CN107353895B - Fluorescent powder compound, LED device and preparation method thereof - Google Patents
Fluorescent powder compound, LED device and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
- Led Device Packages (AREA)
Abstract
The invention relates to the technical field of luminescence and illumination, and particularly provides a fluorescent powder composition which comprises blue fluorescent powder and an encapsulation medium, wherein the blue fluorescent powder does not contain rare earth elements. The invention also provides an LED device based on the fluorescent powder composition and a preparation method thereof. The fluorescent powder composition provided by the invention has the advantages of low toxicity and wide light-emitting range, and is particularly suitable for ultraviolet excitation type LED devices.
Description
Cross Reference to Related Applications
The present application claims a title filed 2016, 11, 10: priority of chinese patent application CN 201610997247.4, "phosphor composites, LED devices and methods of making the same," is incorporated herein by reference in its entirety.
Technical Field
The invention relates to the technical field of luminescence and illumination, in particular to a fluorescent powder compound, an LED device based on the fluorescent powder compound and a preparation method of the LED device.
Background
Light Emitting Diodes (LEDs) are the most potential solid state lighting for energy savings compared to traditional lighting, and White Light Emitting Diodes (WLEDs) in particular have found very widespread use. The most common method for realizing white light is to use yellow phosphor powder Y3Al5O12:Ce3+The (YAG: Ce) and the blue light (the light-emitting waveband is 450-470nm) InGaN light-emitting diode chip are compounded to generate white light. The blue light intensity in the light-emitting spectrum of the white light LED is higher, so that the white light LED has stronger damage effect on retina and can not meet the application requirement of indoor healthy illumination. Compared with the existing blue light excitation type white light LED, the ultraviolet chip excitation type white light LED (UV type white light LED) device has more flexibility in design, can reduce blue light damage, improve color rendering index, reduce color failure and improve thermal stability, and becomes an important direction for the development of the existing white light LED indoor lighting application.
The blue light emitting material is a core material for preparing the UV type white light LED. Currently, blue-light fluorescent powder is mainly concentrated on Eu2+、Ce3+Ion-doped rare earth materials such as phosphate, halophosphate, fluorine and silicate. The rare earth materials usually have a single emission peak, and the emission peak is narrow (the half-peak width is 30-60nm), so that the requirements of a high color rendering index white light LED device on a broad spectrum luminescent material cannot be met. In addition, the rare earth fluorescent powder has the problems of rising price and patent barriers.
In recent years, the field of nano luminescent materials is rapidly developed, and various blue light luminescent materials are provided. Researchers have achieved high-efficiency blue light emission in nano materials such as zinc oxide, gallium oxide, carbon dots, zinc selenide and the like, however, the photo-thermal stability of these nano materials is poor, which limits the application of these nano materials in LEDs. Gibbsite is a group of hydroxide minerals containing aluminum, having a gibbsite (gibbsite,γ-Al(OH)3) Boehmite, or boehmite (boehmite, γ -AlOOH), and diaspore (tohdite,5 Al)2O3·H2Many complex crystal structures such as O), previous studies have been made on the synthetic chemistry of the boehmite mineral material and its luminescence mechanism, and how to obtain a high-performance blue-light-emitting boehmite mineral material, for example, the α -AlOOH natural mineral luminescence was first reported by Garcia-Guinea group in Spain's high scientific society of 20012+、Ti4+Plasma center, the wavelength of light emitted depending on the type of ion center (Garcia-Guinea J., Rubio J., Correcher V., et Al. luminescence of alpha-Al)2O3and alpha-AlOOH natural mixtures[J]Radial Measure, 2001,33(5): 653-. In 2004, the Cun Li group of university of Nanjing university reported a sol-gel preparation method of boehmite gamma-AlOOH whiskers, the luminescence of which comes from oxygen defects (F, F)+)(Yu Z.Q.,Wang C.X.,Gu X.T.,et al.Photoluminescent properties of boehmite whisker prepared bysol-gel[J]J.Lumin,2004,106(2): 153-. In 2010, Paul K.Chu group, university of hong Kong City[23]Preparing Al (OH) by adopting a pulse laser ablation method3Fluorescent colloidal nanocrystals having a peak emission at 383nm (Li T.H., Liu.Z., Wu X.L., et al., Photopharmaceuticals from colloidal conjugates with colloidal crystals with uniform size [ J]Appl.phys.lett,2010,97(12): 121901). The researches show that the boehmite mineral material is a blue light emitting material with great potential. However, the boehmite mine nano luminescent material prepared by the method has the defects of low fluorescence quantum efficiency, insufficient spectrum width, poor controllability of the preparation method and the like, and cannot meet the application requirements of UV type LEDs.
Therefore, developing white LEDs based on non-rare earth broad-spectrum blue fluorescent materials with low toxicity, low cost, and high performance, especially uv-excitation white LEDs, is an important need in the field of lighting.
Disclosure of Invention
One of the purposes of the invention is to provide a fluorescent powder compound, which comprises blue fluorescent powder, wherein the blue fluorescent powder has good comprehensive performance and does not contain rare earth metal elements, and is suitable for being used as a luminescent material of an LED device, in particular an ultraviolet excitation type white light LED device.
The second purpose of the invention is to provide a preparation method of the fluorescent powder compound, which has low cost and easy operation.
It is a further object of the present invention to provide an LED device comprising the phosphor composition provided according to the present invention.
Still another object of the present invention is to provide a method for manufacturing the above LED device.
According to one of the objects of the present invention, a phosphor composition is provided, comprising a blue phosphor and an encapsulation medium, wherein the blue phosphor comprises Al2O3·nH2An aluminum hydroxide of O, wherein n ═ 0.2, 1, or 3; the phosphor composition is free of rare earth elements.
As mentioned above, the blue-light fluorescent material based on rare earth materials has the defects of narrow light-emitting spectrum, high preparation cost and the like. At present, most of the marketed blue fluorescent powder is doped with rare earth ions. The blue fluorescent powder used by the invention is based on aluminum hydroxide, does not contain rare earth elements, and reduces the toxicity and the production cost.
The fluorescent powder compound provided by the invention is suitable for being used as a luminescent material of an LED device, in particular an ultraviolet excitation type white light LED device.
It is to be understood that the blue phosphors used in the present invention may have the available chemical formula Al2O3·nH2Aluminum hydroxide represented by O is the main component. n is 0.2, 1 or 3, respectively, for different stable structures of the aluminum hydroxide. For example, when n is 0.2, Al2O3·nH2O is 5Al2O3·H2O, corresponding to hexagonal gibbsite; when n is 1, Al2O3·nH2O is AlOOH, corresponding to boehmite or boehmite; when n is 3, Al2O3·nH2O is Al (OH)3Corresponding to gibbsite.
According to the invention, in the blue-light phosphor, Al2O3·nH2The content of O is preferably 35 to 60 wt%, more preferably 37 to 58 wt%. Fluorescent in blueThe remaining composition of the powder may include a certain amount of carbon-containing dopant.
For example, in some embodiments, the blue phosphor comprises Al2O3·nH2The content of O is 35 wt%, 37 wt%, 39 wt%, 42 wt%, 44 wt%, 46 wt%, 48 wt%, 50 wt%, 52 wt%, 55 wt%, 57 wt% or 59 wt%.
According to the present invention, preferably, the blue phosphor includes 10 to 40 wt%, preferably 20 to 36 wt%, more preferably 25 to 36 wt% of the carbon element based on the total weight of the blue phosphor. The blue-light fluorescent powder used in the invention is an organic-inorganic hybrid system, the surface of the blue-light fluorescent powder contains organic groups, and the carbon content is 10-40 wt%. The fluorescence of the fluorescent powder compound provided by the invention can be partially from the oxygen defect of the blue fluorescent powder and partially from the doped carbon impurity.
In some preferred embodiments of the present invention, the blue phosphor comprises 12-38 wt% of the carbon element, for example 14 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt%, 32 wt%, 34 wt%, 36 wt%, or 38 wt% of the carbon element.
According to a preferred embodiment of the present invention, in the blue phosphor, the oxygen element content is 45 to 65 wt%, preferably 50 to 60 wt%, based on the total weight of the blue phosphor; the content of aluminum element is 10-25 wt%, preferably 15-22 wt%.
In some preferred embodiments of the present invention, the blue phosphor comprises 50 wt%, 52 wt%, 54 wt%, 56 wt%, 58 wt%, 60 wt%, 62 wt%, or 65 wt% of oxygen element.
In some preferred embodiments of the present invention, the blue phosphor comprises 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt% or 25 wt% of aluminum element.
According to the invention, the fluorescence emission peak of the blue fluorescent powder is in the range of 350-530nm, preferably 380-525nm, and the fluorescence emission peak of the blue fluorescent powder preferably exists in the range of 380-400nm and/or 430-460 nm. That is, in some embodiments, the blue phosphor used in the present invention has a fluorescence emission peak in the range of 380-400nm or in the range of 430-460 nm; in other embodiments, the blue phosphor used in the present invention has fluorescence emission peaks in the range of 380-400nm and the range of 430-460nm, respectively.
According to a preferred embodiment of the present invention, the blue phosphor has a fluorescence emission peak at least in the range of 430-460 nm.
In a preferred embodiment of the invention, the blue phosphor has a first fluorescence emission peak between 380-400nm and a second fluorescence emission peak between 430-460 nm. One outstanding feature of the blue phosphor used in the preferred embodiment provided by the present invention is that it exhibits characteristic fluorescence emission peaks in the two aforementioned light wavelength ranges. The excitation band can be selected in the ultraviolet region (e.g. 340-420nm) or the blue region (e.g. 430-460 nm). The fluorescence spectrum of the blue phosphor can be detected by a steady state fluorescence spectrometer and a transient state fluorescence spectrometer.
