CN105694849A - Rare-earth-free fluorescent powder for white light LED and preparation method of rare-earth-free fluorescent powder - Google Patents
Rare-earth-free fluorescent powder for white light LED and preparation method of rare-earth-free fluorescent powder Download PDFInfo
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Abstract
The invention discloses rare-earth-free fluorescent powder for a white light LED and a preparation method of the rare-earth-free fluorescent powder. The rare-earth-free fluorescent powder is prepared from, by mass, 98-99.98% of metal-organic frame material, 0.01-1% of yellow light or green light emission dyestuff and 0.01-1% of red light emission dyestuff. The preparation method includes the following steps that an aromatic carboxylic acid organic ligand and metal salt are subjected to solvothermal/hydrothermal reaction synthesis to obtain the metal-organic frame material; the metal-organic frame material is soaked in a dyestuff solution, and dyestuff molecules/ions enter the metal-organic frame material. The process is simple, conditions are mild, the yield is high, the prepared fluorescent powder is free of a rare earth element, internal quantum efficiency is higher than 75%, and thermo-chemical stability is high. The rare-earth-free fluorescent powder is combined with a blue light LED chip, the color rending index of the prepared white light LED is higher than 80, the color temperature can be continuously adjusted between 2,500 K and 7,000 K, brightness is high, and under injection at the current density of 20 A/cm<2>, the lighting efficiency is higher than 140 lm/W, and luminous decay is low.
Description
Technical field
The present invention relates to a kind of without fluorescent RE powder and preparation method thereof, especially white light LEDs without fluorescent RE powder and preparation method thereof。
Background technology
White light LEDs due to its luminous efficiency height, life-span length, device is little, respond the features such as fast, quickly grown since the nearly more than ten years, it is believed that be the solid state light emitter that can replace electric filament lamp and fluorescent lamp。White light LEDs has multiple implementation, and the blue-light LED chip that is achieved in that of most main flow excites yellow fluorescent powder to be collectively forming white light at present, and this scheme has that design is simple, luminous efficiency advantages of higher。What current yellow fluorescent powder mainly adopted is yttrium-aluminium-garnet (YAG:Ce) fluorescent material mixing cerium, this material 450-460nm blue-light excited under obtain sending the wide range of about 540nm and launch, obtain white light after the blue light combination sent with chip。But YAG:Ce fluorescent material is owing to lacking the transmitting of red light portion, and its white light LEDs prepared has colour temperature height, the shortcomings such as color rendering index is low。At present, in order to obtain the white light LEDs of high color rendering index (CRI), through frequently with scheme be in bloom, add a certain amount of Hydrargyri Oxydum Rubrum, but the re-absorption between different fluorescent material makes luminous efficiency decline to a great extent, and owing to the aging characteristics between different fluorescent material and temperature characterisitic are inconsistent, white light LEDs in use chromatic characteristic can change。
Additionally, the fluorescent material adopted at present mostly contains the rare earth elements such as Ce, Y, Eu。Rare earth element abundance in the earth's crust is only small, expensive, is a kind of extremely rare resource, in today that LED lamp demand sharply increases, finds the fluorescent material without rare earth element and replaces traditional fluorescent material containing rare earth element to be particularly important。Meanwhile, YAG:Ce fluorescent material is in process of production it is generally required to the high temperature of more than 1000 DEG C is sintered, it is necessary to big energy, and equipment proposes higher requirement。In sum, simple without rare earth element, production technology and there is the single-matrix fluorescent material of superior luminescence performance need badly and developed。
