CN1470593A - Method for preparing red-light rare-earth organic complex electroluminescent material and device - Google Patents
Method for preparing red-light rare-earth organic complex electroluminescent material and device Download PDFInfo
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- CN1470593A CN1470593A CNA031450520A CN03145052A CN1470593A CN 1470593 A CN1470593 A CN 1470593A CN A031450520 A CNA031450520 A CN A031450520A CN 03145052 A CN03145052 A CN 03145052A CN 1470593 A CN1470593 A CN 1470593A
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Abstract
The present invention adopts dibenzoyl methane (DBM) or trifluoroacetyl-thiopheneacetone (TTA) matched with trivalent europium ion energy as first ligand, adopts 3,4,7,8-tetramethyl-1,10-phenanthroline as second ligand, then utilizeks the first ligand and second ligand according to mole ratio of 3:1 and the trivalent europium ion to form ternary europium compounding material, and makes the prepared red light rare earth organic compound material electroluminescent material into the electroluminescent device, its efficiency can be up to 4.7 cd/A, and maximum luminance is 800 cd/sq.m.
Description
Technical field
The invention belongs to a kind of red light rare-earth organic complex electroluminescent material and preparation of devices method.
Background technology
Electroluminescent organic material and device are current international forward position research fields.The display device made from electroluminescent organic material is because to have a driving voltage low, and preparation technology is simple, can be prepared into the big area display unit, and has the advantage of flexible curved, has therefore shown great application prospect in the flat pannel display field.At present, many electroluminescent organic materials have begun commercialization, and part organic display spare has also obtained application at aspects such as mobile phone, automobile audios.Yet the display device that most of organic molecules and polymer luminescent material are made, its emmission spectrum are generally all than broad, and generally between 100-200nm, purity of color is bad for half-breadth.Therefore, do not satisfy the colored requirement that shows of high information content, particularly, compare with blue light material with green glow, the luminescent device made from red light material efficient and stable aspect still have big gap.Therefore, exploitation high-level efficiency, high brightness, high color purity, stable ruddiness electroluminescent organic material and device are of great significance.
Fluorescence organic molecule with common usefulness is compared with polymer electroluminescence material, and rare earth organic complex can realize that high color purity is luminous because distinctive 4f electronic structure itself has determined that this material has narrower emmission spectrum.Simultaneously, the luminous attenuation process that has comprised singlet state and triplet exciton of rare earth organic complex, theoretically, rare earth organic complex can be realized 100% quantum yield.Just because of these inherent characteristics, in recent years, rare earth organic complex had obtained extensive studies in the organic electroluminescent field.
Trivalent europium ion title complex burn red is considered to realize the most promising material system of high color purity ruddiness organic electroluminescence device.1994, people such as Kido deliver on AppliedPhysics Letter and utilize diphenylpropane-1,3-dione(DPPO) and 1, rare earth europium ternary complex and hydroxyquinoline aluminum that adjacent Fei Luolin of 10-and trivalent europium ion reaction obtain are formed three layer devices, obtain up to 460cd/m under the 16V driving DC voltage
2Luminosity, top efficiency is 1.7cd/A.The auspicious grade of Wang Li people had delivered on Chemistry of Materials with the europium complex of oxadiazole functionalization and has done active medium in 2003, adopted the bilayer structure device, and brightness reaches 320cd/m
2, maximum efficiency is 1.9cd/A.People such as the yellow light of spring in 2003 have delivered on ChemicalCommunications with diphenylpropane-1,3-dione(DPPO) and (2-4 '-triphenylamine) imidazoles [4,5-f] 1, and the title complex that adjacent Fei Luolin of 10-and trivalent europium ion are formed has prepared brightness up to 1305cd/m
2Electroluminescent device, its maximum quantum yield is 0.85%.
Be not difficult to find out from above-mentioned, though make the electroluminescent device performance of luminescence medium was significantly improved in recent years of the rare-earth europium title complex, but compare with polymer electroluminescent device with common organic molecule, the efficient of rare earth organic complex electroluminescent device and brightness are still waiting to improve further and improve.