In some embodiments of the invention, the first fluorescence emission peak is between 380-390 nm.
In some embodiments of the invention, the second fluorescence emission peak is between 440-455 nm.
Further, in some embodiments, the blue phosphor also has a third fluorescence emission peak between 490-540 nm.
In some embodiments of the invention, the third fluorescence emission peak is between 500-520 nm.
In some embodiments of the present invention, the blue phosphor has only the second fluorescence emission peak and the third fluorescence emission peak, i.e., the first fluorescence emission peak may not be significantly present.
According to the present invention, the half-width of the fluorescence emission peak of the blue phosphor is preferably in the range of 30 to 130 nm.
Preferably, the half-width of the first fluorescence emission peak is between 27 and 34nm, preferably between 28 and 32 nm.
According to the invention, the half-width of the second fluorescence emission peak is between 30 and 130 nm.
According to the invention, the half-width of the third fluorescence emission peak is between 85 and 105nm, preferably between 88 and 102 nm.
The blue fluorescent powder used by the invention, especially the second fluorescent emission peak and the third fluorescent emission peak have larger half-peak width, so that the provided fluorescent powder compound can increase the color rendering index of a white light LED device when being used for the LED device.
According to the invention, the blue phosphor has a fluorescence quantum yield (PLQYs) of 40-70%, for example 55-70%, measured at an excitation wavelength of 370 nm. Fluorescence quantum yield may be tested by an absolute fluorescence quantum yield test system (e.g., manufactured by hamamatsu corporation).
According to the invention, the blue-light fluorescent powder is preferably amorphous powder, and the particles of the blue-light fluorescent powder are micro-nano spherical bodies.
The blue-light fluorescent powder contained in the fluorescent powder compound provided by the invention is a photoluminescence material.
The blue light emitting powder contained in the fluorescent powder compound provided by the invention has the light emitting wavelength range of 350-600nm, and particularly has a remarkable light emitting effect in the wavelength range of 400-550 nm. Therefore, the blue fluorescent powder used by the invention has wide light-emitting spectrum and can meet the requirement of a white light LED device with high display index on the wide spectrum.
According to a preferred embodiment of the present invention, the content of the blue phosphor is 5 to 80 wt%, preferably 5 to 50 wt%, based on the total weight of the phosphor composite; specifically, the blue phosphor is contained in an amount of, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, or 80 wt%, based on the total weight of the phosphor composite.
The encapsulating medium contained in the phosphor composite provided by the invention is preferably at least one of silica gel, epoxy resin and polymethyl methacrylate (PMMA), and is preferably silica gel and/or epoxy resin. Suitable silicone and epoxy resins may be those conventionally used in the field of LED technology, such as silicone OE6551A, silicone OE6551B, KER-2500A, KER-2055B. In the invention, the packaging medium is mixed with the fluorescent powder to serve as a medium on one hand, and is helpful for improving the light extraction efficiency on the other hand.
According to a preferred embodiment of the present invention, in the phosphor composition, a weight ratio of the blue phosphor to the encapsulating medium is 1: (1-20), preferably 1: (1.5-10).
In some embodiments of the present invention, the phosphor composition is comprised of the blue phosphor described above and an encapsulating medium.
The phosphor composition provided by the present invention preferably contains 0.5 to 32 wt%, more preferably 1 to 18 wt%, and further preferably 2 to 15 wt% of carbon element based on the weight of the phosphor composition.
In some embodiments of the present invention, the phosphor composition may further comprise a nanocrystalline phosphor, preferably a red non-rare earth nanocrystalline phosphor.
In the invention, the nanocrystalline phosphor is preferably non-rare earth CuInS2And (3) nanocrystalline fluorescent powder. The color rendering index of the device can be improved by adding the nanocrystalline fluorescent powder. Suitable non-rare earth CuInS2The nanocrystalline phosphors may be those described In the patent application having application number CN201110259596.3 entitled "a nanocrystalline phosphor and method of making the same", such as Cu-In-Znx-E/ZnS phosphor, wherein E ═ S or Se, and x.gtoreq.0. Wherein, the value of x is preferably between 0 and 1. The entire contents of this patent application are incorporated herein by reference. The non-rare earth CuInS2The nanocrystalline phosphor is red non-rare earth CuInS2And (3) nanocrystalline fluorescent powder.
Preferably, the mass ratio of the nanocrystalline phosphor to the blue phosphor is 1: 20-500, preferably 1: 40-300, and more preferably 1: 40-200. Specifically, the mass ratio of the nanocrystalline phosphor to the blue phosphor may be, for example, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:120, 1:150, 1:180, 1:200, 1:250, or 1: 300.
According to a second aspect of the present invention, there is provided a method for preparing the phosphor composition provided above, including mixing the blue phosphor with the encapsulation medium to obtain the phosphor composition.
In some embodiments, the method for preparing the phosphor composition may include: adding the blue fluorescent powder into the packaging medium, and stirring for a certain time, such as 5-20min, preferably 10-15 min; and then placing for 10-60min at a certain temperature and pressure to obtain the fluorescent powder compound, wherein the temperature is preferably 20-50 ℃, and the pressure is preferably in the range of 0.08-0.1 MPa of vacuum degree. The fluorescent powder compound after the treatment can also be called as fluorescent glue and can be directly used for manufacturing LED devices.
According to a third aspect of the present invention, there is provided an LED device comprising the phosphor composition provided according to the present invention. Further, the LED device comprises fluorescent glue prepared from the fluorescent powder compound provided by the invention. The LED device is preferably a white LED device, more preferably an ultraviolet excitation type LED device. Due to the adoption of the fluorescent powder compound provided by the invention as a luminescent material, the excitation wave band used for the LED device can be selected in an ultraviolet region, such as: 340 and 420 nm. Therefore, the light emitted by the LED device has the advantage of small harm to human eyes, and the device is flexible in structural design.
In the present invention, other components of the provided LED device are not particularly limited, and may be conventional components of the LED device understood by those skilled in the art unless otherwise specified, so that further description of the other components of the LED device is omitted herein.
According to another aspect of the present invention, there is provided a method for preparing an LED device, comprising incorporating the phosphor composition provided according to the present invention into the LED device.
According to the invention, the preparation method of the LED device comprises the steps of preparing the fluorescent powder compound and filling the fluorescent powder compound into the LED and curing the LED.
In some embodiments of the present invention, the method for manufacturing the LED device comprises the steps of:
1) preparation of phosphor composites according to the invention provided as described above: adding blue fluorescent powder or blue fluorescent powder and nanocrystalline fluorescent powder into a packaging medium, stirring, and carrying out degassing bubble treatment;
2) filling the prepared fluorescent powder compound in an LED device;
3) and curing the fluorescent powder compound to obtain the LED device.
In the above step 1), the blue phosphor contains 10 to 40 wt%, preferably 20 to 36 wt%, of the carbon element, based on the total weight of the blue phosphor, as described above; preferably, in the blue phosphor, the content of oxygen element is 45-65 wt% and the content of aluminum element is 10-25 wt%, preferably 15-22 wt%, based on the total weight of the blue phosphor.
In step 1), stirring is preferably always performed in a clockwise direction or always in a counterclockwise direction, and further preferably performed at a rate of 2 to 3 revolutions/second. The stirring time in step 1) is preferably from 5 to 20min, preferably from 8 to 15 min.
In some embodiments of the present invention, the encapsulating medium in step 1) is silica gel OE6551A and/or silica gel OE6551B, preferably in a mass ratio of 1:0.8-1.5 to silica gel OE6551A and silica gel OE 6551B.
In step 1), it is preferable that the defoaming treatment is carried out under a pressure (vacuum degree) of 0.08 to-0.1 MPa. Further, it is preferable that the deaeration treatment is performed at a temperature of 20 to 50 ℃, more preferably 25 to 40 ℃. For example, the mixture produced in step 1) may be put into a vacuum oven to be subjected to a defoaming treatment. Preferably, during the defoaming process, if the solution overflows, the solution is properly deflated to prevent the overflow. The defoaming treatment time is preferably 10 to 90 minutes.
According to a preferred embodiment of the present invention, after the end of the defoaming, the mixture may be continuously stirred at a rate of, for example, 2 to 3 cycles/second at room temperature and atmospheric pressure for a certain period of time, for example, 3 to 10 minutes.
The process of phosphor compound loading within the LED device is commonly referred to as dispensing. In step 2), dispensing can be carried out with the aid of a syringe. Specifically, the mixture can be transferred into a 5mL syringe, and bubbles are prevented from being generated when the mixture is poured; and (3) installing an air inlet pipe on the needle cylinder, and applying pressure to the air inlet pipe to enable the mixture in the needle cylinder to slowly drip into a groove in the center of the patch type LED cup bowl for example until the mixture is in a flat cup shape (flush with the groove opening) in the cup bowl, so as to obtain the LED integral device before curing.
In the step 3), the LED support filled with the phosphor compound in the step 2) may be placed in a drying oven for curing.
Step 3) the curing is preferably carried out at 100-150 ℃, preferably at 110-130 ℃. Preferably, the curing time is from 0.5 to 4 hours, preferably from 2 to 3.5 hours.
It is easy to understand that when the prepared LED device does not contain the nanocrystalline fluorescent powder, only the blue fluorescent powder is added into the packaging medium in the step 1) and mixed and stirred; when the fluorescent powder compound also comprises the nanocrystalline fluorescent powder, the blue fluorescent powder and the nanocrystalline fluorescent powder are added and stirred together in the step 1) when the corresponding LED device is prepared.
