescence, and the characteristic is that the region of the color coordinate value is 0.90=S(x+y)=0.95, mainly adding the component (BF ₄ ) to the phosphor powder. ^-1 .

In the process of invention, we have shown that the minimum Gd ⁺³ ion component in the phosphor powder component and the color coordinate of the component (BF ₄ ) ^-1 =0.05 atomic fraction are S(x+y)≒0.86, if the composition is increased. (BF ₄ ) ^-1 to 0.1 atomic fraction, the color coordinates increase to S(x+y) ≒ 0.90, and the maximum luminescence spectrum wavelength is λ = 565.8 nm.

As the concentration of Gd ⁺³ ions increases and the composition increases (BF ₄ ) ^-1 = 0.2 atomic fraction, a very large maximum spectral shift will be produced, up to λ = 568.8 nm and the color coordinate value S (x + y) = 0.94, The data measurement was measured by a professional spectrometer from Sensing.

This actual color coordinate value, in the production of white light emitting diodes, can produce a uniform color white light emitting diode than the standard fluorescent powder, that is, the color coordinates are more concentrated.

In the phosphor powder proposed by the present invention, an important advantage is that it has a bright yellow luminescence, which is characterized in that the change of the half-wave width for the maximum spectral radiation is from λ _0.5 = 116 to 121 nm, mainly in the phosphor powder. Add ingredient (BF ₄ ) ^-1 . In the course of the invention, we pointed out that the standard fluorescent powder spectral radiation curve is based on Gauss's law, and after adding the component (BF ₄ ) ^-1 , the spectral radiation curve is no longer symmetrical, mainly in terms of long wavelength. increase.

In the process work of the invention, it is pointed out that the phosphor powder proposed by the present invention has [Y/Gd] ≒42 in the composition, and the activation concentration 铈 ion [Ce ⁺³ ]=0.03 atomic fraction and (BF ₄ ) ^-1 At the atomic fraction of =0.031, the half-width of the spectrum is only λ _0.5 =116 nm. When [Y/Gd]≒31 and (BF ₄ ) ^-1 =0.1 atomic fraction, the spectral half-wave width increases to λ _0.5 =119.7. Nm.

The advantage of the boron fluoride fluorescent powder of the invention is characterized in that it is related to the change of the color temperature of the radiation, and the range of the color temperature change is 3500~4500K, which is mainly based on the content of boron fluoride (BF ₄ ) ^-1 .

White light can be distinguished according to the color temperature. The color temperature is greater than 6500K, which is usually cold white light. The color temperature is 6500~4500K, which is normal white light. The color temperature is less than 3500K, which is warm white light. The color temperature is from 3500~4500K. name.

The color temperature of the phosphor powder proposed by the present invention is in this interval. For the phosphor powder containing the low concentration of Gd ⁺³ ions, the color temperature is T=3548K, and the material has more Gd ⁺³ ions and more fluorination. The boron component has a color temperature of T = 3598K, which is also located in this range.

On a sunny day with no clouds, the general color temperature is at T=6500K. At sunset, there is more and more red radiation of sunlight, when the color temperature drops to T = 3500K. All lighting technology equipment is usually low color temperature, and most gas discharge sources are of high color temperature.

In the invention of the diode having the guaranteed bright yellow luminescence, the invention ensures The color temperature is at T=3500~4500K.

As far as we know, the higher the content (concentration) of Gd in the standard phosphor powder, the lower the thermal stability of the phosphor powder (that is, the higher the temperature, the lower the light conversion efficiency), and the present invention proposes In the phosphor powder, the content of Gd is only [Gd]=0.04~0.2, and contains a large number of (BF ₄ ) ^-1 , so the phosphor powder is more heat-resistant and has higher thermal stability.

A very important characteristic of the boron fluoride phosphor of the present invention is characterized in that the light conversion efficiency is not more than 25% when the phosphor particles are heated to T = 100 °C.

The following describes the preparation method of the boron fluoride fluorescent powder of the present invention: according to the chemical formula, the oxide of the desired rare earth element and the desired fluoride and boride are collected, and then all the materials are thoroughly mixed, and then placed at 300~ The 500ml crucible is fully compacted; the crucible is placed in an electric furnace to start the hot processing, and the thermal processing is divided into three stages; the temperature of the first stage is increased by 5 ° C / min to 1150 ° C, 2 to 4 hours, the second stage The temperature rises from 5 ° C / min to 1350 ~ 1550 ° C, 2 ~ 6 hours; the third processing temperature is the reduction speed of about 4 ° C / min to room temperature, during the hot processing process with the reducing gas H ₂ : N ₂ =5:95 protection; the product after hot processing is reused (HCl or HNO ₃ ) for pickling, and a thickness of 50 nm is formed on the surface of the phosphor powder particles. The SiO ₂ film layer; after the obtained phosphor powder passed through a 1000 mesh screen, its parameters were measured.