Summary of the invention
It is an object of the present invention to provide a kind of white light LEDs without fluorescent RE powder and preparation method thereof, this fluorescent material is without rare earth element, and production technology is simple, and after preparing into white light LEDs, brightness is high, and color rendering index is high, and adjustable color, light decay is little。
The white light LEDs of the present invention without fluorescent RE powder, its composition and mass percentage content be: metal-organic framework materials 98 ~ 99.98%, gold-tinted or green light emitting dye 0.01 ~ 1%, red light emitting dyes 0.01 ~ 1%。
The preparation method without fluorescent RE powder of the white light LEDs of the present invention, comprises the following steps:
(1) preparation of metal-organic framework materials:
The aromatic carboxylic acids part of 0.1 ~ 1mmol and 0.2 ~ 3mmol slaine are dissolved in the mixed solvent of 10 ~ 100mL organic solvent and 1 ~ 50mL water, or it is dissolved in 10 ~ 100mL aqueous solution, it is added dropwise over putting in airtight reactor after the nitric acid that 0 ~ 0.5mL mass fraction is 65% stirs, 40 ~ 150oC isothermal reaction 5 ~ 72h, obtains metal-organic framework materials；
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
The red light emitting dyes of the gold-tinted or green light emitting dye and 0.1 ~ 5mg that take 0.1 ~ 5mg is dissolved in the water of 10 ~ 100mL or is dissolved in 10 ~ 100mL organic solvent, inwardly add metal-organic framework materials immersion 5 ~ 48h prepared by 0.1 ~ 1g step (1) again, clean with alcohol solvent after filtration, dry, obtain white light LEDs without fluorescent RE powder。
Heretofore described aromatic carboxylic acids part can be trimesic acid, Pyromellitic Acid, 5-amino-isophthalic acid, 3,3', 5,5'-bibenzene tetracarboxylic, 1,3,5-tri-(4-carboxyl benzene) benzene, 3,4', 5-biphenyl tricarboxylic acids, oreinol diacid, 4,4'-oxydibenzoic acid or 4,4', 4 ' '-triazine-1,3,5-tri-para-amino benzoic acid。
Heretofore described slaine can be zinc salt, indium salts, aluminium salt, zirconates or chromic salts。Zinc salt can be zinc nitrate, zinc chloride or zinc acetate；Indium salts can be indium nitrate, indium chloride or indium acetate；Aluminium salt can be aluminum chloride or aluminum nitrate；Zirconates can be zirconium chloride or basic zirconium chloride；Chromic salts can be chromic nitrate, Chlorizate chromium or chromium acetate。
In the present invention, the organic solvent described in step (1) and step (2) can be N, N-dimethylformamide, N, the mixing of any one or arbitrarily several any ratio in N-dimethyl acetylamide, N, N-diethylformamide, methanol, ethanol, dioxane, oxolane and acetone。
Heretofore described gold-tinted or green light emitting dye can be that in coumarin 6, coumarin 460, coumarin 314, acriflavinium chloride, fluorescein, Fluorescein isothiocyanate and solvent yellow, any one or arbitrarily several arbitrarily ratios mix。
Heretofore described red light emitting dyes is the mixing of any one or the arbitrarily several any ratio in pyronine B, pyronin Y, rhodamine 6G, rhodamine B, resorufin, oxazines 1 and Nile red。
The beneficial effects of the present invention is:
1, the fluorescent material of the present invention is composited by metal-organic framework materials and organic dyestuff, is different from the inorganic fluorescent powders such as traditional YAG:Ce, without rare and expensive rare earth element, the protection of resource is significant。
2, the fluorescent material of the present invention provides the transmitting of HONGGUANG wave spectrum section by red light emitting dyes, solves commercial YAG:Ce fluorescent material and lacks the shortcoming that red light portion is launched, and therefore color rendering index is greatly improved。