For step 2) above, it can be further understood that the prepared phosphor compound is filled in the groove of the LED holder. The LED support, as understood by a person skilled in the art, refers to an LED device not loaded with luminescent material, and may also be understood as a precursor of a complete LED device. The LED support has a groove structure, the blue light or ultraviolet LED wafer is located inside the groove, and the two ends of the support are provided with positive and negative pins.
The LED device provided by the invention can be a patch type, a direct insertion type, a high-power type or a thin film type white LED. Accordingly, the LED device used in the above step 2) may be a mount of a patch type, a direct insertion type, a high power type or a thin film type white LED.
According to the present invention, in some embodiments, the method for preparing the phosphor composition or the method for preparing the LED device further comprises a step for preparing the blue phosphor, comprising: and heating and decomposing the organic aluminum salt precursor in an inert atmosphere to obtain the blue fluorescent powder.
In the preparation step of the blue fluorescent powder, the organic aluminum salt precursor is directly heated and decomposed to prepare the boehmite ore nano luminescent material, and the organic aluminum salt is used as an aluminum source and provides a surface ligand in the thermal decomposition process, so the method can be called as a thermal decomposition in-situ coordination method. The blue fluorescent powder can be prepared by a gas phase method in the invention because the blue fluorescent powder is directly heated and decomposed in a gas atmosphere.
Preferably, the organic aluminum salt precursor is heated to a reaction temperature of 290-340 ℃, preferably 300-330 ℃, and more preferably 310-330 ℃ under an inert atmosphere.
Preferably, the reaction temperature is maintained for 1 to 5 hours, preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours.
In the prior art, in the heating reaction stage for preparing the blue fluorescent powder, reaction conditions of high temperature and long-time reaction are often adopted, for example, the reaction is carried out for several hours at high temperature of up to 800 ℃. However, in the present invention, under a simple process concept, the precursor is heated to 290-340 ℃ in an inert atmosphere for a certain time, for example, 1-3 hours, so as to obtain the high-performance blue-light fluorescent material. Therefore, the preparation steps of the blue fluorescent powder provided by the invention are simple to operate, the energy consumption is low, and the efficiency is high.
According to the present invention, it is preferable that the organic aluminum salt precursor is decomposed into the blue phosphor by heating under continuous introduction of an inert atmosphere. The organic aluminum salt precursor is heated and reacted in the continuously introduced inert gas, so that the organic aluminum salt precursor is ensured to react in a fresh and sufficient inert atmosphere all the time, and unnecessary gas components generated by heating are taken away in time by the passing inert gas, thereby being beneficial to accelerating the reaction process and optimizing reaction products.
In some embodiments of the present invention, the preparation of the blue phosphor comprises the steps of: grinding the organic aluminum salt precursor; placing the ground organic aluminum salt precursor into a reaction tube, and introducing inert gas into the reaction tube; heating the reaction tube to ensure that the organic aluminum salt precursor is heated and decomposed under the condition of introducing inert gas; wherein the inert gas is introduced at a rate of 10 to 300sccm (sccm, Standard Cubic Centimeter per Minute), and preferably at a heating rate of 29 to 34 ℃/min; and cooling to obtain the blue-light fluorescent powder.
Under the proper temperature raising program and reaction temperature, the organic aluminum salt precursor is thermally decomposed fast and stably into the required blue fluorescent powder.
In some embodiments, the organic aluminum salt precursor is ground before the reaction, so that the reaction is sufficiently and uniformly performed to obtain a uniform powdery fluorescent material.
Preferably, the reaction tube is a quartz tube, and the organic aluminum salt precursor is placed in a quartz boat in the quartz tube.
Preferably, the reaction tube is heated using a tube furnace.
Preferably, the inert gas is nitrogen.
According to the present invention, in the above-mentioned method (vapor phase method), the organic aluminum salt precursor may be selected from one or more of aluminum hydroxide acetate, aluminum triacetate, aluminum isooctanoate, aluminum acetylacetonate, aluminum monostearate, aluminum butyrate and aluminum glycinate, preferably one or more of aluminum hydroxide acetate, aluminum stearate and aluminum acetylacetonate, more preferably aluminum hydroxide acetate.
In a preferred embodiment of the present invention, basic aluminum acetate is used as the organic aluminum salt precursor in the above method (gas phase), and the blue phosphor prepared by the method has a first fluorescence emission peak between 380-400nm and a second fluorescence emission peak between 440-460 nm. In some more preferred embodiments, the resulting blue phosphor also has a third fluorescence emission peak between 510-530 nm.
According to the present invention, there is also provided a further preparation step of the blue phosphor contained in the phosphor composition of the present invention, comprising: mixing an organic aluminum salt precursor with an organic solvent to obtain a reaction mixture; heating the reaction mixture to a first temperature in vacuo; introducing inert gas, continuously heating to a second temperature, and reacting the reaction mixture at the second temperature for a certain time; the second temperature is higher than the first temperature.
The preparation method of the blue fluorescent powder is that the mixed reaction solution reacts for a certain time under the vacuum condition and then continues to react for a certain time under the inert atmosphere, and compared with the previous gas phase method, the method can be called as a liquid phase method. In the liquid phase method, the organic aluminum salt precursor is preferably decomposed by heating in a double-row system, i.e., under a condition where an inert gas is introduced under vacuum. The double pipe system may be, for example, the Schlenk line system.
According to the present invention, in the above liquid phase method, the organic solvent preferably contains C12-C22Preferably one or more selected from oleylamine, oleic acid, octadecene and paraffin, more preferably octadecene.
According to the present invention, in the above liquid phase method, the ratio of the amount of the organic aluminum salt precursor to the amount of the organic solvent is preferably 0.1 to 10g of the organic aluminum salt precursor per mL of the organic solvent.
According to the present invention, in the above liquid phase process, the first temperature is preferably 80 to 120 ℃, more preferably 95 to 105 ℃.
According to the present invention, in the liquid phase method, the second temperature is preferably 290-. Preferably, the temperature is maintained for 20 to 40 minutes after the inert gas is introduced, and then the heating is continued to the second temperature.
According to the present invention, in the above liquid phase process, the reaction mixture is preferably stirred at the first temperature for 15 to 50 minutes, preferably 20 to 40 minutes.
According to the present invention, in the above liquid phase process, it is preferable that the reaction mixture is reacted at the second temperature for 1 to 24 hours, preferably 2 to 8 hours, more preferably 3 to 6 hours.
Also, in the liquid phase process of the present invention, the organic aluminum salt precursor may be selected from one or more of basic aluminum acetate, aluminum triacetate, aluminum isooctanoate, aluminum acetylacetonate, aluminum monostearate, aluminum butyrate and aluminum glycinate, preferably one or more of basic aluminum acetate, aluminum acetylacetonate and aluminum glycinate.
In a preferred embodiment of the invention, basic aluminum acetate is used as an organic aluminum salt precursor in the liquid phase method for preparing the blue phosphor, and the prepared blue phosphor has a first fluorescence emission peak between 380-400nm and a second fluorescence emission peak between 440-460 nm. In some more preferred embodiments, the resulting blue phosphor also has a third fluorescence emission peak between 510-530 nm.
According to the present invention, the liquid phase method further comprises a post-treatment step of: and carrying out solid-liquid separation on the mixture obtained by the reaction, washing and drying the solid to obtain the blue fluorescent powder.
The solid-liquid separation can be completed by centrifugation, and in the centrifugation process, the solid is washed by toluene and acetone to obtain diaspore ore blue light material solid. Further, the solid is dried in vacuum at 40-60 ℃ to obtain the powdery diaspore blue light material.
In the liquid phase method, a proper reaction mixture system reacts under the control of proper reaction temperature and reaction time under two reaction procedures (vacuum-inert atmosphere) to obtain the blue fluorescent powder with high fluorescence quantum efficiency and wide fluorescence emission spectrum.
Non-exhaustively, advantages of the present invention include the following.
The blue fluorescent material used by the fluorescent powder compound provided by the invention does not contain rare earth elements, and has the characteristics of low toxicity, adjustable light-emitting wavelength, large light-emitting wavelength range (350-. When the fluorescent powder compound is used for an LED device, an ultraviolet excitation type white light LED device with high color rendering index can be prepared.
The LED device provided by the invention has the advantages of higher color rendering index, adjustable color temperature, high luminous brightness, good thermal stability, long service life and low energy consumption.
The preparation method of the LED device provided by the invention comprises the preparation step of the blue fluorescent powder, has the advantages of simple process, high yield of the blue fluorescent powder, low cost, environmental protection, easy operation and large-scale production.
Drawings
FIG. 1 is a fluorescence emission spectrum of the blue phosphor prepared in example 1;
FIG. 2 is a fluorescence emission spectrum of the blue phosphor prepared in example 2;
FIG. 3 is a fluorescence emission spectrum of the blue phosphor prepared in example 3;
FIG. 4 is a fluorescence emission spectrum of the blue phosphor prepared in example 4;
FIG. 5 is a fluorescence emission spectrum of the blue phosphors prepared in examples 5 and 6;
FIG. 6 is a fluorescence emission spectrum of the blue phosphor prepared in example 7;
FIG. 7 is a fluorescence emission spectrum of the blue phosphor prepared in example 8;
FIG. 8 is a fluorescence emission spectrum of the blue phosphor prepared in example 9;
FIG. 9 is a white light spectrum of an LED device prepared in example 1;
FIG. 10 is a white light spectrum of an LED device prepared in example 2;
FIG. 11 is a white light spectrum of an LED device prepared in example 3;
FIG. 12 is a white light spectrum of an LED device prepared in example 4;
FIG. 13 is a white light spectrum of an LED device prepared in example 8;
FIG. 14 is a white light spectrum of an LED device prepared in example 10;
fig. 15 is a white light spectrum of the LED device prepared in example 11.