An embodiment and a preparation method thereof are as follows: The following raw material Y ₂ O _{3 is first} weighed: 28.82 g Al ₂ O ₃ : 24.48 g Gd ₂ O ₃ : 6.53 g AlF ₃ . 3H ₂ O: 3.68 g CeO ₂ : 1.55 g B ₂ O ₃ : 0.69 g Then all the materials are thoroughly mixed, and then placed in a 300-500 ml crucible for compaction; the crucible is placed in an electric furnace to start hot processing. The thermal processing is divided into three stages: the temperature rise of the first stage is 5 ° C / min to 1150 ° C, 2.5 hours, the temperature of the second stage rises 5 ° C / min to 1490 ° C, 4.5 hours; the temperature of the third processing is reduced The speed is about 4 ° C / min to room temperature, and the whole process is protected with a reducing gas H ₂ :N ₂ =5:95 during the hot working process; the product after the hot working treatment is further washed with HNO ₃ in the phosphor powder. The surface of the particles is formed to a thickness of 50 nm ZnO. SiO ₂ film layer. After the obtained phosphor powder passes through a 1000-mesh sieve, its parameters are measured.

The samples prepared in the above examples were the samples 1 in Table 1.

In addition, the present invention also discloses a light emitting diode. Please refer to FIG. 4 , which is a schematic structural view of a light emitting diode according to a preferred embodiment of the present invention. As shown in the figure, the light-emitting diode of the present invention is based on a nitride heterojunction 1 (InGaN), comprising: a crystal holder 2, a conical optical damper 3, a lens cover 4, and at least one conductive The input end 5 and an illuminating converter 6 are combined according to the radiation contact of the surface of the nitride heterojunction 1, characterized in that the illuminating converter 6 has the boron fluoride fluoron particles as described above and A ruthenium polymer having its own chemical composition linking O-Si-O-C.

Wherein, the molecular weight of the cerium-containing polymer is M=15000-25000 carbon units.

Wherein, the illuminating converter 6 adopts the same thickness, the thickness is 80-250 micrometers, the center crossing diagonal line is located on the vertical axis of the instrument, and the radiation lead passes through the lens cover 4 in the form of a spherical mirror to remit light.

The electric power of the light-emitting diode is W=3 watt, the luminous flux value is F>280 lumens, the radiation color temperature is T=3500~4500K, and the luminous efficiency is different according to the number of currents, and the rate range is η=132~96 lumens. /watt.

The phosphor of the present invention is used in the white light emitting diode as described above, wherein a nitride heterojunction 1 is utilized. The standard light-emitting diode structure is fixed in the conical accumulator 3 of the surface of the nitride heterojunction 1 by the crystal holder 2, not only the nitride The heterojunction 1 plane collects radiation and its facets are equally acceptable. On the surface of the nitride heterojunction 1 and the facet of the luminescence converter 6, the phosphor powder of the present invention is distributed together with a polymer (not shown) which requires very stable heat resistance and electrical conductivity.

We have found that for polymer materials, such as the use of organic germanium polymers, a relatively stable light-emitting diode can be obtained, which chemically bonds O-Si-O-Si. It also shows that the optimum molecular weight for organic ruthenium polymers ranges from M = 15,000 to 25,000 carbon units (degree of polymerization from 150 to 200).

In the test of the proposed light-emitting diode of the present invention, we have considered another very important requirement of the light-emitting diode, that is, the working temperature condition must be from 40 ° C to 80 ° C, which is present in the light-emitting diode. The demand in the body, low temperature working conditions, such as professional signal lights on the navigation river. Another aspect of high temperature occurs inside the light-emitting diode and is used in high temperature summer (40~50°C) without exceeding its operating temperature range. At different temperature working conditions, the polymer does not lose its own. fluidity.

Previously, an epoxy resin or a ruthenium polymer was generally used as the luminescence converter 6 in the light-emitting diode, but it is very important that the light transmittance of the luminescence converter 6 is destroyed at a high temperature, and 矽 is employed in the present invention. The polymer can eliminate the effects of temperature and make it work stably.

An important advantage of the proposed light-emitting diode of the present invention is that the illuminating converter 6 has a uniform thickness form and a thickness of 80-250 micrometers, and the center diagonal crossing is an optical device for the vertical axis. The light radiation of the light-emitting diode is derived by passing through the spherical lens cover 4.

An important advantage of the proposed light-emitting diode of the present invention is that the electric power W=3 watt, the luminous flux value thereof is increased by F>280 lumens, the radiation color temperature is T=3500~4500K, and the luminous efficiency is different according to the number of currents. The rate range is η=132~96 lumens/watt.