3, by regulating the kind of fluorescent dye, concentration and ratio in dye solution, can change easily finally give without the kind of dyestuff, concentration and ratio in fluorescent RE powder, make colour temperature continuously adjustabe between 2500-7000K of the white light LEDs prepared by this fluorescent material, be applicable to different application occasion。
4, the light efficiency without fluorescent RE powder of the present invention is high, electric current density 20A/cm2Under injection, light efficiency is more than 140lm/W。
5, the light decay without fluorescent RE powder of the present invention is little, good reliability, 55 DEG C, electric current density be 120A/cm2Aging condition under, after 168h, light decay is less than 2%。
6, the present invention need not use high temperature in preparation process without fluorescent RE powder, production technology is simple, low for equipment requirements。
Accompanying drawing explanation
Fig. 1 be white light LEDs without fluorescent RE powder emission spectrum under 460nm is blue-light excited。
Detailed description of the invention
Embodiment 1:
(1) preparation of metal-organic framework materials:
Weigh the 1 of 1mmol, 3,5-tri-(4-carboxyl benzene) benzene and 3mmol indium chloride are dissolved in the N of 60mL, in the mixed solvent of dinethylformamide, 40mL dioxane and 50mL water, being subsequently adding after the nitric acid that 0.5mL mass fraction is 65% stirs puts in airtight reactor, and heating is to 130oC isothermal reaction 24h, obtains metal-organic framework materials；
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
Take 5mg green light emitting dye coumarin 6 and 0.5mg red light emitting dyes pyronine B is dissolved in the N of 100mL, in N-dimethylformamide solvent, inwardly add metal-organic framework materials immersion 24h prepared by 1g step (1) again, with ethanol purge after filtration, dry, obtain white light LEDs without fluorescent RE powder。
Containing metal-organic framework materials 99.74wt% in this fluorescent material, coumarin 6 content 0.12wt%, pyronine B content 0.14wt%, its emission spectrum under 460nm is blue-light excited is shown in Fig. 1, and its internal quantum efficiency is 78%。After using this fluorescent material to form white light LEDs with blue-light LED chip combination, color rendering index is 82, and colour temperature is 3038K, and light efficiency is 172lm/W(electric current density 20A/cm2)。55 DEG C, electric current density be 120A/cm2Aging condition under, after 168h, light decay is only 0.29%。
Embodiment 2:
(1) preparation of metal-organic framework materials:
Weigh the 1 of 1mmol, 3,5-tri-(4-carboxyl benzene) benzene and 3mmol indium chloride are dissolved in the N of 60mL, in the mixed solvent of dinethylformamide, 40mL dioxane and 50mL water, being subsequently adding after the nitric acid that 0.5mL mass fraction is 65% stirs puts in airtight reactor, and heating is to 130oC isothermal reaction 24h, obtains metal-organic framework materials；
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
Take 5mg green light emitting dye coumarin 6 and 0.3mg red light emitting dyes pyronine B is dissolved in the N of 100mL, in N-dimethylformamide solvent, inwardly add metal-organic framework materials immersion 24h prepared by 1g step (1) again, with ethanol purge after filtration, dry, obtain white light LEDs without fluorescent RE powder。
Containing metal-organic framework materials 99.77wt% in this fluorescent material, coumarin 6 content 0.12wt%, pyronine B content 0.11wt%, its internal quantum efficiency is 80%。After using this fluorescent material to form white light LEDs with blue-light LED chip combination, color rendering index is 80, and colour temperature is 6310K, and light efficiency is 177lm/W(electric current density 20A/cm2)。55 DEG C, electric current density be 120A/cm2Aging condition under, after 168h, light decay is only 0.31%。
Embodiment 3:
(1) preparation of metal-organic framework materials:
The 5-amino-isophthalic acid and the 3mmol aluminum chloride that weigh 1mmol are dissolved in the mixed solvent of 60mL ethanol and 10mL water, put in airtight reactor, and heating is to 40oC isothermal reaction 5h, obtains metal-organic framework materials；