Detailed Description
The invention will be further described with reference to specific embodiments, it being understood that the scope of the invention is not limited to these illustrative embodiments.
Example 1
(1) Preparation of blue phosphor
Taking a proper amount of basic aluminum acetate (Al (OH) (Ac) as an organic aluminum salt precursor2) And fully grinding. Weighing 0.5000g to 2.0000g of ground aluminum hydroxide acetate powder.
Putting the weighed aluminum hydroxide powder into a quartz boat, putting the quartz boat into a quartz tube, and putting the quartz tube into a heating area of a tube furnace. And (4) connecting an exhaust system, checking the air tightness of the system after sealing is finished, and setting heating conditions after confirming that the air tightness is good.
And introducing nitrogen into the quartz tube for 30min for exhausting, continuing introducing nitrogen at the rate of 50sccm after exhausting is finished, and starting the heating program of the tube furnace system. The initial temperature was room temperature and the ramp rate was 26 deg.C/min. After the temperature is raised to 290 ℃, the system is kept at 290 ℃ for 2 h.
And after the heat preservation of the tube furnace system is finished and the tube furnace system is automatically stopped, opening the tube furnace under the condition that the sample is cooled to room temperature along with the furnace, taking out the quartz boat and the obtained non-rare earth blue fluorescent powder, and calculating the yield to be 50%.
The aluminum hydroxide Al contained in the obtained non-rare earth blue fluorescent powder is determined through the tests of an X-ray diffractometer (XRD) and a Fourier transform infrared spectrum analyzer (FTIR)2O3·nH2N of O is 1.
The content of C, O, Al in the obtained non-rare earth blue fluorescent powder is respectively determined by a scanning electron microscope-energy dispersive spectrometer (SEM-EDS): 28.93 wt%, 55.55 wt%, 15.36 wt%.
The fluorescence quantum yield of the obtained non-rare earth blue fluorescent powder is measured to be 60.9% by using a hamamatsu absolute fluorescence quantum yield test system and adopting an excitation wavelength of 370 nm.
The fluorescence emission spectrum of the obtained non-rare earth blue fluorescent powder is tested by using a steady-state fluorescence spectrometer, and the result is shown in figure 1. The fluorescent powder has fluorescence emission peaks at 388nm, 451nm and 515nm respectively, and the light-emitting spectral range is about 350-600 nnm.
(2) Preparation of LED device
Step one, preparation
Adding the prepared blue fluorescent powder into an encapsulation medium to obtain a mixture, and stirring the mixture by using a glass rod; the stirring speed is 2-3 circles/second, clockwise stirring is carried out in one direction, excessive bubbles are avoided, and stirring is carried out for 10 min.
In the mixture, the mass percentage of the blue fluorescent powder is 10 wt%. The packaging medium is silica gel OE6551A and silica gel OE6551B, and the mass of the silica gel OE6551A is as follows: the mass of the silica gel OE6551B was 1: 2.
Step two, defoaming
And (3) placing the stirred mixture into a vacuum drying box, and defoaming at 30 ℃ under the vacuum degree of 0.09MPa for 60 min. During the defoaming process, if the solution overflows, the solution is properly deflated to prevent the solution from overflowing. And after defoaming, taking out the mixture, and slowly stirring the mixture for 5 minutes in one direction at the speed of 2-3 seconds per circle by using a glass rod, wherein bubbles are prevented from being generated during stirring.
Step three, dispensing
And (4) transferring the mixture treated in the step two into a 5mL syringe, and avoiding generating air bubbles when pouring. And (3) installing an air inlet pipe on the needle cylinder, and applying pressure to the air inlet pipe, so that the mixture in the needle cylinder slowly drips into the groove in the center of the patch type LED cup bowl until the mixture is in a flat cup shape (flush with the groove opening) in the cup bowl, and obtaining the LED integral device before curing.
Step four, curing
And placing the LED integral device before curing into a drying oven, and baking for 3 hours at 120 ℃ to obtain the patch type LED device, thereby realizing the application of the non-rare earth blue fluorescent powder in the white light LED.
The prepared non-rare earth blue fluorescent powder white light LED is detected, and the detection steps are as follows: sequentially turning on a high-precision rapid spectral radiometer power supply, a precision digital display direct current stabilized current voltage stabilizing power supply and an LEDspec testing software, and selecting a conventional measuring mode; placing the LED at the entrance of the integrating sphere, connecting the positive and negative pins of the LED with a precise digital display direct current stabilized voltage supply, and applying a specified forward current I to the LEDFAt 20mA, the photometric detection system measures the luminous flux. And displaying the white light spectrum, CIE 1931 chromaticity coordinates, the color rendering index, the color temperature and the efficiency parameters on software, and exporting data and analyzing the spectrum.
And analyzing to obtain a non-rare earth blue fluorescent powder white light LED spectrogram shown in figure 9. It can be seen that the LED has characteristic peaks at 405nm (LED chip band, ultraviolet region), 462nm, and 520nm (blue region), indicating that the emitted visible light is mainly in the blue region.
Software analysis shows that the light emitted by the LED is in a blue light region as proved by the fact that the CIE chromaticity coordinates are (0.165, 0.248), the color rendering index is 38.4, the color temperature is 8746K and the lumen efficiency is 37.0 lm/W.
Example 2
(1) Preparation of blue phosphor
Taking a proper amount of basic aluminum acetate (Al (OH) (Ac) as an organic aluminum salt precursor2) And fully grinding. 1.25g of ground aluminum oxyacetate powder was weighed.
Putting the weighed aluminum hydroxide powder into a quartz boat, putting the quartz boat into a quartz tube, and putting the quartz tube into a heating area of a tube furnace. And (4) connecting an exhaust system, checking the air tightness of the system after sealing is finished, and setting heating conditions after confirming that the air tightness is good.
And introducing nitrogen into the quartz tube for 30min for exhausting, continuing introducing nitrogen at the rate of 50sccm after exhausting is finished, and starting the heating program of the tube furnace system. The initial temperature was room temperature and the ramp rate was 30 deg.C/min. After the temperature is raised to 300 ℃, the system is kept at 300 ℃ for 2.5 h.
And after the heat preservation of the tube furnace system is finished and the tube furnace system is automatically stopped, opening the tube furnace under the condition that the sample is cooled to room temperature along with the furnace, taking out the quartz boat and the obtained non-rare earth blue fluorescent powder, and calculating the yield to be 54%.
The aluminum hydroxide Al contained in the obtained non-rare earth blue fluorescent powder is determined by XRD and FTIR tests2O3·nH2N of O is 3.
The obtained non-rare earth blue fluorescent powder contains C, O, Al contents determined by SEM-EDS and respectively comprises the following components: 28.42 wt%, 55.82 wt%, 15.61 wt%. The fluorescence quantum yield of the obtained non-rare earth blue fluorescent powder is measured to be 62.0% by using a hamamatsu absolute fluorescence quantum yield test system and adopting an excitation wavelength of 370 nm.
The fluorescence emission spectrum of the obtained non-rare earth blue fluorescent powder is tested by using a steady-state fluorescence spectrometer, and the result is shown in fig. 2. The fluorescent powder has fluorescence emission peaks at 388nm, 451nm and 515nm respectively. The second fluorescence emission peak (451nm) of the present example was greater in intensity than the second fluorescence emission peak of example 1, as compared with example 1. As can be seen, the emission spectrum of the phosphor is about 350-600 nnm.
(2) Preparation of LED device
Step one, preparation
Adding the prepared blue fluorescent powder into an encapsulation medium to obtain a mixture, and stirring the mixture by using a glass rod; the stirring speed is 2-3 circles/second, clockwise stirring is carried out in one direction, excessive bubbles are avoided, and stirring is carried out for 10 min.
The packaging medium is silica gel OE6551A and silica gel OE6551B, and the mass of the silica gel OE6551A is as follows: the mass of the silica gel OE6551B was 1: 1. In the mixture, the mass percentage of the blue fluorescent powder is 12 wt%.
Step two, defoaming
And (3) placing the stirred mixture into a vacuum drying box, and carrying out defoaming treatment for 50min at 40 ℃ under the negative pressure condition. During the defoaming process, if the solution overflows, the solution is properly deflated to prevent the solution from overflowing. And after defoaming, taking out the mixture, and slowly stirring the mixture for 7 minutes in one direction at the speed of 2-3 seconds per circle by using a glass rod, wherein bubbles are prevented from being generated during stirring.
Step three, dispensing
And (4) transferring the mixture treated in the step two into a 5mL syringe, and avoiding generating air bubbles when pouring. And (3) installing an air inlet pipe on the needle cylinder, and applying pressure to the air inlet pipe, so that the mixture in the needle cylinder slowly drips into the groove in the center of the patch type LED cup bowl until the mixture is in a flat cup shape (flush with the groove opening) in the cup bowl, and obtaining the LED integral device before curing.
Step four, curing
And placing the whole LED device before curing into a drying oven, and baking for 3 hours at 110 ℃ to obtain the patch type LED device, thereby realizing the application of the non-rare earth blue fluorescent powder in the white light LED.