Summary of the invention
The purpose of this invention is to provide a kind of ruddiness rare-earth europium title complex electroluminescent organic material.
Another object of the present invention provides a kind of preparation method of ruddiness rare-earth europium title complex electroluminescent organic material.
The 3rd purpose of the present invention provides a kind of purposes of ruddiness rare-earth europium complex material.
Rare earth compounding is luminous is to be produced by the intramolecular energy transfer that the 4f of the electronic level of part excited state and rare earth ion can inter-stage, rather than since directly exciting of rare earth ion cause.When the resonance level of the excited triplet state energy level of part and rare earth ion reaches certain energy difference, can produce the optimal luminescent quantum yield, if this energy difference is too little or too metropolitan cause the rare earth compounding luminous quantum efficiency low or not luminous.
Diphenylpropane-1,3-dione(DPPO) (DBM) or trifluoroacetyl thiophene acetone (TTA) that employing of the present invention and trivalent europium ion energy are flux matched are made first part, employing has 3 of elevation plane structure, 4,7,8-tetramethyl--1, the adjacent Fei Luolin of 10-is as second part, and first part and second part are formed the ternary europium complex by 3: 1 mol ratio and tervalent europium ion; On the device architecture, select N, N '-two (3-aminomethyl phenyl)-N, N '-phenylbenzene-1,1 '-phenylbenzene-4,4 '-diamines (TPD) and oxine aluminium (AlQ) are respectively as hole and electron transfer layer, with 2,9-dimethyl-4,7-phenylbenzene-1,10-neck Fei Luolin (BCP) is electric transmission/hole blocking layer.Because 4,4-N, being transmitted between the 390-420nm of N-two carbazole biphenyl (CBP) has overlappingly preferably with the absorption 250nm-420nm of the part of above-mentioned two kinds of europium complexes, can form effective transmission ofenergy.Therefore, adopt CBP, rare earth compounding is doped in the middle of the CBP as parent.Device architecture is an ITO/TPD/Eu complex:CBP/BCP/AlQ/ metal electrode.
The structural formula of ruddiness rare-earth europium complex material provided by the present invention is as follows:
R1=phenyl wherein; R2=phenyl or R1=trifluoromethyl, the R2=2-thienyl; Preparation process:
Will as the diphenylpropane-1,3-dione(DPPO) (DBM) of first part or trifluoroacetyl thiophene acetone (TTA) with as 3 of second part, 4,7,8-tetramethyl--1, the adjacent Fei Luolin of 10-(Tmphen) is dissolved in ethanol or the chloroform by 3: 1 mol ratio, the sodium hydroxide or the triethylamine of mole numbers such as the adding and first part under stirring condition, then, the solution of the trivalent europium ion of mole numbers such as the adding and second part, temperature of reaction is between 30 ℃-80 ℃, and in 0.5 hour-4 hours reaction times, product is washed, alcohol is washed, and obtains compd E u (DBM)
3(Tmphen) or Eu (TTA)
3(Tmphen), and do active medium with them and prepare organic electroluminescence device, device electroluminescent spectrum that makes and photoluminescence spectra basically identical, show that electroluminescent and photoluminescence all derive from the feature emission of rare earth trivalent europium ion, main peak is at 612nm, and half-breadth is less than 5nm, has good monochromaticity, the electroluminescent device of making, efficient can be up to 4.7cd/A, and high-high brightness is 800cd/m
2Its luminous efficiency and luminosity can obtain authentication from accompanying drawing 1,2,3.
Description of drawings
Fig. 1 is the electric current-brightness-voltage response of electroluminescent device.
Fig. 2 is the luminous efficiency-current characteristics curve of electroluminescent device.
Fig. 3 is the electroluminescent spectrum of device.
