CN104592988B - The preparation method of a kind of fluorescent material for LED component - Google Patents
The preparation method of a kind of fluorescent material for LED component Download PDFInfo
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- CN104592988B CN104592988B CN201510047362.0A CN201510047362A CN104592988B CN 104592988 B CN104592988 B CN 104592988B CN 201510047362 A CN201510047362 A CN 201510047362A CN 104592988 B CN104592988 B CN 104592988B
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Abstract
The present invention is the preparation method of a kind of fluorescent material for LED component, and the method comprises the steps: that water and composite dye are mixed by (1), then stirs evenly, obtains mixing solutions; The described composite dye in step (1) is the mixture of rhodamine B and organic fluorescent dye; (2) mixing solutions obtained in step (1) adds porous boron nitride, then mixing solutions is stirred 2-24h; (3) filter step (2) obtains mixing solutions, by gained solid vacuum drying, the fluorescent material for LED component can be obtained. The product that the present invention obtains is take porous boron nitride as the blue-light excited fluorescent material of supporter, and the raw material of employing is porous boron nitride and organic fluorescent dye, have that raw material is easy to get, environmental protection, advantage that cost is low. This fluorescent material has excellent luminescent properties, high thermostability and light durability, and the preparation method of fluorescent material is simple, environmental friendliness, reliable, and applicable large-scale production.
Description
Technical field
The present invention relates to high efficiency embedded photoluminescent material, is specially the preparation method of a kind of fluorescent material for white semiconductor photodiode (LED) device.
Background technology
Between the more than ten years in past, solid luminescent material because it is energy-conservation, long lifetime, environmental friendliness, fast response and obtain investigation and application widely without premium propertiess such as mercury pollution. As third generation light source, white light LEDs obtains a wide range of applications in fields such as outdoor lighting, backlight, automobile headlamp and compact illumination systems. At present, white light LED part adopts up-conversion luminescence mode to make usually, and namely the light-converting material of coated light emission blue-light excited, orange on the InGaN chip launching blue light, obtains white light source after light mixes. Currently, most widely used smooth conversion fluorescence powder material is Y3Al5O12:Ce3+,Gd3+(YAG:Ce3+,Gd3+). This kind of fluorescent material is used a large amount of rare earth elements, has not only increased cost, and a large amount of rare earth resources need to have been consumed.
In addition, the also Shortcomings in the performances such as colour rendering index of the LED for preparing of inorganic fluorescent powder is adopted. The people such as Sakuma are with YAG:Ce3+For the display index of the white light LED part of conversion phosphor making is only 60 (K.Sakuma, K.Omichi, N.Kimura, M.Ohashi, D, Tanaka, N.Hirosaki, Y.Yamamoto, R.J.Xie, T.Suehiro, Opt.Let.2004,29,2001). The people such as Xie are with Sr2Si5N8:Eu2+The colour rendering index of the white light LEDs prepared for fluorescent material is 82 (R.J.Xie, N.Hirosaki, N.Kimura, K.Sakuma, M.Mitomo, Appl.Phys.Lett.2007,90,191101). The people such as Jang are luminescence chip taking CdSe quantum dot, with Sr3SiO5:Ce3+,Li+The colour rendering index of the white light LEDs prepared for fluorescent material is 90.1 (H.S.Jang, H.Yang, S.W.Kim, J.Y.Han, S.G.Lee, D.Y.Jeon, Adv.Mater.2008,20,2696). Sr-��-SiAlON:Eu prepared by the people such as Xie2+The colour rendering index of the white light LEDs prepared for fluorescent material is about 90 (R.J.Xie, N.Hirosaki, K.Sakuma, N.Kimura, J.Phys.D:Appl.Phys.2008,41,144013). The people such as Kimura are with BaSi2O2N2:Eu2+The colour rendering index of the white light LEDs prepared for fluorescent material is 91.5 (N.Kimura, K.Sakuma, S.Hirafune, K.Asano, Appl.Phys.Lett.2007,90,051109). At present, the low blue light excitability of inorganic fluorescent powder, low luminous efficiency, low thermal stability and unsatisfactory light color developing cause white light LEDs can't meet the requirement of illumination completely.
Summary of the invention
Technical problem to be solved by this invention is: provide the fluorescent material for LED component that a kind of excellent Lan Guangke excites, high luminous efficiency, strong thermostability, colour temperature are soft, color developing is good. This kind of fluorescent material adopts two step preparations: the first step, is dissolved in aqueous by compound organic fluorescent dye; 2nd step, makes compound organic fluorescent dye get involved in porous boron nitride duct by adsorption, obtains the fluorescent material for LED component. This kind of novel fluorescent material for LED component does not need employing rare-earth ion activated, can save a large amount of rare earth resources, and synthesis simple (not needing pyroprocessing), is easy to scale operation, thus reduces the manufacturing cost of fluorescent material. Porous boron nitride has big surface-area, high pore volume, unreactiveness, electrical insulating property, high heat conduction, abundant hydroxyl and organic surface pipe and can roll into a ball, and at the high photopermeability of ultraviolet to visible region, be conducive to improving luminous efficiency and the thermostability of fluorescence dye. Therefore, porous boron nitride is the carrier of a desirable organic fluorescent dye. Meanwhile, this kind have novel texture for LED component fluorescent material wavelength be the blue-light excited lower efficiency of light absorption of 466 nanometers and external quantum efficiency respectively up to 92% and 75%, far away higher than traditional YAG:Ce3+The efficiency of light absorption (70%) of the fluorescent material of series and external quantum efficiency (40%). What is more important, under blue-light excited, its can emission wavelength ranges from the visible ray of 500 to 710 nanometers. Therefore gained composite fluorescence powder overcomes traditional rare earth, and to mix light-emitting phosphor efficiency low, thermostability is low and the defect of display property difference, is with a wide range of applications at lighting field.