The prepared non-rare earth blue phosphor white light LED was detected by the same test method as in example 1 to obtain a non-rare earth blue phosphor white light LED spectrum shown in fig. 10. It can be seen that the LED has characteristic peaks at 405nm (LED chip band, ultraviolet region), 463nm, 523nm (blue region), indicating that the emitted visible light is mainly in the blue region.
Software analysis shows that the CIE chromaticity coordinates are (0.258, 0.269), the color rendering index is 53.4, the color temperature is 8654K, and the lumen efficiency is 31.0lm/W, so that the light emitted by the LED is in the blue light region.
Example 3
(1) Preparation of blue phosphor
Taking a proper amount of basic aluminum acetate (Al (OH) (Ac) as an organic aluminum salt precursor2) And fully grinding. 1.25g of ground aluminum oxyacetate powder was weighed out.
Putting the weighed aluminum hydroxide powder into a quartz boat, putting the quartz boat into a quartz tube, and putting the quartz tube into a heating area of a tube furnace. And (4) connecting an exhaust system, checking the air tightness of the system after sealing is finished, and setting heating conditions after confirming that the air tightness is good.
And introducing nitrogen into the quartz tube for 30min for exhausting, continuing introducing nitrogen at the rate of 100sccm after exhausting is finished, and starting a heating program of the tube furnace system. The initial temperature was room temperature and the ramp rate was 32 deg.C/min. After the temperature is raised to 320 ℃, the system is kept at 320 ℃ for 2.5 h.
And after the heat preservation of the tube furnace system is finished and the tube furnace system is automatically stopped, opening the tube furnace under the condition that the sample is cooled to room temperature along with the furnace, taking out the quartz boat and the obtained non-rare earth blue fluorescent powder, and calculating the yield to be 66%.
The aluminum hydroxide Al contained in the obtained non-rare earth blue fluorescent powder is determined by XRD and FTIR tests2O3·nH2N of O is 3.
The obtained non-rare earth blue fluorescent powder contains C, O, Al contents determined by SEM-EDS and respectively comprises the following components: 27.17 wt%, 56.63 wt%, 16.10 wt%. The fluorescence quantum yield of the obtained non-rare earth blue fluorescent powder is measured to be 70% by using a hamamatsu absolute fluorescence quantum yield test system and adopting an excitation wavelength of 370 nm.
The fluorescence emission spectrum of the obtained non-rare earth blue fluorescent powder was measured by a steady-state fluorescence spectrometer, and the result is shown in fig. 3. The fluorescent powder has fluorescence emission peaks at 390nm, 448nm and 515nm respectively. Compared with examples 1 and 2, the first fluorescence emission peak (390nm) of the present example is smaller in intensity than the first fluorescence emission peaks of examples 1 and 2, and the second fluorescence emission peak (448nm) is larger in intensity than the second fluorescence emission peaks of examples 1 and 2. As can be seen, the emission spectrum of the phosphor is about 350-600 nnm. (2) Preparation of LED device
Step one, preparation
Adding the prepared blue fluorescent powder into an encapsulation medium to obtain a mixture, and stirring the mixture by using a glass rod; the stirring speed is 2-3 circles/second, clockwise stirring is carried out in one direction, excessive bubbles are avoided, and stirring is carried out for 10 min.
The packaging medium is silica gel OE6551A and silica gel OE6551B, and the mass of the silica gel OE6551A is as follows: the mass of the silica gel OE6551B was 1: 1. In the mixture, the mass percentage of the blue fluorescent powder is 10 wt%.
Step two, defoaming
And (3) placing the stirred mixture into a vacuum drying box, and carrying out defoaming treatment for 40min at 35 ℃ under the negative pressure condition. During the defoaming process, if the solution overflows, the solution is properly deflated to prevent the solution from overflowing. And after defoaming, taking out the mixture, and slowly stirring the mixture for 8 minutes in one direction at the speed of 2-3 seconds per circle by using a glass rod, wherein bubbles are prevented from being generated during stirring.
Step three, dispensing
And (4) transferring the mixture treated in the step two into a 5mL syringe, and avoiding generating air bubbles when pouring. And (3) installing an air inlet pipe on the needle cylinder, and applying pressure to the air inlet pipe, so that the mixture in the needle cylinder slowly drips into the groove in the center of the patch type LED cup bowl until the mixture is in a flat cup shape (flush with the groove opening) in the cup bowl, and obtaining the LED integral device before curing.
Step four, curing
And (3) placing the whole LED device before curing into a drying oven, and baking for 1 hour at 140 ℃ to obtain the patch type LED device, thereby realizing the application of the non-rare earth blue fluorescent powder in the white light LED.
Detecting the prepared non-rare earth blue fluorescent powder white light LED by the same test method as the embodiment 1 to obtain a non-rare earth blue fluorescent powder white light LED spectrogram shown in figure 11; it can be seen that the LED has characteristic peaks at 405nm (LED chip band, ultraviolet region), 475nm, 521nm (blue region), indicating that the emitted visible light is mainly in the blue region.
Software analysis shows that the light emitted by the LED is in a blue light region as proved by the fact that the CIE chromaticity coordinates are (0.248, 0.412), the color rendering index is 56.6, the color temperature is 7569K, and the lumen efficiency is 28.2 lm/W.
Example 4
(1) Preparation of blue phosphor
Taking a proper amount of organic aluminum salt precursor aluminum stearate (Al (St)3) And fully grinding. 0.88g of the aluminum stearate powder after grinding was weighed.
And putting the weighed aluminum stearate powder into a quartz boat, putting the quartz boat into a quartz tube, and putting the quartz tube into a heating area of a tube furnace. And (4) connecting an exhaust system, checking the air tightness of the system after sealing is finished, and setting heating conditions after confirming that the air tightness is good.
And introducing nitrogen into the quartz tube for 30min for exhausting, continuing introducing nitrogen at the rate of 150sccm after exhausting is finished, and starting a heating program of the tube furnace system. The initial temperature was room temperature and the ramp rate was 33 deg.C/min. After the temperature is raised to 330 ℃, the system is kept at 330 ℃ for 4 h.
And after the heat preservation of the tube furnace system is finished and the tube furnace system is automatically stopped, opening the tube furnace under the condition that the sample is cooled to room temperature along with the furnace, taking out the quartz boat and the obtained non-rare earth blue fluorescent powder, and calculating the yield to be 64%.
The aluminum hydroxide Al contained in the obtained non-rare earth blue fluorescent powder is determined by XRD and FTIR tests2O3·nH2N of O is 0.2.
The obtained non-rare earth blue phosphor contained C, O, Al in an amount of 35.2 wt%, 45.3 wt%, 19.3 wt%, respectively, as determined by SEM-EDS. The fluorescence quantum yield of the obtained non-rare earth blue fluorescent powder is measured to be 45% by using a hamamatsu absolute fluorescence quantum yield test system and adopting an excitation wavelength of 370 nm.
The fluorescence emission spectrum of the obtained non-rare earth blue fluorescent powder was measured by a steady-state fluorescence spectrometer, and the result is shown in fig. 4. The fluorescent powder has fluorescence emission peaks at 431nm and 493nm respectively. As can be seen from the figure, the luminescence spectrum of the phosphor is about 360-600 nm.
(2) Preparation of LED device
Step one, preparation
Adding the prepared blue fluorescent powder into an encapsulation medium to obtain a mixture, and stirring the mixture by using a glass rod; the stirring speed is 2-3 circles/second, clockwise stirring is carried out in one direction, excessive bubbles are avoided, and stirring is carried out for 10 min.
The packaging medium is silica gel OE6551A and silica gel OE6551B, and the mass of the silica gel OE6551A is as follows: the mass of the silica gel OE6551B was 1: 1. In the mixture, the mass percentage of the blue fluorescent powder is 40 wt%.
Step two, defoaming
And (3) placing the stirred mixture into a vacuum drying box, and carrying out defoaming treatment for 20min at the temperature of 45 ℃ under the negative pressure condition. During the defoaming process, if the solution overflows, the solution is properly deflated to prevent the solution from overflowing. And after defoaming, taking out the mixture, and slowly stirring the mixture for 5 minutes in one direction at the speed of 2-3 seconds per circle by using a glass rod, wherein bubbles are prevented from being generated during stirring.
Step three, dispensing
And (4) transferring the mixture treated in the step two into a 5mL syringe, and avoiding generating air bubbles when pouring. And (3) installing an air inlet pipe on the needle cylinder, and applying pressure to the air inlet pipe, so that the mixture in the needle cylinder slowly drips into the groove in the center of the patch type LED cup bowl until the mixture is in a flat cup shape (flush with the groove opening) in the cup bowl, and obtaining the LED integral device before curing.
Step four, curing
And (3) placing the whole LED device before curing into a drying oven, and baking for 3 hours at 150 ℃ to obtain the patch type LED device, thereby realizing the application of the non-rare earth blue fluorescent powder in the white light LED.
Detecting the prepared non-rare earth blue fluorescent powder white light LED by the same test method as the embodiment 1 to obtain a non-rare earth blue fluorescent powder white light LED spectrogram shown in figure 12; it can be seen that the LED has characteristic peaks at 405nm (LED chip band, ultraviolet region), 446nm, and 480nm (blue region), indicating that the emitted visible light is mainly in the blue region.
Software analysis shows that the light emitted by the LED is in a blue light region as proved by the fact that the CIE chromaticity coordinates are (0.225, 0.234), the color rendering index is 42.3, the color temperature is 9563K, and the lumen efficiency is 27.5 lm/W.
Example 5
Taking a proper amount of organic aluminum salt precursor aluminum acetylacetonate (Al (acac)3) And fully grinding. The milled aluminum acetylacetonate powder (1.62 g) was weighed out.