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
Take 5mg yellow light emitting dyes fluorescein and 0.5mg red light emitting dyes rhodamine B is dissolved in the water of 100mL, inwardly add metal-organic framework materials immersion 24h prepared by 0.8g step (1) again, with ethanol purge after filtration, dry, obtain white light LEDs without fluorescent RE powder。
Containing metal-organic framework materials 99.45wt% in this fluorescent material, fluorescein content 0.31wt%, rhodamine B content 0.24wt%, its internal quantum efficiency is 81%。After using this fluorescent material to form white light LEDs with blue-light LED chip combination, color rendering index is 80, and colour temperature is 2809K, and light efficiency is 161lm/W(electric current density 20A/cm2)。55 DEG C, electric current density be 120A/cm2Aging condition under, after 168h, light decay is only 0.36%。
Embodiment 4:
(1) preparation of metal-organic framework materials:
Weigh the 3,3' of 1mmol, 5,5'-bibenzene tetracarboxylic and 3mmol chromic nitrate are dissolved in the N of 100mL, in the mixed solvent of N-diethylformamide and 50mL water, being subsequently adding after the nitric acid that 0.5mL mass fraction is 65% stirs and put in airtight reactor, heating is to 120oC isothermal reaction 48h, obtains metal-organic framework materials；
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
Take 0.1mg green light emitting dye coumarin 460,0.1mg yellow light emitting dyes solvent yellow and 0.1mg red light emitting dyes resorufin and be dissolved in the acetone solvent of 10mL, inwardly add metal-organic framework materials immersion 48h prepared by 0.1g step (1) again, with ethanol purge after filtration, dry, obtain white light LEDs without fluorescent RE powder。
Containing metal-organic framework materials 99.89wt% in this fluorescent material, coumarin 460 content 0.03wt%, solvent yellow content 0.04wt%, resorufin content 0.04wt%, its internal quantum efficiency is 76%。After using this fluorescent material to form white light LEDs with blue-light LED chip combination, color rendering index is 89, and colour temperature is 5506K, and light efficiency is 157lm/W(electric current density 20A/cm2)。55 DEG C, electric current density be 120A/cm2Aging condition under, after 168h, light decay is only 0.79%。
Embodiment 5:
(1) preparation of metal-organic framework materials:
The Pyromellitic Acid and the 0.2mmol zinc nitrate that weigh 0.1mmol are dissolved in the DMF of 100mL and the mixed solvent of 1mL water, are subsequently adding after the nitric acid that 0.3mL mass fraction is 65% stirs and put in airtight reactor, and heating is to 130oC isothermal reaction 72h, obtains metal-organic framework materials；
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
Take 5mg yellow light emitting dyes Fluorescein isothiocyanate and 0.5mg red light emitting dyes rhodamine 6G, 1mg red light emitting dyes oxazines 1 are dissolved in the N of 100mL, in N dimethyl amide solvent, inwardly add metal-organic framework materials immersion 24h prepared by 1g step (1) again, with ethanol purge after filtration, dry, obtain white light LEDs without fluorescent RE powder。
Containing metal-organic framework materials 98wt% in this fluorescent material, Fluorescein isothiocyanate content 1wt%, rhodamine 6G content 0.55wt%, oxazines 1 content 0.45wt%, its internal quantum efficiency is 78%。After using this fluorescent material to form white light LEDs with blue-light LED chip combination, color rendering index is 86, and colour temperature is 2500K, and light efficiency is 141lm/W(electric current density 20A/cm2)。55 DEG C, electric current density be 120A/cm2Aging condition under, after 168h, light decay is only 0.88%。
Embodiment 6:
(1) preparation of metal-organic framework materials:
Weighing the 3,4' of 0.5mmol, 5-biphenyl tricarboxylic acids and 1.2mmol zinc acetate are dissolved in the aqueous solution of 100mL, are subsequently adding after the nitric acid that 0.3mL mass fraction is 65% stirs and put in airtight reactor, and heating is to 90oC isothermal reaction 24h, obtains metal-organic framework materials；