In summary, the method for preparing a boron fluoride fluorescent powder, a light emitting diode and a fluorescent powder of the present invention has the properties of improving the yttrium aluminum garnet of the light emitting technology and reducing the first level heterojunction The advantages of the reflectivity of the nitride radiation, and thus, the disadvantages of the conventional light-emitting diode and its fluorescent powder can be improved.

While the invention has been described above by way of a preferred embodiment, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Nitride heterojunction ‧‧1

Crystal support ‧‧‧2

Conical accumulator ‧‧3

Lens cover ‧‧4

Conductive input ‧‧‧5

Luminous converter ‧‧6

Step 1‧‧‧Weigh the desired rare earth element oxides and the required fluorides and borides according to the chemical formula, then thoroughly mix all the materials and put them into the crucible for compaction;

Step 2‧‧‧ Put the crucible into the electric furnace to start the hot processing. The hot processing is divided into three stages, and the whole process is protected with reducing gases H ₂ and N ₂ during the hot processing;

Step 3‧‧‧ After the hot-processed product is reused for pickling, ZnO is formed on the surface of the phosphor powder particles. SiO ₂ film layer and

Step 4‧‧‧ The obtained phosphor powder is sieved and then its parameters are measured.

1 is a schematic view showing a radiation spectrum of a fluorescent powder of Sample 1 in Table 1.

2 is a schematic view showing the radiation spectrum of the phosphor powder of the sample 2 in Table 1.

3 is a schematic view showing the radiation spectrum of the phosphor powder of the sample 3 in Table 1.

4 is a schematic view showing the structure of a light emitting diode according to a preferred embodiment of the present invention.

Claims (12)

A boron fluoride fluorescent powder which uses yttrium as an activator to convert blue light emitted by a nitride heterojunction into bright yellow light, characterized in that the chemical formula is: Ln ₃ Al ⁺³ _2-x ( AlO ₄ ) ^-5 _3-x (BF ₄ ) ^-1 _2x , wherein Ln=Y _1-yz Gd _y Ce _z , and a boron fluoride component (BF ₄ ) ^-1 is added to the phosphor powder to replace (AlO ₄ ) ^-5 in some garnet lattices, wherein the stoichiometric parameters of the chemical formula are x=0.001~1, y=0.04~0.2, z=0.005~0.1. For example, the boron fluoride fluorescent powder described in claim 1 has a cubic lattice parameter a>11.9 Å. The boron fluoride fluorescent powder according to claim 1, wherein the blue light emitted by the nitride heterojunction has an excitation wavelength of λ=430~470 nm and a radiation of λ=530~580 nm, wherein the atomic fraction is The ratio is 4 = (Y / Gd) < 20. The boron fluoride fluorescent powder according to claim 1, wherein the fluorescent powder has a reflection coefficient of less than 20% in the first-order short-wavelength light of the nitride heterojunction, and is added to the fluorescent powder. After the (BF ₄ ) ^-1 content, the reflection coefficient parameter decreases. For example, the boron fluoride fluorescent powder described in claim 1 has a color coordinate value of 0.80. Σ(x+y) 0.95. The boron fluoride phosphor according to claim 1, wherein the main component (BF ₄ ) ^-1 is added to the phosphor component, and the spectral half-wave width is from λ _0.5 = 115 to 121 nm. For example, the boron fluoride fluorescent powder described in claim 1 has a color temperature of T=3500~4500K. The boron fluoride fluorescent powder according to claim 1, wherein when the phosphor powder is heated to T=100° C., the light conversion efficiency is not more than 25%. The boron fluoride fluorescent powder according to claim 1, wherein the particles of the fluorescent powder are bright yellow particles and have high light transmittance. A light-emitting diode is based on a nitride heterojunction (InGaN), comprising: a crystal holder, a conical accumulator, a lens cover, at least one guide An electric input terminal and a luminescence converter according to the radiation contact of the surface of the nitride heterojunction, wherein the luminescence converter has the boron fluoride phosphor powder particles and the ruthenium-containing polymer according to claim 1 It has its own chemical composition to connect O-Si-OC. The illuminating diode of claim 10, wherein the illuminating converter has the same thickness, the thickness is 80-250 microns, the center cross diagonal is located on the vertical axis of the instrument, and the radiation lead passes through the lens. The cover retracts the light. The light-emitting diode according to claim 10, wherein the electric power is W 3 watts, its luminous flux value F> 280 lumens, radiation color temperature T = 3500 ~ 4500K, the luminous efficiency varies according to the number of currents, the rate range is η = 132 ~ 96 lumens / watt.