The technical scheme of the present invention is:
For a preparation method for the fluorescent material of LED component, comprise the steps:
(1) water and composite dye are mixed, then stir, obtain mixing solutions; Wherein, material proportion is mass ratio is water: composite dye=1:10-7��10-5; The described composite dye in step (1) is the mixture of rhodamine B and organic fluorescent dye, and its proportioning is that quality is than rhodamine B and organic fluorescent dye=0.5��2:1;
(2) mixing solutions obtained in step (1) adds porous boron nitride, then mixing solutions is stirred 2-24h; Wherein, quality proportioning is mixing solutions: porous boron nitride=1:10-5��10-1;
(3) filter step (2) obtains mixing solutions, by gained solid vacuum drying, the organic fluorescence materials that porous boron nitride supports can be obtained, namely for the fluorescent material of LED component
Described organic fluorescent dye is one or more in the serial fluorescence dye (Reactiveandconjugated line fluorescent dyestuff) of activity and conjugation, fluorochemical line fluorescent dyestuff (AlexaFluor line fluorescent dyestuff), Cy line fluorescent dyestuff, cell function line fluorescent dyestuff and fluorescin line fluorescent dyestuff.
Active and conjugation series fluorescence dye preferably fluorescein isothiocyanate or fluorescent yellow (Luciferyellow) in organic fluorescent dye in described step (1); Fluorochemical line fluorescent dyestuff is preferably AlexaFluor532; Cy line fluorescent dyestuff is preferably Cy3; Cell function line fluorescent dyestuff is preferably dichlorofluorescein (DCFH); Fluorescin line fluorescent dyestuff is preferably mKeima-Red.
The invention has the beneficial effects as follows:
1. the product that the inventive method obtains is take porous boron nitride as the blue-light excited fluorescent material of supporter, and it does not need doped with rare-earth elements, not only reduces cost, and decreases environmental pollution. As shown in Figure 1, when being 466 nanometers blue-light excited with wavelength, the wavelength region of the transmitting light of this fluorescent material is from 500 to 710 nanometers. And now widely used YAG:Ce3+Not only light conversion efficiency is low for series phosphor powder, and emission wavelength ranges is at 500 to 600 nanometers. Fig. 2 shows the fluorescent material photoluminescence quantum efficiencies variation with temperature rule that the present invention obtains, and when working temperature reaches 200 DEG C, its photoluminescence quantum efficiencies still can reach 60%, far away higher than YAG:Ce3+The light conversion efficiency (20%) of series phosphor powder under 200 DEG C of working temperatures, illustrates that this kind of fluorescent material has excellent thermostability. Fig. 3 demonstrates fluorescent material that the present invention obtains after the blue light (blue-light LED chip is the blue light that 20mA sends at working current) that wavelength is 466 nanometers irradiates 7 months, its photoluminescence quantum efficiencies remains unchanged substantially, has absolutely proved that it has excellent light durability. Gained fluorescent material of the present invention is coated in gained luminescent spectrum figure on blue-light LED chip that working current is 20mA by Fig. 4, the chromaticity coordinates of the white light LED part of preparation is (0.33,0.34), close to sunlight chromaticity coordinates, fluorescent material colour temperature is soft, color developing good to prove this kind.
2. the raw material that the present invention adopts is porous boron nitride, and organic fluorescent dye, raw material is easy to get, cost is low.
3. present method has excellent luminescent properties for the preparation of the fluorescent material of LED component, high thermostability and light durability, and method is simple, environmental friendliness, reliable, and applicable mass-producing preparation. Gained fluorescent material is with a wide range of applications at lighting field.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further described with concrete enforcement.
Fig. 1 is the fluorescent material of preparation in the example 1 transmitting collection of illustrative plates under wavelength is 466 nanometers blue-light excited;
The fluorescent material photoluminescence quantum efficiencies for LED component that Fig. 2 is preparation in example 1 varies with temperature figure;
Fig. 3 is photoluminescence quantum efficiencies variation diagram in time under the blue light illumination of 466 nanometers launched at the blue-light LED chip that working current is 20mA of the fluorescent material of preparation in example 1;
Fig. 4 is the luminescent spectrum figure that the fluorescent material of preparation in example 1 is coated in obtained device on blue-light LED chip that working current is 20mA.
