CN1164712C - Organic electroluminescence material and device - Google Patents
Organic electroluminescence material and device Download PDFInfo
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- CN1164712C CN1164712C CNB021133824A CN02113382A CN1164712C CN 1164712 C CN1164712 C CN 1164712C CN B021133824 A CNB021133824 A CN B021133824A CN 02113382 A CN02113382 A CN 02113382A CN 1164712 C CN1164712 C CN 1164712C
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- luminescent
- luminescent material
- aluminium
- electroluminescent
- oxine
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Abstract
The present invention relates to an organic electroluminescent material and an electroluminescent device thereof. An aluminum 8-hydroxyquinolinate derivative luminescent material is designed and synthesized by introducing a base group onto the 5-bit of a quinoline ring of aluminum 8-hydroxyquinolinate. The luminescent material not only keeps the favorable luminescent performance and the electronic transmission capability of aluminum 8-hydroxyquinolinate, but also is uniformly dissolved in organic polymers. The luminescent material can also be made into novel luminescent materials by compounding kinds and proportion according to luminescent colors. The electroluminescent device prepared by the luminescent material has a single layer composite function film; the compounded luminescent material can make the luminescent device emit light of various colors, comprising white light. The electroluminescent device of the present invention has the advantages of simple structure, easy regulation and control and material saving. The present invention overcomes the disadvantages that luminescent polymer materials have large manufacture difficulty, difficult refinement and single color, small molecule luminescent materials need high vacuum vapor deposition and complex manufacture technology when used for manufacturing luminescent devices, etc.
Description
One, technical field
The present invention relates to technical field of electronic materials, particularly relate to electroluminescent organic material and electroluminescent device thereof.
Two, background technology
Organic electroluminescent (OEL) is that organic materials is excited and luminous phenomenon under the extra electric field effect, promptly by organic materials electric energy is directly changed into a kind of energy transformation mode of luminous energy.This be one in the emerging cross discipline that just obtains over past ten years developing rapidly, it relates to fields such as organic functional material, photoelectron technology and physics, information and display material and technology.Because it has and common indicating meter incomparable advantage as flat-panel monitor, so become the focus of current international research.
As far back as the sixties, just there is people's experimental observation to arrive the blue coloured electroluminous of anthracene.To obtain epoch-making development be in the late nineteen eighties and electroluminescent organic material is used for luminescent device (OELD), for example the human small molecules electroluminescent materials such as C.W.Tang of U.S. Eastman kodak company are produced double-deck electroluminescent device, send green glow [Appl.Phys.Lett, 51 (1987) 913] under the low voltage.Subsequently, people such as J.H.Bveronghs of univ cambridge uk has made the electroluminescent device [Nature, 347 (1990) 539] of single layer structure first of polymer electroluminescence material.From then on, the research of electroluminescent organic material is developed in depth and breadth to organism small molecules and polymkeric substance both direction, and becomes the another focus of flat-panel monitor research.
At present, the making of electroluminescent device mainly contains two kinds of methods---vacuum evaporation and spin-coating film.The small molecules luminescent material is used to make luminescent device and mainly adopts Vacuum Coating method, generally is to be 10 in vacuum tightness
-4In the vacuum chamber of handkerchief, on tin indium oxide (ITO) the conductive glass substrate in order on the evaporation buffer layer, hole transmission layer, luminescent layer and electron transfer layer at interior organic functional material, metal electrode on the last evaporation.Scoop up the multilayer small molecules electroluminescent device of wild true instrument, assistant rattan Cui fine making with a dustpan as Japan, its structure is: ITO/ anode buffer layer/hole transmission layer/luminescent layer/electron transfer layer/Ca.[day disclosure special permission communique, the spy opens flat 11-16680].The small molecules luminescent material is used to make its vacuum tightness requirement height of method of luminescent device, thereby cost of manufacture is also high, the processing requirement relative complex, and fabrication cycle is longer, and realizes that big area shows certain difficulty.With the method that polymer electroluminescence material is made luminescent device, ripe, commonly used is spin-coating method at present.At first polymer electroluminescence material is dissolved in the organic solvent, is added drop-wise to again on the ito glass substrate, throw away very thin film, metal electrode in the last vacuum evaporation with sol evenning machine.Luminescent device structure: ITO/PVK+TAZ (20nm) (whirl coating)/Alq3 (40nm) (evaporation)/Mg.Ag.[Chem.Lett, 1991,1267].