And putting the weighed acetylacetone aluminum powder into a quartz boat, putting the quartz boat into a quartz tube, and putting the quartz tube into a heating area of a tube furnace. And (4) connecting an exhaust system, checking the air tightness of the system after sealing is finished, and setting heating conditions after confirming that the air tightness is good.
And introducing nitrogen into the quartz tube for 40min for exhausting, continuing introducing nitrogen at the rate of 200sccm after exhausting is finished, and starting the heating program of the tube furnace system. The initial temperature was room temperature and the ramp rate was 33 deg.C/min. After the temperature is raised to 330 ℃, the system is kept at 330 ℃ for 4 h.
And after the heat preservation of the tube furnace system is finished and the tube furnace system is automatically stopped, opening the tube furnace under the condition that the sample is cooled to room temperature along with the furnace, taking out the quartz boat and the obtained non-rare earth blue fluorescent powder, and calculating the yield to be 60%.
The aluminum hydroxide Al contained in the obtained non-rare earth blue fluorescent powder is determined by XRD and FTIR tests2O3·nH2N of O is 0.2.
The obtained non-rare earth blue fluorescent powder contains C, O, Al contents determined by SEM-EDS and respectively comprises the following components: 26.2 wt%, 51.6 wt%, 22.1 wt%. The fluorescence quantum yield of the obtained non-rare earth blue fluorescent powder is 47% by using a hamamatsu absolute fluorescence quantum yield testing system and adopting an excitation wavelength of 370 nm.
The fluorescence emission spectrum of the obtained non-rare earth blue fluorescent powder is tested by using a steady-state fluorescence spectrometer, and the result is shown in fig. 5. The fluorescent powder has fluorescence emission peaks at 391nm and 453nm respectively. As can be seen, the luminescence spectrum of the phosphor is in the range of about 340-600 nm.
Example 6
(1) Preparation of blue phosphor
The experimental procedure of example 5 was repeated except that after warming to 330 ℃ the system was incubated at 330 ℃ for 24 h. The fluorescence emission spectrum of the obtained non-rare earth blue phosphor is shown in fig. 5. As can be seen from the results of the fluorescence emission spectrum tests (fig. 5) in the comparative examples 5 and 6, as the heating time is prolonged, the first fluorescence emission peak of the prepared non-rare earth blue phosphor gradually weakens, and the second fluorescence emission peak is gradually obvious, so that the light emitting performance of the non-rare earth blue phosphor can be adjusted, and the peak intensity of the blue region is increased, which is beneficial to improving the color rendering index when the non-rare earth blue phosphor is applied to a white LED device.
(2) Preparation of LED device
Step one, preparation
Adding the prepared blue fluorescent powder into an encapsulation medium to obtain a mixture, and stirring the mixture by using a glass rod; the stirring speed is 2-3 circles/second, clockwise stirring is carried out in one direction, excessive bubbles are avoided, and stirring is carried out for 15 min.
In the mixture, the mass percentage of the blue fluorescent powder is 30 wt%. The packaging medium is silica gel KER2500A and silica gel KER2500B, and the mass of the silica gel KER2500A is as follows: the mass of the silica gel KER2500B is 1: 2.
Step two, defoaming
And (3) placing the stirred mixture into a vacuum drying box, and defoaming at 30 ℃ under the vacuum degree of 0.09MPa for 60 min. And after defoaming, taking out the mixture, and slowly stirring the mixture for 5 minutes in one direction at the speed of 2-3 seconds per circle by using a glass rod, wherein bubbles are prevented from being generated during stirring.
Step three, dispensing
And (4) transferring the mixture treated in the step two into a 5mL syringe, and avoiding generating air bubbles when pouring. And (3) installing an air inlet pipe on the needle cylinder, and applying pressure to the air inlet pipe, so that the mixture in the needle cylinder slowly drips into the groove in the center of the patch type LED cup bowl until the mixture is in a flat cup shape (flush with the groove opening) in the cup bowl, and obtaining the LED integral device before curing.
Step four, curing
And placing the LED integral device before curing into a drying oven, and baking for 3 hours at 120 ℃ to obtain the patch type LED device, thereby realizing the application of the non-rare earth blue fluorescent powder in the white light LED.
The prepared non-rare earth blue phosphor white LED was tested in a similar test method as in example 1. The LED has characteristic peaks at 405nm (LED chip wave band, ultraviolet region), 461nm and 516nm (blue region), which indicates that the emitted visible light is mainly in the blue region.
Software analysis shows that the light emitted by the LED is in a blue light region, the CIE chromaticity coordinates are (0.254 and 0.385), the color rendering index is 35, the color temperature is 8726K, and the lumen efficiency is 35.0l m/W.
Example 7
0.8105g of basic aluminum acetate and 20mL of octadecene were put into a 100mL three-necked flask and mixed to obtain a mixed solution. The mixed solution was heated to 100 ℃ under vacuum and stirred for 30 min. Then nitrogen is introduced for keeping for 30min, the temperature is increased to 300 ℃, the solution changes from white to light yellow, and the constant temperature reaction is carried out for 5 h.
And adding the solution prepared in the step into a 100mL centrifuge tube to a position half as high as the tube, and performing centrifugal separation to obtain a bottom substance and a supernatant. After the supernatant was removed, the mixture was washed twice with 3mL of toluene and 60mL of acetone, centrifuged, and the supernatant was removed to obtain a diaspore blue-light material.
And (3) drying the obtained boehmite fluorescent material for 1h in vacuum at the temperature of 50 ℃ to obtain a powdery product. The detection proves that the powdery product is the diaspore blue fluorescent powder.
The aluminum hydroxide Al contained in the obtained non-rare earth blue fluorescent powder is determined by XRD and FTIR tests2O3·nH2N of O is 1.
The obtained non-rare earth blue fluorescent powder contains C, O, Al contents determined by SEM-EDS and respectively comprises the following components: 26.5 wt%, 53.4 wt%, 20.0 wt%. The fluorescence quantum yield of the obtained non-rare earth blue fluorescent powder is measured to be 46.1% by using a hamamatsu absolute fluorescence quantum yield test system and adopting an excitation wavelength of 370 nm.
The fluorescence emission spectrum of the obtained non-rare earth blue fluorescent powder was measured by a steady-state fluorescence spectrometer, and the result is shown in fig. 6. The fluorescent powder has fluorescence emission peaks at 390nm, 452nm and 513nm respectively. As can be seen, the emission spectrum of the phosphor is about 350-600 nnm.
(2) Preparation of LED device
Step one, preparation
Adding the prepared blue fluorescent powder into an encapsulation medium to obtain a mixture, and stirring the mixture by using a glass rod; the stirring speed is 2-3 circles/second, clockwise stirring is carried out in one direction, excessive bubbles are avoided, and stirring is carried out for 15 min.
In the mixture, the mass percentage of the blue fluorescent powder is 30 wt%. The packaging medium is silica gel KER2500A and silica gel KER2500B, and the mass of the silica gel KER2500A is as follows: the mass of the silica gel KER2500B is 1: 2.
Step two, defoaming
And (3) placing the stirred mixture into a vacuum drying box, and defoaming at 30 ℃ under the vacuum degree of 0.09MPa for 60 min. And after defoaming, taking out the mixture, and slowly stirring the mixture for 5 minutes in one direction at the speed of 2-3 seconds per circle by using a glass rod, wherein bubbles are prevented from being generated during stirring.
Step three, dispensing
And (4) transferring the mixture treated in the step two into a 5mL syringe, and avoiding generating air bubbles when pouring. And (3) installing an air inlet pipe on the needle cylinder, and applying pressure to the air inlet pipe, so that the mixture in the needle cylinder slowly drips into the groove in the center of the patch type LED cup bowl until the mixture is in a flat cup shape (flush with the groove opening) in the cup bowl, and obtaining the LED integral device before curing.
Step four, curing
And placing the LED integral device before curing into a drying oven, and baking for 3 hours at 120 ℃ to obtain the patch type LED device, thereby realizing the application of the non-rare earth blue fluorescent powder in the white light LED.
The prepared non-rare earth blue phosphor white LED was tested in a similar test method as in example 1. The LED has characteristic peaks at 405nm (LED chip wave band, ultraviolet light region), 473nm and 517nm (blue light region), and the emitted visible light is mainly in the blue light region.
Software analysis shows that the light emitted by the LED is in a blue light region, the CIE chromaticity coordinates are (0.180, 0.230), the color rendering index is 45, the color temperature is 8650K, and the lumen efficiency is 39.0l m/W.
Example 8
(1) Preparation of blue phosphor
0.8105g of basic aluminum acetate and 20mL of octadecene were put into a 100mL three-necked flask and mixed to obtain a mixed solution. The mixed solution was heated to 100 ℃ under vacuum and stirred for 30 min. Then nitrogen is introduced for keeping for 30min, the temperature is raised to 330 ℃, the solution changes from white to light yellow, and the constant temperature reaction is carried out for 3 h.
And adding the solution prepared in the step into a 100mL centrifuge tube to a position half as high as the tube, and performing centrifugal separation to obtain a bottom substance and a supernatant. After the supernatant was removed, the mixture was washed twice with 3mL of toluene and 60mL of acetone, centrifuged, and the supernatant was removed to obtain a diaspore blue-light material.
And (3) drying the obtained boehmite fluorescent material for 1h in vacuum at the temperature of 50 ℃ to obtain a powdery product. The detection proves that the powdery product is the diaspore blue fluorescent powder.
The aluminum hydroxide Al contained in the obtained non-rare earth blue fluorescent powder is determined by XRD and FTIR tests2O3·nH2N of O is 3.
