CN1243146A - Process for synthesizing organic/inorganic nanometer hybridized luminous material containing rare earth - Google Patents
Process for synthesizing organic/inorganic nanometer hybridized luminous material containing rare earth Download PDFInfo
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- CN1243146A CN1243146A CN 98116430 CN98116430A CN1243146A CN 1243146 A CN1243146 A CN 1243146A CN 98116430 CN98116430 CN 98116430 CN 98116430 A CN98116430 A CN 98116430A CN 1243146 A CN1243146 A CN 1243146A
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Abstract
The present invention adopts sol-gel method to make precursor compound N-(propyl-gamma-triethoxysilicane ester)-4-carboxyl-phthalimide I form sol under the catalysis of hydrochrochloric acid, then adds the rare earth ion or rare earth ion and organic dye N-(propyl-gamma-triethoxysilicane ester)-4,4'-diphenyl tetracarboxylic acid bisimide II to said sol, and utilizes the processes of whirl coating, film-forming and gelatination to obtain the invented organic/inorganic nanometer hybrid optical transparent solid film which contains rare earth and can emit red, green, yellow and white fluorescence.
Description
The invention belongs to the synthetic method that contains rare earth organic/inorganic nano hybrid luminescent materials.
Rare earth compounding is luminous to be inorganic light-emitting and organic light emission, noctilcent cross discipline, and the emergence along with fast development, the especially photon technology of information science and technology in recent years makes the research of rare earth compounding become the research focus of Materials science.Rare earth compounding has been obtained breakthrough in material fields such as LB film, sol-gel (Sol-gel), electroluminescent.Successful assembling as ultra-thin LB film of multilayer order and rare earth compounding electroluminescent device.But at present yet there are a lot of problems in the research of rare earth compounding, and Qian Dongjin etc. are at Acta PhySico-Chimica Sinica, 1993,9,148 disclose a kind of LB film of rare earth beta-diketon class title complex, have reported that the optical stability of this title complex is very poor, and K.Z.Wang is at Thin Solid Films 1994,252,139 have also reported rare earth compounding LB film, and the film-forming properties or the film transfer performance of rare earth compounding individual layer LB film are relatively poor, and multilayer is poorer, and the glow color kind is single, does not especially have the luminous of white fluorescent.In the sol-gel field optimization modification of luminescence center and control techniques thereof, luminescent material in matrix homodisperse and ooze out effect yet existing problems.In addition, well-known, in electroluminescent luminescent layer still with prepared by heat evaporation, complex technical process not only, and easily cause the decomposition of luminescent material.
The purpose of this invention is to provide a kind of synthetic method that contains rare earth organic/inorganic nano hybrid luminescent materials, adopt Sol-gel precursor compound N-(propyl group-γ-triethoxy estersil)-4-carboxyl-phthalic imidine I in present method, N-(propyl group-γ-triethoxy estersil)-4,4 '-bibenzene tetracarboxylic double imide II and trivalent rare earth ions europium or terbium are raw material, original position (In-situ) forms rare earth carboxylate ligand compound, obtain optically transparent organic/inorganic nano hydridization solid film via the Sol-gel process, and can realize red, green, yellow and even white luminous.
Synthetic technology of the present invention is the inorganic polycondensation based on traditional preparation glass, pottery, and prepares organic/machine nano hybridization light-emitting solid film by the Sol-gel process.Polymerization mechanism is inorganic condensation polymerization.
Sol-gel precursor compound I structural formula is as follows among the present invention:
The structural formula of the organic dye II that adopts is as follows:
The rare earth ion that adopts is provided by the nitrate or the hydrochloride of trivalent europium and terbium;
The object of the present invention is achieved like this, at first adopt Sol-gel precursor compound N-(propyl group-γ-triethoxy estersil)-4-carboxyl-phthalic imidine I hydrolysis to form colloidal sol, directly with rare earth ion or rare earth ion and the functionalized organic dye N-(propyl group-γ-triethoxy estersil)-4 of another kind of silicon alkoxyl group, 4 '-bibenzene tetracarboxylic double imide II adds in this colloidal sol, rare earth ion and precursor compound I original position (In-situ) form rare earth carboxylate ligand compound, organic dye II hydrolysis in colloidal sol, afterwards condensation participates in the hybridization network with it, pass through spin-coating film, and gel at a certain temperature, obtain optically transparent organic/inorganic nano hydridization light-emitting solid film.