Embodiment
Porous boron nitride of the present invention is well known materials, can obtain according to the method preparation of patent ZL201210475879.6 report.
Embodiment 1
(1) remove ionized water 1L, and add fluorescein isothiocyanate and rhodamine B mixture 10 wherein-3G, the mass ratio of two kinds of dyestuff fluorescein isothiocyanates and rhodamine B is 2:1, is then stirred by mixture 1 hour, obtains uniform mixing solutions;
(2) it is 1:10 by the mixing solutions obtained in step (1) and porous boron nitride taking mass ratio-4Mixing, namely adds the porous boron nitride of 0.1g, then vigorous stirring 3h, to ensure that organic fluorescent dye is adsorbed on porous boron nitride in mixing solutions;
(3) filtering obtaining mixing solutions in step (2), 50 DEG C of vacuum drying ovens put into by gained solid, insulation 7h; Obtain the organic fluorescence materials that porous boron nitride supports, namely for the fluorescent material of LED component.
As shown in Figure 1, when being 466 nanometers when exciting with wavelength, blue light can be converted into the visible ray of long wavelength by this fluorescent material efficiently, and wavelength region, from 500 to 710 nanometers, meets the Requirement of Spectrum making white light LED part. Fig. 2 shows the fluorescent material photoluminescence quantum efficiencies that the present invention obtains and varies with temperature rule, and when working temperature reaches 200 DEG C, the quantum yield of this fluorescent material still can arrive 60%, illustrates that it has very excellent thermostability. It is the blue light illumination of 466 nanometers after 7 months that Fig. 3 demonstrates fluorescent material that the present invention obtains through wavelength, and its photoluminescence quantum efficiencies remains unchanged substantially, has absolutely proved that it has excellent light durability. Fig. 4 is the luminescent spectrum figure that gained fluorescent material of the present invention covers obtained device on blue-light LED chip that working current is 20mA, the chromaticity coordinates of the white light LED part of preparation is (0.33,0.34), close to sunlight chromaticity coordinates, fluorescent material colour temperature is soft, color developing good to prove this kind.
Embodiment 2
Changing the mass ratio of fluorescein isothiocyanate and rhodamine B in step (1) composite dye in embodiment 1 into 0.5:1, other operations is all identical with embodiment 1, obtains product with embodiment 1
Embodiment 3, example 4, example 5
Change the consumption of fluorescein isothiocyanate and rhodamine B mixture in step (1) in embodiment 1 into 10 respectively-4Gram, 2 �� 10-3Gram, 5 �� 10-2Gram, the mass ratio of fluorescein isothiocyanate and rhodamine B is still 2:1, and other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 6, example 7, example 8, example 9, example 10
Step (1) organic fluorescent dye fluorescein isothiocyanate in embodiment 1 is changed into respectively fluorescent yellow (active and conjugation series fluorescence dye), AlexaFluor532 (fluorochemical line fluorescent dyestuff), Cy3 (Cy line fluorescent dyestuff), dichlorofluorescein (cell function line fluorescent dyestuff), mKeima-Red (fluorescin line fluorescent dyestuff), other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 11, example 12, example 13
The churning time of step (1) in embodiment 1 is changed into 0.5 hour respectively, 2 hours, 3 hours, other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 14, example 15, example 16
Change the consumption of step (2) porous boron nitride in embodiment 1 into 10 respectively-2Gram, 2 �� 10-1Gram, 102Gram, other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 17, example 18, example 19
The churning time of step (2) in embodiment 1 is changed into 0.5 hour respectively, 2 hours, 6 hours, other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 20, example 21, example 22
Changing the bake out temperature of step (3) in embodiment 1 into 25 DEG C, 40 DEG C, 75 DEG C, other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 23, example 24, example 25
The soaking time of step (3) in embodiment 1 is changed into 3 hours respectively, 6 hours, 10 hours, other operations is all identical with embodiment 1, obtains product with embodiment 1.
Unaccomplished matter of the present invention is known technology.
Claims (1)
1., for the preparation method of fluorescent material for LED component, it is characterized by the method and comprise the steps:
(1) water and composite dye are mixed, then stir, obtain mixing solutions; Wherein, material proportion is mass ratio is water: composite dye=1:10-7~10-5; The described composite dye in step (1) is the mixture of rhodamine B and organic fluorescent dye, its proportioning be quality than organic fluorescent dye: rhodamine B=0.5��2:1;
(2) mixing solutions obtained in step (1) adds porous boron nitride, then mixing solutions is stirred 2-24h; Wherein, quality proportioning is mixing solutions: porous boron nitride=1:10-5~10-1;
(3) filter step (2) obtains mixing solutions, by gained solid vacuum drying, the organic fluorescence materials that porous boron nitride supports can be obtained, namely for the fluorescent material of LED component;
In described step (1), organic fluorescent dye is one or more in fluorescein isothiocyanate, fluorescent yellow, AlexaFluor532, Cy3, dichlorofluorescein and mKeima-Red.
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