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
Take 1mg green light emitting dye coumarin 314 and 0.1mg red light emitting dyes pyronin Y is dissolved in the N of 50mL, in N bis-base formamide solvent, inwardly add metal-organic framework materials immersion 5h prepared by 0.6g step (1) again, ethanol purge is used after filtration, dry, obtain white light LEDs without fluorescent RE powder。
Containing metal-organic framework materials 99.98wt% in this fluorescent material, coumarin 314 content 0.01wt%, pyronin Y content 0.01wt%, its internal quantum efficiency is 81%。After using this fluorescent material to form white light LEDs with blue-light LED chip combination, color rendering index is 84, and colour temperature is 4672K, and light efficiency is 161lm/W(electric current density 20A/cm2)。55 DEG C, electric current density be 120A/cm2Aging condition under, after 168h, light decay is only 0.31%。
Embodiment 7:
(1) preparation of metal-organic framework materials:
The oreinol diacid and the 2mmol zirconium chloride that weigh 0.5mmol are dissolved in the solution of water of 60mL, are subsequently adding after the nitric acid that 0.5mL mass fraction is 65% stirs and put in airtight reactor, and heating is to 130oC isothermal reaction 48h, obtains metal-organic framework materials；
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
Take 3mg green light emitting dye coumarin 6,3mg acriflavinium chloride and 0.5mg red light emitting dyes pyronine B and be dissolved in the alcohol solvent of 100mL, inwardly add metal-organic framework materials immersion 24h prepared by 1g step (1) again, ethanol purge is used after filtration, dry, obtain white light LEDs without fluorescent RE powder。
Containing metal-organic framework materials 98.79wt% in this fluorescent material, coumarin 6 content 0.33wt%, acriflavinium chloride content 0.26wt%, pyronine B content 0.62%, its internal quantum efficiency is 76%。After using this fluorescent material to form white light LEDs with blue-light LED chip combination, color rendering index is 90, and colour temperature is 7000K, and light efficiency is 153lm/W(electric current density 20A/cm2)。55 DEG C, electric current density be 120A/cm2Aging condition under, after 168h, light decay is only 1.21%。
Embodiment 8:
(1) preparation of metal-organic framework materials:
Weigh the 4 of 0.4mmol, 4'-oxydibenzoic acid and 1mmol zinc acetate are dissolved in the N of 60mL, in the mixed solvent of dinethylformamide, 20mL oxolane and 10mL water, being subsequently adding after the concentrated nitric acid that 0.2mL mass fraction is 65% stirs and put in airtight reactor, heating is to 150oC isothermal reaction 72h, obtains metal-organic framework materials；
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
Take 5mg green light emitting dye coumarin 314 and 4mg red light emitting dyes Nile red is dissolved in the tetrahydrofuran solvent of 10mL, inwardly add metal-organic framework materials immersion 48h prepared by 1g step (1) again, ethanol purge several times are used after filtration, dry, obtain white light LEDs without fluorescent RE powder。
Containing metal-organic framework materials 99.70wt% in this fluorescent material, coumarin 314 content 0.11wt%, Nile red content 0.19wt%, its internal quantum efficiency is 75%。After using this fluorescent material to form white light LEDs with blue-light LED chip combination, color rendering index is 80, and colour temperature is 5890K, and light efficiency is 149lm/W(electric current density 20A/cm2)。55 DEG C, electric current density be 120A/cm2Aging condition under, after 168h, light decay is only 0.96%。
Embodiment 9:
(1) preparation of metal-organic framework materials:
The trimesic acid and the 0.8mmol chromic nitrate that weigh 0.1mmol are dissolved in 10mL aqueous solution, are subsequently adding after the concentrated nitric acid that 0.5mL mass fraction is 65% stirs and put in airtight reactor, and heating is to 80oC isothermal reaction 72h, obtains metal-organic framework materials。
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