The present invention is dissolved in N with Sol-gel precursor compound I, in the dinethylformamide (DMF), is hydrolyzed into colloidal sol under 0.1N～0.3N aqueous hydrochloric acid catalysis, presses rare earth ion Eu
3+Or Tb
3+With the mole proportioning of carboxylic acid is 1 ‰-1/3 to add in the colloidal sol, room temperature spin coating system film, and in 40～120 ℃ of vacuum drying ovens gel 10～36 hours, obtain optically transparent hybrid solid film, this film can send very strong redness, green fluorescence under UV-irradiation; Same quadrat method is with Eu
3+And Tb
3+Ratio with 10/1～1/10 adds in the above-mentioned colloidal sol, and acquisition can be sent the solid film from orange to yellow so that yellow-green fluorescence; With Eu
3+, Tb
3+Reach Compound I I and add in the above-mentioned colloidal sol, obtain to send the solid hybrid film of white fluorescent in 1/1～1.5/2～3 ratios.
Characteristics of the present invention are on the basis of traditional Sol-gel method, break through general rare earth compounding organic/inorganic hybridization material on the one hand and adopt the method that adds the small molecules organic rare-earth ligand, directly rare earth ion is joined in the colloidal sol of carboxylic Sol-gel precursor compound I, original position forms rare earth compounding and then forms the gel-film of hybrid; The organic molecule that organic dye neither be general on the other hand, but the oxyalkylated organic dye of silicon, this organic dye participates in hydrolytic condensation, enters hybridization network, thereby has avoided drawbacks such as the inhomogeneous and small molecules of luminescence center dispersion of materials oozes out.The preparation condition gentleness of whole material, method is simple, and preparation cycle is short, is easy to industrialization.
Specific embodiments of the invention are as follows: embodiment 1
The preparation of green hybrid luminescent film:
Get 1 * 10
-3The DMF solution 2ml of M Compound I adds 0.1N aqueous hydrochloric acid 0.1ml, adds 2.5 * 10 again
-3MTb (NO
3)
3DMF solution 0.5ml, stirring at room 3h.Take a morsel and drip on the quartz plate of cleaning, spin coating forms film on sol evenning machine, this diaphragm is placed 40 ℃ of vacuum drying oven bakings 10 hours, transfer in 120 ℃ of vacuum drying ovens and dried by the fire 20 hours, promptly get optically transparent SOLID ORGANIC/inorganic hybrid membrane, diaphragm sends very strong green fluorescence under ultraviolet lamp.Embodiment 2
The preparation of red hybrid luminescent film
Get 1 * 10
-3The DMF solution 2ml of M Compound I adds 0.1N aqueous hydrochloric acid 0.1ml, adds 4 * 10 again
-3M Eu (NO
3)
3DMF solution 0.2ml, stirring at room 3h.Take a morsel and drip on the quartz plate of cleaning, spin coating forms film on sol evenning machine, this diaphragm is placed 40 ℃ of vacuum drying oven bakings 10 hours, transfer in 100 ℃ of vacuum drying ovens and dried by the fire 36 hours, promptly get optically transparent SOLID ORGANIC/inorganic hybrid membrane, diaphragm sends very strong red fluorescence under ultraviolet lamp.Embodiment 3
The preparation of yellow hybrid luminescent film
Get 1 * 10
-3The DMF solution 2ml of M Compound I adds 0.1N aqueous hydrochloric acid 0.1ml, adds 2.5 * 10 again
-3M Tb (NO
3)
3DMF solution 0.04ml, 4 * 10
-3M Eu (NO
3)
3DMF solution 0.025ml, stirring at room 3h.Take a morsel and drip on the quartz plate of cleaning, spin coating forms film on sol evenning machine, this diaphragm is placed 40 ℃ of vacuum drying oven bakings 10 hours, transfer in 120 ℃ of vacuum drying ovens and dried by the fire 20 hours, promptly get optically transparent SOLID ORGANIC/inorganic hybrid membrane, diaphragm sends very strong green fluorescence under ultraviolet lamp.Embodiment 4
The preparation of white hybrid luminescent film
Get 1 * 10
-3The DMF solution 2ml of M Compound I adds 0.1N aqueous hydrochloric acid 0.1ml, adds 2.5 * 10 again
-3M Tb (NO
3)
3DMF solution 0.04ml, 4 * 10
-3M Eu (NO
3)
3DMF solution 0.025ml, 3 * 10
-3The DMF solution 0.05ml of M Compound I I, stirring at room 3h.Take a morsel and drip on the quartz plate of cleaning, spin coating forms film on sol evenning machine, this diaphragm is placed 40 ℃ of vacuum drying oven bakings 20 hours, transfer in 120 ℃ of vacuum drying ovens and dried by the fire 40 hours, promptly get optically transparent SOLID ORGANIC/inorganic hybrid membrane, diaphragm sends very strong white fluorescent embodiment 5 under ultraviolet lamp
The preparation of white hybrid luminescent film
Get 1 * 10
-3The DMF solution 2ml of M Compound I adds 0.1N aqueous hydrochloric acid 0.1ml, adds 2.5 * 10 again
-3M Tb (NO
3)
3DMF solution 0.1ml, 4 * 10
-3M Eu (NO
3)
3DMF solution 0.05ml, 3 * 10
-3The DMF solution 0.25ml of M Compound I I, stirring at room 3h.Take a morsel and drip on the quartz plate of cleaning, spin coating forms film on sol evenning machine, this diaphragm is placed 40 ℃ of vacuum drying oven bakings 10 hours, transfer in 120 ℃ of vacuum drying ovens and dried by the fire 20 hours, promptly get optically transparent SOLID ORGANIC/inorganic hybrid membrane, diaphragm sends very strong white fluorescent under ultraviolet lamp.