The obtained non-rare earth blue fluorescent powder contains C, O, Al contents determined by SEM-EDS and respectively comprises the following components: 37.2 wt%, 52.1 wt%, 10.7 wt%. The fluorescence quantum yield of the obtained non-rare earth blue fluorescent powder is measured to be 65.4% by using a hamamatsu absolute fluorescence quantum yield test system and adopting an excitation wavelength of 440 nm.
The fluorescence emission spectrum of the obtained non-rare earth blue fluorescent powder was measured by a steady-state fluorescence spectrometer, and the result is shown in fig. 7. The fluorescent powder has fluorescence emission peaks at 396nm, 455nm and 512nm respectively. As can be seen, the emission spectrum of the phosphor is about 350-640 nnm.
(2) Preparation of LED device
Step one, preparation
Adding the prepared blue fluorescent powder into an encapsulation medium to obtain a mixture, and stirring the mixture by using a glass rod; the stirring speed is 2-3 circles/second, clockwise stirring is carried out in one direction, excessive bubbles are avoided, and stirring is carried out for 10 min.
The packaging medium is silica gel OE6551A and silica gel OE6551B, and the mass of the silica gel OE6551A is as follows: the mass of the silica gel OE6551B was 1: 1. In the mixture, the mass percentage of the blue fluorescent powder is 13 wt%.
Step two, defoaming
And (3) placing the stirred mixture into a vacuum drying box, and carrying out defoaming treatment for 20min at the temperature of 50 ℃ under the negative pressure condition. During the defoaming process, if the solution overflows, the solution is properly deflated to prevent the solution from overflowing. And after defoaming, taking out the mixture, and slowly stirring the mixture for 3 minutes in one direction at the speed of 2-3 seconds per circle by using a glass rod, wherein bubbles are prevented from being generated during stirring.
Step three, dispensing
And (4) transferring the mixture treated in the step two into a 5mL syringe, and avoiding generating air bubbles when pouring. And (3) installing an air inlet pipe on the needle cylinder, and applying pressure to the air inlet pipe, so that the mixture in the needle cylinder slowly drips into the groove in the center of the patch type LED cup bowl until the mixture is in a flat cup shape (flush with the groove opening) in the cup bowl, and obtaining the LED integral device before curing.
Step four, curing
And (3) placing the whole LED device before curing into a drying oven, and baking for 4 hours at 100 ℃ to obtain the patch type LED device, thereby realizing the application of the non-rare earth blue fluorescent powder in the white light LED.
The prepared non-rare earth blue fluorescent powder white light LED is detected by the same test method as the example 1.
And detecting to obtain the non-rare earth blue fluorescent powder white light LED spectrogram shown in figure 13. Fig. 13 shows that the LED has characteristic peaks at 405nm (wavelength band of LED chip, ultraviolet region), 481nm, and 519nm (blue region), indicating that the emitted visible light is mainly in the blue region.
Software analysis shows that the light emitted by the LED is in a blue light region as proved by the fact that the CIE chromaticity coordinates are (0.243, 0.386), the color rendering index is 50.7, the color temperature is 8356K and the lumen efficiency is 32.1 lm/W.
Example 9
(1) Preparation of blue phosphor
0.1351g of aluminum glycinate and 20mL of oleylamine were put into a 100mL three-necked flask and mixed to obtain a mixed solution. The mixed solution was heated to 90 ℃ under vacuum and stirred for 40 min. Then nitrogen is introduced for keeping for 30min, the temperature is raised to 340 ℃, the solution is changed from white to light yellow, and the constant temperature reaction is carried out for 6 h.
And adding the solution prepared in the step into a 100mL centrifuge tube to a position half as high as the tube, and performing centrifugal separation to obtain a bottom substance and a supernatant. After the supernatant was removed, the mixture was washed twice with 2mL of toluene and 50mL of acetone, centrifuged, and the supernatant was removed to obtain a diaspore blue-light material.
And (3) drying the obtained boehmite fluorescent material for 2h under vacuum at the temperature of 60 ℃ to obtain a powdery product. The detection proves that the powdery product is the diaspore blue fluorescent powder.
The aluminum hydroxide Al contained in the obtained non-rare earth blue fluorescent powder is determined by XRD and FTIR tests2O3·nH2N of O is 3.
The obtained non-rare earth blue fluorescent powder contains C, O, Al contents determined by SEM-EDS and respectively comprises the following components: 25.3 wt%, 50.2 wt%, 24.3 wt%. The fluorescence quantum yield of the obtained non-rare earth blue fluorescent powder is measured to be 65.4% by using a hamamatsu absolute fluorescence quantum yield test system and adopting an excitation wavelength of 440 nm.
The fluorescence emission spectrum of the obtained non-rare earth blue fluorescent powder is tested by using a steady-state fluorescence spectrometer, and the result is shown in fig. 8. The fluorescent powder has fluorescence emission peaks at 388nm and 455nm respectively. As can be seen, the emission spectrum of the phosphor is about 350-600 nnm.
(2) Preparation of LED device
Step one, preparation
Adding the prepared blue fluorescent powder into an encapsulation medium to obtain a mixture, and stirring the mixture by using a glass rod; the stirring speed is 2-3 circles/second, clockwise stirring is carried out in one direction, excessive bubbles are avoided, and stirring is carried out for 15 min.
In the mixture, the mass percentage of the blue fluorescent powder is 40 wt%. The packaging medium is bisphenol A type epoxy resin EP-400A, and the mass ratio of the bisphenol A type epoxy resin EP-400A is as follows: the mass of the epoxy resin curing agent EP-400B is 1: 1.
Step two, defoaming
And (3) placing the stirred mixture into a vacuum drying box, defoaming and standing for 60min at the temperature of 35 ℃ and the vacuum degree of 0.06 MPa. And after defoaming, taking out the mixture, and slowly stirring the mixture for 5 minutes in one direction at the speed of 2-3 seconds per circle by using a glass rod, wherein bubbles are prevented from being generated during stirring.
Step three, dispensing
And (4) transferring the mixture treated in the step two into a 5mL syringe, and avoiding generating air bubbles when pouring. And (3) installing an air inlet pipe on the needle cylinder, and applying pressure to the air inlet pipe, so that the mixture in the needle cylinder slowly drips into the groove in the center of the patch type LED cup bowl until the mixture is in a flat cup shape (flush with the groove opening) in the cup bowl, and obtaining the LED integral device before curing.
Step four, curing
And (3) placing the whole LED device before curing into a drying oven, and baking for 3.5 hours at 110 ℃ to obtain the patch type LED device, thereby realizing the application of the non-rare earth blue fluorescent powder in the white light LED.
The prepared non-rare earth blue fluorescent powder white light LED is detected by the same test method as the example 1. The LED has characteristic peaks at 405nm (LED chip wave band, ultraviolet light region), 475nm and 522nm (blue light region), and the emitted visible light is mainly in the blue light region.
Software analysis shows that the light emitted by the LED is in a blue light region, the CIE chromaticity coordinate is (0.175, 0.268), the color rendering index is 42.2, the color temperature is 8860K, and the lumen efficiency is 35.0 lm/W.
Example 10
The experimental procedure of example 8 was repeated except that in step (2), step one of the preparation of the LED device, CuInS was added2Red phosphor (prepared in CN 201110259596.3), and the weight ratio of the red phosphor to the blue phosphor is 1: 100.
The obtained blue phosphor and red CuInS were subjected to the same test method as in example 12And detecting the white light LED of the nanocrystalline fluorescent powder to obtain a non-rare earth blue fluorescent powder white light LED spectrogram shown in figure 14. FIG. 14 shows that the LED has a wavelength of 405nm (wavelength of LED chip, ultraviolet region), 476nm, 524nm (Al (OH))3Blue phosphor, blue region), 622nm (CuInS)2Nanocrystalline phosphor, red region) has a characteristic peak indicating that the emitted visible light consists primarily of blue-green light and red light.
Software analysis obtains the CIE chromaticity coordinates of (0.337, 0.352), the color rendering index of 94.3, the color temperature of 5301K, the lumen efficiency of 25.1lm/W, and proves that the light emitted by the LED is in a positive white light region.
Example 11
The experimental procedure of example 2 was repeated except that in step (2) one of the preparation of the LED device, CuInS was added2The red phosphor (refer to the Cu-In-S/ZnS nanocrystalline phosphor prepared In CN201110259596.3 example 1) and the weight ratio of the red phosphor to the blue phosphor is 1: 80.
The obtained blue phosphor and red CuInS were subjected to the same test method as in example 12And detecting the white light LED of the nanocrystalline fluorescent powder. Obtaining a non-rare earth blue fluorescent powder white light LED spectrogram shown in figure 15; the LED can be seen in 405nm (LED chip wave band, ultraviolet light region), 462nm, 518nm (Al (OH)3Blue phosphor, blue region), 619nm (CuInS)2Nanocrystalline phosphor, red region) has a characteristic peak indicating that the emitted visible light consists primarily of blue-green light and red light.
Software analysis obtains the CIE chromaticity coordinates (0.313 and 0.291), the color rendering index (91.2), the color temperature (6930K) and the lumen efficiency (20.7 lm/W), and the light emitted by the LED is proved to be in a positive white light region.
By adopting the method provided by the invention, the blue fluorescent powder prepared in the above exemplary embodiment contains Al in chemical formula2O3·nH2Aluminum hydroxide of O and carbon-doped components, and does not contain non-rare earth metal elements. The method provided by the inventionThe method is simple, convenient and effective, simplifies the procedure, saves the cost, and the prepared blue fluorescent powder has higher fluorescence quantum yield and wide luminescence spectrum.