Embodiment
Embodiment 1:
Get diphenylpropane-1,3-dione(DPPO) (DBM) 3 mmoles and 3,4,7,8-tetramethyl--1, adjacent Fei Luolin 1 mmole of 10-is dissolved in the ethanol, adds the aqueous solution of 3 mmole sodium hydroxide then, under the condition of stirring heating, slowly drip 10 milliliters of the europium chloride aqueous solution of every milliliter of 0.1 mmole.In 60 ℃ of reacting by heating 30 minutes, the product washing, ethanol is washed, and recrystallization obtains Eu (DBM)
3(Tmphen).With Eu (DBM)
3(Tmphen) being prepared into structure is ITO/TPD/Eu (DBM)
3(Tmphen): the electroluminescent device of CBP/BCP/AlQ/LiF/Al, in vacuum tightness 10
-3Organic and the metal electrode layer of evaporation under the pressure of handkerchief, the evaporation rate-controlling of organic layer is at 4 /s, and the vaporator rate of LiF is controlled 0.5 /s, and the evaporation rate-controlling of metal is at 5 /s, and doping content is controlled at 1%.Wherein, the TPD layer thickness is 40nm, Eu (DBM)
3(Tmphen): CBP layer 30nm, BCP layer are 20nm, and the AlQ layer is 30nm, LiF layer 1nm, Al layer 100nm.The obtained device direct voltage drive can obtain pure rare-earth europium ionic feature emission, and maximum efficiency is 4.4cd/A, and high-high brightness can reach 790cd/m
2
Embodiment 2:
Get diphenylpropane-1,3-dione(DPPO) (DBM) 6 mmoles and 3,4,7,8-tetramethyl--1, adjacent Fei Luolin 2 mmoles of 10-are dissolved in the chloroform, add 6 mmole triethylamines then, under the condition of stirring heating, slowly drip 20 milliliters of the europium chloride ethanolic solns of every milliliter of 0.1 mmole.40 ℃ of reacting by heating 1 hour, remove reaction solvent, obtain Eu (DBM)
3(Tmphen), washing, ethanol is washed, recrystallization.With Eu (DBM)
3(Tmphen) being prepared into structure is ITO/TPD/Eu (DBM)
3(Tmphen): the electroluminescent device of CBP/BCP/AlQ/LiF/Al, in vacuum tightness 10
-4Organic and the metal electrode layer of evaporation under the pressure of handkerchief, the evaporation rate-controlling of organic layer is at 2 /s, and the vaporator rate of LiF is controlled 1 /s, and the evaporation rate-controlling of metal is at 8 /s, and doping content is controlled at 3%.Wherein, the TPD layer thickness is 30nm, Eu complex:CBP layer 20nm, and the BCP layer is 10nm, the AlQ layer is 30nm, LiF layer 0.8nm, Al layer 200nm.The obtained device direct voltage drive can obtain pure rare-earth europium ionic feature emission, and maximum efficiency is 4.3cd/A, and high-high brightness can reach 800cd/m
2
Embodiment 3:
Get trifluoroacetyl thiophene acetone (TTA) 3 mmoles and 3,4,7,8-tetramethyl--1, adjacent Fei Luolin 1 mmole of 10-is dissolved in the ethanol, adds the aqueous solution of 3 mmole sodium hydroxide then, under the condition of stirring heating, slowly drip 10 milliliters of the europium chloride aqueous solution of every milliliter of 0.1 mmole.70 ℃ of reacting by heating 4 hours, washing, ethanol is washed, and recrystallization obtains Eu (TTA)
3(Tmphen), with Eu (TTA)
3(Tmphen) being prepared into structure is ITO/TPD/Eu (TTA)
3(Tmphen): the electroluminescent device of CBP/BCP/AlQ/LiF/Al, in vacuum tightness 3 * 10
-6Organic and the metal electrode layer of evaporation under the pressure of handkerchief, the evaporation rate-controlling of organic layer is at 1 /s, and the vaporator rate of LiF is controlled 0.2 /s, and the evaporation rate-controlling of metal is at 10 /s, and doping content is controlled at 5%.Wherein, the TPD layer thickness is 35nm, Eu (TTA)