Take 5mg green light emitting dye coumarin 6,3mg calcein and 0.5mg red light emitting dyes rhodamine B and be dissolved in 30mL ethanol and 30mLN, in the mixed solvent of dinethylformamide, inwardly add metal-organic framework materials immersion 24h prepared by 1g step (1) again, with ethanol purge after filtration, dry, obtain white light LEDs without fluorescent RE powder。
Containing metal-organic framework materials 99.56wt% in this fluorescent material, coumarin 6 content 0.13wt%, calcein content 0.09wt%, rhodamine B content 0.22%, its internal quantum efficiency is 76%。After using this fluorescent material to form white light LEDs with blue-light LED chip combination, color rendering index is 89, and colour temperature is 4892K, and light efficiency is 161lm/W(electric current density 20A/cm2)。55 DEG C, electric current density be 120A/cm2Aging condition under, after 168h, light decay is only 1.32%。
Embodiment 10:
(1) preparation of metal-organic framework materials:
Weigh the 4 of 0.1mmol, 4', 4 ' '-triazine-1,3,5-tri-para-amino benzoic acid and 3mmol aluminum chloride are dissolved in the N of 60mL, in the mixed solvent of dinethylformamide, 40mL acetone and 10mL water, being subsequently adding after the concentrated nitric acid that 0.5mL mass fraction is 65% stirs and put in airtight reactor, heating is to 130oC isothermal reaction 24h, obtains metal-organic framework materials；
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
Take 1mg green light emitting dye acriflavinium chloride and 1mg red light emitting dyes pyronine B is dissolved in the N of 20mL, in N-dimethylformamide solvent, inwardly add metal-organic framework materials immersion 24h prepared by 1g step (1) again, with ethanol purge after filtration, dry, obtain white light LEDs without fluorescent RE powder。
Containing metal-organic framework materials 99.83wt% in this fluorescent material, acriflavinium chloride content 0.08wt%, pyronine B content 0.09wt%, its internal quantum efficiency is 75%。After using this fluorescent material to form white light LEDs with blue-light LED chip combination, color rendering index is 80, and colour temperature is 5556K, and light efficiency is 141lm/W(electric current density 20A/cm2)。55 DEG C, electric current density be 120A/cm2Aging condition under, after 168h, light decay is only 0.98%。
Embodiment 11:
(1) preparation of metal-organic framework materials:
Weigh the trimesic acid of 0.1mmol and 0.4mmol basic zirconium chloride is dissolved in the N of 100mL, in the mixed solvent of dinethylformamide and 50mL water, being subsequently adding after the concentrated nitric acid that 0.5mL mass fraction is 65% stirs puts in airtight reactor, and heating is to 130oC isothermal reaction 48h, obtains metal-organic framework materials。
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
Take 2mg green light emitting dye coumarin 6,2mg yellow light emitting dyes fluorescein and 0.5mg red light emitting dyes pyronine B, 0.8mg red dye resorufin and be dissolved in the N of 100mL, in N-dimethylformamide solvent, inwardly add metal-organic framework materials immersion 48h prepared by 1g step (1) again, with ethanol purge after filtration, dry, obtain white light LEDs without fluorescent RE powder。
Containing metal-organic framework materials 99.32wt% in this fluorescent material, coumarin 6 content 0.12wt%, fluorescein content 0.16wt%, pyronine B content 0.17%, resorufin content 0.23%, its internal quantum efficiency is 75%。After using this fluorescent material to form white light LEDs with blue-light LED chip combination, color rendering index is 91, and colour temperature is 5604K, and light efficiency is 145lm/W(electric current density 20A/cm2)。55 DEG C, electric current density be 120A/cm2Aging condition under, after 168h, light decay is only 0.84%。
Claims (8)
1. a white light LEDs without fluorescent RE powder, it is characterised in that its composition and mass percentage content be: metal-organic framework materials 98～99.98%, gold-tinted or green light emitting dye 0.01～1%, red light emitting dyes 0.01～1%。