The blue fluorescent powder prepared according to the invention and the packaging medium are taken as luminescent materials, and the prepared LED device has the advantages of higher color rendering index, adjustable color temperature, high luminous brightness, good thermal stability, long service life and low energy consumption.
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Further, it should be understood that the various aspects recited herein, portions of different embodiments, and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.
Claims (3)
1. A preparation method of an LED device comprises the following steps:
(1) preparing non-rare earth blue fluorescent powder:
taking a proper amount of organic aluminum salt precursor aluminum acetylacetonate, and fully grinding; weighing 1.62g of ground acetylacetone aluminum powder;
putting the weighed acetylacetone aluminum powder into a quartz boat, putting the quartz boat into a quartz tube, and putting the quartz tube into a heating area of a tube furnace; connecting an exhaust system, checking the air tightness of the system after sealing is finished, and setting a heating condition after confirming that the air tightness is good;
and introducing nitrogen into the quartz tube for 40min for exhausting, after exhausting is finished, continuously introducing nitrogen at the rate of 200sccm, and starting a heating program of a tube furnace system: the initial temperature is room temperature, and the heating rate is 33 ℃/min; after the temperature is raised to 330 ℃, the system is insulated for 24 hours at 330 ℃; when the sample is cooled to room temperature along with the furnace, obtaining non-rare earth blue fluorescent powderAluminum hydroxide Al contained in rare earth blue fluorescent powder2O3·nH2N of O is 0.2;
(2) preparing an LED device:
step one, preparation:
adding the prepared non-rare earth blue fluorescent powder into a packaging medium to obtain a mixture, and stirring the mixture by using a glass rod; stirring at the stirring speed of 2-3 circles/second clockwise in one direction to avoid generating excessive bubbles, and stirring for 15 min;
in the mixture, the mass percentage of the non-rare earth blue fluorescent powder is 30 wt%; the packaging medium is silica gel KER2500A and silica gel KER2500B, and the mass of the silica gel KER2500A is as follows: the mass of the silica gel KER2500B is 1: 2;
step two, defoaming:
placing the stirred mixture in a vacuum drying oven, and defoaming at 30 ℃ and under the vacuum degree of 0.09MPa for 60 min; after defoaming, taking out the mixture, and slowly stirring the mixture for 5 minutes in one direction at the speed of 2-3 seconds per circle by using a glass rod, wherein bubbles are prevented from being generated during stirring;
step three, dispensing:
transferring the mixture treated in the step two into a 5mL syringe, and avoiding generating bubbles when pouring the mixture; installing an air inlet pipe on the needle cylinder, and applying pressure to the air inlet pipe to enable the mixture in the needle cylinder to slowly drip into the groove in the center of the patch type LED cup bowl until the mixture is in a flat cup state flush with the groove opening in the cup bowl, so that an LED integral device before curing is obtained;
step four, curing
And (3) placing the LED integral device before curing into a drying oven, and baking for 3 hours at 120 ℃ to obtain the patch type LED device.
2. A preparation method of an LED device comprises the following steps:
(1) preparing non-rare earth blue fluorescent powder:
0.8105g of basic aluminum acetate and 20mL of octadecene are added into a 100mL three-neck flask and mixed to obtain a mixed solution; heating the mixed solution to 100 ℃ in vacuum and stirring for 30 min; then introducing nitrogen and keeping the temperature for 30min, then heating the solution to 300 ℃, changing the solution from white to light yellow, and reacting the solution at constant temperature for 5 h;
adding the solution prepared in the step into a 100mL centrifuge tube to a position half as high as the tube, and carrying out centrifugal separation to obtain a bottom substance and a supernatant; after the supernatant liquid is poured out, washing twice with 3mL of toluene and 60mL of acetone, centrifugally separating, and pouring out the supernatant liquid to obtain the diaspore ore blue-light material;
vacuum drying the obtained blue-light material of the gibbsite at 50 ℃ for 1h to obtain a powdery product, wherein the powdery product is gibbsite non-rare earth blue fluorescent powder, and aluminum hydroxide Al contained in the non-rare earth blue fluorescent powder2O3·nH2N of O is 1;
(2) preparing an LED device:
step one, preparation:
adding the prepared non-rare earth blue fluorescent powder into a packaging medium to obtain a mixture, and stirring the mixture by using a glass rod; stirring at the stirring speed of 2-3 circles/second clockwise in one direction to avoid generating excessive bubbles, and stirring for 15 min;
in the mixture, the mass percentage of the non-rare earth blue fluorescent powder is 30 wt%; the packaging medium is silica gel KER2500A and silica gel KER2500B, and the mass of the silica gel KER2500A is as follows: the mass of the silica gel KER2500B is 1: 2;
step two, defoaming:
placing the stirred mixture in a vacuum drying oven, and defoaming at 30 ℃ and under the vacuum degree of 0.09MPa for 60 min; after defoaming, taking out the mixture, and slowly stirring the mixture for 5 minutes in one direction at the speed of 2-3 seconds per circle by using a glass rod, wherein bubbles are prevented from being generated during stirring;
step three, dispensing:
transferring the mixture treated in the step two into a 5mL syringe, and avoiding generating bubbles when pouring the mixture; installing an air inlet pipe on the needle cylinder, and applying pressure to the air inlet pipe to enable the mixture in the needle cylinder to slowly drip into the groove in the center of the patch type LED cup bowl until the mixture is in a flat cup state flush with the groove opening in the cup bowl, so that an LED integral device before curing is obtained;
step four, curing:
and (3) placing the LED integral device before curing into a drying oven, and baking for 3 hours at 120 ℃ to obtain the patch type LED device.
3. A preparation method of an LED device comprises the following steps:
(1) preparing non-rare earth blue fluorescent powder:
0.1351g of aluminum glycinate and 20mL of oleylamine are added into a 100mL three-neck flask and mixed to obtain a mixed solution; heating the mixed solution to 90 ℃ in vacuum and stirring for 40 min; then introducing nitrogen and keeping the temperature for 30min, then heating the solution to 340 ℃, changing the solution from white to light yellow, and reacting the solution at constant temperature for 6 h;
adding the solution prepared in the step into a 100mL centrifuge tube to a position half as high as the tube, and carrying out centrifugal separation to obtain a bottom substance and a supernatant; after the supernatant liquid is poured out, washing twice with 2mL of toluene and 50mL of acetone, centrifugally separating, and pouring out the supernatant liquid to obtain the diaspore ore blue-light material;
vacuum drying the obtained blue-light material of the gibbsite at 60 ℃ for 2h to obtain a powdery product, wherein the powdery product is gibbsite non-rare earth blue fluorescent powder, and aluminum hydroxide Al contained in the non-rare earth blue fluorescent powder2O3·nH2N of O is 3;
(2) preparing an LED device:
step one, preparation:
adding the prepared non-rare earth blue fluorescent powder into a packaging medium to obtain a mixture, and stirring the mixture by using a glass rod; stirring at the stirring speed of 2-3 circles/second clockwise in one direction to avoid generating excessive bubbles, and stirring for 15 min;
in the mixture, the mass percentage of the non-rare earth blue fluorescent powder is 40 wt%; the packaging medium is bisphenol A type epoxy resin EP-400A and epoxy resin curing agent EP-400B, and the mass of the bisphenol A type epoxy resin EP-400A is as follows: the mass of the epoxy resin curing agent EP-400B is 1: 1;
step two, defoaming:
placing the stirred mixture in a vacuum drying oven, defoaming and standing for 60min at 35 ℃ under the vacuum degree of 0.06 MPa; after defoaming, taking out the mixture, and slowly stirring the mixture for 5 minutes in one direction at the speed of 2-3 seconds per circle by using a glass rod, wherein bubbles are prevented from being generated during stirring;
step three, dispensing:
transferring the mixture treated in the step two into a 5mL syringe, and avoiding generating bubbles when pouring the mixture;
installing an air inlet pipe on the needle cylinder, and applying pressure to the air inlet pipe to enable the mixture in the needle cylinder to slowly drip into the groove in the center of the patch type LED cup bowl until the mixture is in a flat cup state flush with the groove opening in the cup bowl, so that an LED integral device before curing is obtained;
step four, curing:
and (3) placing the LED integral device before curing into a drying oven, and baking for 3.5 hours at 110 ℃ to obtain the patch type LED device.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102694110A (en) * | 2012-06-08 | 2012-09-26 | 北京理工大学 | Non-rare earth nanocrystalline fluorescent powder-containing packaging material, preparation method and application |
| CN106566537A (en) * | 2016-11-10 | 2017-04-19 | 北京理工大学 | Blue fluorescent material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102694110A (en) * | 2012-06-08 | 2012-09-26 | 北京理工大学 | Non-rare earth nanocrystalline fluorescent powder-containing packaging material, preparation method and application |
| CN106566537A (en) * | 2016-11-10 | 2017-04-19 | 北京理工大学 | Blue fluorescent material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Bingkun Chen et al..Mesoporous Aluminum Hydroxide Synthesized by a Single-Source Precursor-Decomposition Approach as a High-Quantum-Yield Blue Phosphor for UV-Pumped White-Light-Emitting Diodes.《Adv. Mater.》.2016,第29卷第1604284页. * |
| Mesoporous Aluminum Hydroxide Synthesized by a Single-Source Precursor-Decomposition Approach as a High-Quantum-Yield Blue Phosphor for UV-Pumped White-Light-Emitting Diodes;Bingkun Chen et al.;《Adv. Mater.》;20161109;第29卷;第1604284页 * |
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