3(Tmphen): CBP layer 250nm, BCP layer are 20nm, and the AlQ layer is 30nm, LiF layer 1nm, Al layer 80nm.The obtained device direct voltage drive can obtain pure rare-earth europium ionic feature emission, and maximum efficiency is 4.0cd/A, and high-high brightness can reach 750cd/m
2
Embodiment 4:
Get trifluoroacetyl thiophene acetone (TTA) 6 mmoles and 3,4,7,8-tetramethyl--1, adjacent Fei Luolin 2 mmoles of 10-are dissolved in the chloroform, add 6 mmole triethylamines then, under the condition of stirring heating, slowly drip 20 milliliters of the europium chloride ethanolic solns of every milliliter of 0.1 mmole.40 ℃ of reacting by heating 1 hour, remove reaction solvent, products therefrom Eu (TTA)
3(Tmphen) washing, ethanol is washed, recrystallization.With Eu (TTA)
3(Tmphen) being prepared into structure is ITO/TPD/Eu (TTA)
3(Tmphen): the electroluminescent device of CBP/BCP/AlQ/LiF/Al, in vacuum tightness 10
-4Organic and the metal electrode layer of evaporation under the pressure of handkerchief, the evaporation rate-controlling of organic layer is at 3 /s, and the vaporator rate of LiF is controlled 1 /s, and the evaporation rate-controlling of metal is at 5 /s, and doping content is controlled at 2%.Wherein, the TPD layer thickness is 40nm, Eu (TTA)
3(Tmphen) x:CBP layer 30nm, BCP layer are 20nm, and the AlQ layer is 30nm, LiF layer 1nm, Al layer 100nm.The obtained device direct voltage drive can obtain pure rare-earth europium ionic feature emission, and maximum efficiency is 4.1cd/A, and high-high brightness can reach 700cd/m
2
Embodiment 5:
Get trifluoroacetyl thiophene acetone (TTA) 6 mmoles and 3,4,7,8-tetramethyl--1, adjacent Fei Luolin 2 mmoles of 10-are dissolved in the chloroform, add 6 mmole triethylamines then, under the condition of stirring heating, slowly drip 20 milliliters of the europium chloride ethanolic solns of every milliliter of 0.1 mmole.50 ℃ of reacting by heating 1 hour, remove reaction solvent, products therefrom Eu (TTA)
3(Tmphen) washing, ethanol is washed, recrystallization.With Eu (TTA)
3(Tmphen) being prepared into structure is ITO/TPD/Eu (TTA)
3(Tmphen): the electroluminescent device of CBP/BCP/AlQ/LiF/Al, in vacuum tightness 10
-4Organic and the metal electrode layer of evaporation under the pressure of handkerchief, the evaporation rate-controlling of organic layer is at 4 /s, and the vaporator rate of LiF is controlled 1 /s, and the evaporation rate-controlling of metal is at 5 /s, and doping content is controlled at 1%.Wherein, the TPD layer thickness is 40nm, Eu (TTA)
3(Tmphen): CBP layer 30nm, BCP layer are 20nm, and the AlQ layer is 30nm, LiF layer 1nm, and Ca layer 10nm, the Al layer is greater than 100nm.The obtained device direct voltage drive can obtain pure rare-earth europium ionic feature emission, and maximum efficiency is 4.7cd/A, and high-high brightness can reach 800cd/m
2
Claims (3)
1. red light rare-earth organic complex electroluminescent material has following structure:
R1=phenyl wherein; The R2=phenyl; Or the R1=trifluoromethyl, the R2=2-thienyl.
2. the preparation method of a red light rare-earth organic complex electroluminescent material is characterized in that preparation process is:
Will as the diphenylpropane-1,3-dione(DPPO) of first part or trifluoroacetyl thiophene acetone with as 3 of second part, 4,7,8-tetramethyl--1, the adjacent Fei Luolin of 10-is dissolved in ethanol or the chloroform by 3: 1 mol ratio, the sodium hydroxide or the triethylamine of mole numbers such as the adding and first part under stirring condition, then, the solution of the trivalent europium ion of mole numbers such as the adding and second part, temperature of reaction is between 30 ℃-80 ℃, in 0.5 hour-4 hours reaction times, product washing, alcohol are washed, drying.