2. the method without fluorescent RE powder of preparation white light LEDs described in claim 1, it is characterised in that comprise the following steps:
(1) preparation of metal-organic framework materials:
The aromatic carboxylic acids part of 0.1～1mmol and 0.2～3mmol slaine are dissolved in the mixed solvent of 10～100mL organic solvent and 1～50mL water, or it is dissolved in 10～100mL aqueous solution, it is added dropwise over putting in airtight reactor after the nitric acid that 0～0.5mL mass fraction is 65% stirs, at 40～150 DEG C of isothermal reaction 5～72h, obtain metal-organic framework materials；
(2) gold-tinted or green light emitting dye and red light emitting dyes are loaded into metal-organic framework materials:
The red light emitting dyes of the gold-tinted or green light emitting dye and 0.1～5mg that take 0.1～5mg is dissolved in the water of 10～100mL or is dissolved in 10～100mL organic solvent, inwardly add metal-organic framework materials immersion 5～48h prepared by 0.1～1g step (1) again, clean with alcohol solvent after filtration, dry, obtain white light LEDs without fluorescent RE powder。
3. the preparation method without fluorescent RE powder of white light LEDs according to claim 2, it is characterised in that described aromatic carboxylic acids part be trimesic acid, Pyromellitic Acid, 5-amino-isophthalic acid, 3,3', 5,5'-bibenzene tetracarboxylics, 1,3,5-tri-(4-carboxyl benzene) benzene, 3,4', 5-biphenyl tricarboxylic acids, oreinol diacid, 4,4'-oxydibenzoic acid or 4,4', 4 "-triazine-1,3,5-tri-para-amino benzoic acid。
4. the preparation method without fluorescent RE powder of white light LEDs according to claim 2, it is characterised in that described slaine is zinc salt, indium salts, aluminium salt, zirconates or chromic salts。
5. the preparation method without fluorescent RE powder of white light LEDs according to claim 4, it is characterised in that described zinc salt is zinc nitrate, zinc chloride or zinc acetate；Described indium salts is indium nitrate, indium chloride or indium acetate；Described aluminium salt is aluminum chloride or aluminum nitrate；Described zirconates is zirconium chloride or basic zirconium chloride；Described chromic salts is chromic nitrate, Chlorizate chromium or chromium acetate。
6. the method without fluorescent RE powder of White-light LED illumination according to claim 2, it is characterized in that the organic solvent described in step (1) and step (2) is N, N-dimethylformamide, N, the mixing of any one or arbitrarily several any ratio in N-dimethyl acetylamide, N, N-diethylformamide, methanol, ethanol, dioxane, oxolane and acetone。
7. the preparation method without fluorescent RE powder of white light LEDs according to claim 2, it is characterised in that described gold-tinted or green light emitting dye are that in coumarin 6, coumarin 460, coumarin 314, acriflavinium chloride, fluorescein, Fluorescein isothiocyanate and solvent yellow, any one or arbitrarily several arbitrarily ratios mix。
8. the preparation method without fluorescent RE powder of white light LEDs according to claim 2, it is characterised in that described red light emitting dyes is the mixing of any one or the arbitrarily several any ratio in pyronine B, pyronin Y, rhodamine 6G, rhodamine B, resorufin, oxazines 1 and Nile red。
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| CN109738408A (en) * | 2019-01-07 | 2019-05-10 | 温州大学 | A kind of organic MOFS wraps up the application of fluorescein composite material and its detection mercury ion |
| CN109768151A (en) * | 2019-01-04 | 2019-05-17 | 浙江大学 | It is a kind of to illuminate and show with multi-colored led and preparation method thereof |
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| CN110734761A (en) * | 2019-10-29 | 2020-01-31 | 南京邮电大学 | Preparation method and application of two-primary-color white light OLED material |
| CN111187419A (en) * | 2020-01-10 | 2020-05-22 | 浙江大学 | Dye/metal-organic framework composite material with fluorescence up-conversion performance, preparation method thereof and biological imaging application |
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