Though polymer electroluminescence material is easy to make luminescent device and second-order transition temperature height by spin-coating method, be not prone to the interface and divide equal problem, but be difficult to when it is synthetic separate and purify, and the superpolymer that will obtain narrow molecular weight distribution is difficult more, thereby directly influences the effect of luminescent device.
Oxine is at present as a best compound of the performance of green light in the electroluminescent organic material.But oxine is insoluble to common organic solvent, then be difficult to make electroluminescent device by even glue process, thereby existing method all is that method with vacuum evaporation coating just can reach film-formation result.
Three, summary of the invention
The present invention then is at above-mentioned electroluminescent organic material and is used for making the existing defective of electroluminescent device, proposition is transformed the structure that oxine closes aluminium, promptly introduce group on 5 on quinoline ring, design synthesizes the series derivates that oxine closes aluminium.They are to close aluminium and grip altogether under the prerequisite of system not influencing oxine, have both kept its good luminous property and electron transport ability, can be dissolved in the compounds in the organic polymer again uniformly and stably mutually.It is miscible in organic solvent that oxine is closed the derivative of aluminium and carrier transmission material and polymer support, stir into a homogeneous solution, then this solution is spin-coated on the electroluminescent device that then can be made into the individual layer composite function film on the substrate, this luminescent device is simple in structure, easy to operate, and economical with materials.
The present invention designs the synthetic organic electro luminous material 8-hydroxy quinoline and closes the aluminium derivative, has following structure:
Y representative in the said structure formula: O, S;
R representative: contain the alkyl of 1-12 carbon atom, cycloalkyl, thiazolinyl, alkynyl, aryl or virtue
Alkyl;
-COR
1,-COOR
1, R wherein
1=H, contain 1-6 carbon atom alkyl and
/ or cycloalkyl and/or aromatic base.
The preferred electroluminescent organic material of the present invention is that 5-alkoxyl-methyl-oxine closes the aluminium derivative, and its structure is as follows:
R=-CH in the said structure formula
3(compound 1);
=-C
2H
5(compound 2);
=CH
2CH
2CH
3(compound 3);
=-CH
2CH
2CH
2CH
3(compound 4);
The another preferred electroluminescent organic material of the present invention is that 5-alkyl sulfide methyl-oxine closes the aluminium derivative, and its structure is as follows:
R=-CH in the said structure formula
3(compound 6);
=-C
2H
5(compound 7);
=-CH
2CH
2CH
3(compound 8);
=-CH
2CH
2CH
2CH
3(compound 9);
The above compound all is to have good photoluminescence and electroluminescent properties and electron transport ability, and is soluble in organic solvent and highly stable in the matrix of organic polymer, and fused mutually.
Electroluminescent organic material of the present invention both can be that oxine closes the aluminium derivative, it also can be the luminescent material of other kinds, it can also be the mixture of two kinds or above electroluminescent organic material, promptly can be composite in addition to its kind and ratio by the glow color requirement, make new electroluminescent material.
Electroluminescent organic material of the present invention has following characteristics:
1, the present invention has avoided polymer electroluminescence material molecular weight distribution in building-up process to be difficult to the difficulty of controlling and separating, purify.
2, luminescent material of the present invention has overcome oxine and has closed the shortcoming that aluminium is insoluble in organic solvent.
3, electroluminescent organic material of the present invention can be composite in addition to its kind and ratio by the glow color requirement, makes new luminescent material.
4, electroluminescent organic material of the present invention after the even glue film forming of the composite dissolving of polymer support, can form even, clear films owing to be soluble in organic solvent.
Four, description of drawings
Fig. 1 is the double layer sandwich structure light-emitting device architecture synoptic diagram that prior art small molecules electroluminescent material adopts vacuum vapour deposition to make.
Fig. 2 adds the individual layer sandwich structure luminescent device structural representation that vapour deposition method is made for the prior art polymer electroluminescence material adopts spin-coating method.