3. as claim 1 and 2 described red light rare-earth organic complex electroluminescent materials, it is characterized in that being used to prepare electroluminescent device, luminous efficiency reaches 4.7cd/A, and high-high brightness is 800cd/m
2
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313565C (en) * | 2004-07-23 | 2007-05-02 | 北京化工大学 | Rare earth/polymer composite luminous material and its preparation method |
| CN100355857C (en) * | 2005-07-06 | 2007-12-19 | 太原理工大学 | Preparation method of organic electro luminous material rare earth europium organic metal complex |
| CN102002062A (en) * | 2010-09-26 | 2011-04-06 | 中科院广州化学有限公司 | Polynuclear rare earth organic complex, and preparation method and application thereof |
| CN102584872A (en) * | 2012-02-10 | 2012-07-18 | 赵学辉 | Rare earth complex red flourescent material and preparation method thereof |
| CN101565364B (en) * | 2009-06-02 | 2012-10-03 | 安徽佳先功能助剂股份有限公司 | Synthetic method of Beta-diketone metal salt |
| CN104004121A (en) * | 2014-05-29 | 2014-08-27 | 常州大学 | Method for preparing aromatic carboxylic acid macromolecular fluorescent rare-earth complex |
| CN107176938A (en) * | 2016-03-11 | 2017-09-19 | 赵学辉 | A kind of triketone organic compound and preparation method and application |
| CN107176939A (en) * | 2016-03-11 | 2017-09-19 | 赵学辉 | A kind of new tripodia ketone ligand organic compound and preparation method and application |
| CN107946412A (en) * | 2017-12-25 | 2018-04-20 | 青岛大学 | A kind of preparation method of rare-earth complex solution and modified solar battery |
| CN108586505A (en) * | 2018-07-03 | 2018-09-28 | 广州工程技术职业学院 | Europium complex red light material and preparation method based on two the first ligands of difference |
| CN114437118A (en) * | 2022-01-26 | 2022-05-06 | 南京邮电大学 | Thienyl phenanthroline europium (III) complex material and preparation method and application thereof |
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- 2003-06-17 CN CNA031450520A patent/CN1470593A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313565C (en) * | 2004-07-23 | 2007-05-02 | 北京化工大学 | Rare earth/polymer composite luminous material and its preparation method |
| CN100355857C (en) * | 2005-07-06 | 2007-12-19 | 太原理工大学 | Preparation method of organic electro luminous material rare earth europium organic metal complex |
| CN101565364B (en) * | 2009-06-02 | 2012-10-03 | 安徽佳先功能助剂股份有限公司 | Synthetic method of Beta-diketone metal salt |
| CN102002062A (en) * | 2010-09-26 | 2011-04-06 | 中科院广州化学有限公司 | Polynuclear rare earth organic complex, and preparation method and application thereof |
| CN102002062B (en) * | 2010-09-26 | 2012-10-03 | 中科院广州化学有限公司 | Polynuclear rare earth organic complex, and preparation method and application thereof |
| CN102584872B (en) * | 2012-02-10 | 2015-11-11 | 赵学辉 | A kind of preparation method of rare earth compounding red fluorescence material and rare earth compounding red fluorescence material |
| CN102584872A (en) * | 2012-02-10 | 2012-07-18 | 赵学辉 | Rare earth complex red flourescent material and preparation method thereof |
| CN104004121A (en) * | 2014-05-29 | 2014-08-27 | 常州大学 | Method for preparing aromatic carboxylic acid macromolecular fluorescent rare-earth complex |
| CN107176938A (en) * | 2016-03-11 | 2017-09-19 | 赵学辉 | A kind of triketone organic compound and preparation method and application |
| CN107176939A (en) * | 2016-03-11 | 2017-09-19 | 赵学辉 | A kind of new tripodia ketone ligand organic compound and preparation method and application |
| CN107946412A (en) * | 2017-12-25 | 2018-04-20 | 青岛大学 | A kind of preparation method of rare-earth complex solution and modified solar battery |
| CN108586505A (en) * | 2018-07-03 | 2018-09-28 | 广州工程技术职业学院 | Europium complex red light material and preparation method based on two the first ligands of difference |
| CN114437118A (en) * | 2022-01-26 | 2022-05-06 | 南京邮电大学 | Thienyl phenanthroline europium (III) complex material and preparation method and application thereof |
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