Claims (1)
1. synthetic method that contains rare earth organic/inorganic nano hybrid luminescent materials is characterized in that adopting following structure Sol-gel precursor compound:
N-(propyl group-γ-triethoxy estersil)-4-carboxyl-phthalic imidine I
N-(propyl group-γ-triethoxy estersil)-4,4 '-bibenzene tetracarboxylic double imide II
The rare earth ion that adopts is provided by the nitrate or the hydrochloride of trivalent europium and terbium;
In preparation process, I is dissolved among the DMF with the synthetic Sol-gel of institute precursor compound, is hydrolyzed into colloidal sol under aqueous hydrochloric acid catalysis, presses rare earth ion Eu
3+Or Tb
3+With the mole proportioning of carboxylic acid is 1 ‰-1/3 to add in the colloidal sol, room temperature spin coating system film, and in 40～120 ℃ of vacuum drying ovens gel 10～36 hours, obtain optically transparent hybrid solid film, this film can send very strong redness, green fluorescence under UV-irradiation; Same quadrat method is with Eu
3+And Tb
3+Add in the above-mentioned colloidal sol with 10/1～1/10 ratio, promptly obtain to send solid film from orange to yellow and even yellow-green fluorescence; With Eu
3+, Tb
3+Reach Compound I I and add in the above-mentioned colloidal sol, obtain to send the solid hybrid film of white fluorescent in 1/1～1.5/2～3 ratios.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98116430A CN1101440C (en) | 1998-07-27 | 1998-07-27 | Process for synthesizing organic/inorganic nanometer hybridized luminous material containing rare earth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98116430A CN1101440C (en) | 1998-07-27 | 1998-07-27 | Process for synthesizing organic/inorganic nanometer hybridized luminous material containing rare earth |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1243146A true CN1243146A (en) | 2000-02-02 |
| CN1101440C CN1101440C (en) | 2003-02-12 |
Family
ID=5225064
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98116430A Expired - Fee Related CN1101440C (en) | 1998-07-27 | 1998-07-27 | Process for synthesizing organic/inorganic nanometer hybridized luminous material containing rare earth |
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|---|---|
| CN (1) | CN1101440C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297820C (en) * | 2001-01-09 | 2007-01-31 | 普罗托赛拉株式会社 | Novel proteome analysis method and devices therefor |
| CN100352887C (en) * | 2006-01-25 | 2007-12-05 | 山东大学 | Method for preparing highly effective green light rare earth compound film |
| CN100440567C (en) * | 2005-06-15 | 2008-12-03 | 北京大学 | Liftout optical electrode and its preparation method |
| CN1876752B (en) * | 2005-06-06 | 2011-04-20 | 森实茂 | Method of manufacturing light emitting material |
| CN108795416A (en) * | 2017-04-28 | 2018-11-13 | 东北林业大学 | A kind of preparation method of Si modification terbium coordination compound fluorescent powder |
| CN113025107A (en) * | 2021-05-10 | 2021-06-25 | 中山大学 | Preparation method and application of cuprous iodide-based hybrid fluorescent coating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100247817B1 (en) * | 1993-02-18 | 2000-03-15 | 손욱 | A fluorescent of blue for fluorescent lamp |
-
1998
- 1998-07-27 CN CN98116430A patent/CN1101440C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297820C (en) * | 2001-01-09 | 2007-01-31 | 普罗托赛拉株式会社 | Novel proteome analysis method and devices therefor |
| CN1876752B (en) * | 2005-06-06 | 2011-04-20 | 森实茂 | Method of manufacturing light emitting material |
| CN100440567C (en) * | 2005-06-15 | 2008-12-03 | 北京大学 | Liftout optical electrode and its preparation method |
| CN100352887C (en) * | 2006-01-25 | 2007-12-05 | 山东大学 | Method for preparing highly effective green light rare earth compound film |
| CN108795416A (en) * | 2017-04-28 | 2018-11-13 | 东北林业大学 | A kind of preparation method of Si modification terbium coordination compound fluorescent powder |
| CN113025107A (en) * | 2021-05-10 | 2021-06-25 | 中山大学 | Preparation method and application of cuprous iodide-based hybrid fluorescent coating |
| CN113025107B (en) * | 2021-05-10 | 2021-12-21 | 中山大学 | Preparation method and application of cuprous iodide-based hybrid fluorescent coating |
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| Publication number | Publication date |
|---|---|
| CN1101440C (en) | 2003-02-12 |
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