Fig. 3 closes the individual layer composite function film luminescent device structural representation that aluminium derivative electroluminescent organic material is made for 8-hydroxyl caye quinoline of the present invention.
1 is glass substrate among the figure, and 2 is the ITO conductive layer, and 3 is anode buffer layer, and 4 is hole transmission layer, and 5 is luminescent layer, and 6 is electron transfer layer, and 7 is metal electrode, and 8 is composite function film.
Five, embodiment
Below in conjunction with embodiment the electroluminescent organic material that the present invention proposes is described further.
The preferred electroluminescent organic material of the present invention is that 5-alkoxyl-methyl-oxine closes the aluminium derivative, and its structure is as follows:
R=-CH in the said structure formula
3(compound 1);
=-C
2H
5(compound 2);
=-CH
2CH
2CH
3(compound 3);
=-CH
2CH
2CH
2CH
3(compound 4);
At first prepare midbody compound:
Synthesizing of midbody compound 5-chloromethyl-oxine hydrochloride:
Get 15 gram oxines and put into reaction flask, adds 36 milliliters of formaldehyde solutions, 36 milliliters of concentrated hydrochloric acids place in the ice-water bath, the feeding hydrogen chloride gas reacted 4 hours.Suction filtration precipitates then, and washes precipitation 2 times with ether, and infrared lamp is oven dry down, promptly gets product 18 grams, fusing point, 283 ℃ (decomposition).
Embodiment one (synthesizing of compound 1):
Change the preparation that contains matter sample:
Got 10 gram 5-chloromethyl-oxine hydrochlorides and 100 ml methanol back flow reaction 3 hours, reaction solution is poured in 250 ml waters, with yellow soda ash (Na
2CO
3) the solution neutralization, have a large amount of solids to separate out this moment, carries out suction filtration solid product, washing again, and the normal hexane recrystallization gets 8.3 gram 5-methoxyl methyl-oxines, 79～80 ℃ of fusing points (mp).
3 gram 5-methoxyl methyl-oxines are dissolved in the mixing solutions of 20 milliliters of ethanol and 7 ml waters, drip the aqueous solution that contains 0.78 gram aluminum chloride, stirred 20 minutes, use Na
2CO
3(yellow soda ash) solution adjust pH is separated out precipitation to 5-6, takes out the Shanghai precipitation, wash crude product 1.9 grams, recrystallization gets pure product compound 1 in the ethanol.Its structure is proved by nuclear magnetic resonance spectrum and ultimate analysis.
Embodiment two (synthesizing of compound 2):
The preparation of compound sample:
Method according to synthetic compound 1 is carried out, as long as change methyl alcohol into ethanol, crude product gets final product with ethanol and ether mixed solvent purifying.
Embodiment three (synthesizing of compound 3):
The preparation of compound sample:
Method according to synthetic compound 1 is carried out, as long as change methyl alcohol into n-propyl alcohol, crude product gets final product with ethanol and ether mixed solvent purifying.
Embodiment four (synthesizing of compound 4):
The preparation of compound sample:
Got 5-methoxyl methyl-oxine 10 gram and 100 milliliters of propyl carbinol back flow reaction 4 hours, cool off, separate out yellow solid 5-fourth oxygen methyl-8 hydroxyquinoline hydrochloride, suction filtration, wash with ether, vacuum-drying gets 9.2 grams, the preparation method of complex compound is the same, gets final product with ethanol and ether mixed solvent purifying.
Embodiment five (synthesizing of compound 5):
The preparation of compound sample:
Method according to synthetic compound 4 is carried out, as long as change 100 milliliters of propyl carbinols into different the eleventh of the twelve Earthly Branches alcohol.
Below in conjunction with accompanying drawing electroluminescent device of the present invention is described further.
Electroluminescent device of the present invention is made up of ITO conductive layer 2, composite function film 8 and the metal electrode 7 of glass substrate 1, low-resistance.Composite function film 8 has substituted anode buffer layer 3, hole transmission layer 4, luminescent layer 5 and electron transfer layer 6.Composite function film is oxine to be closed aluminium derivative luminous organic material, hole mobile material and carrier polymer are miscible to stir into a homogeneous solution in organic solvent, again this homogeneous solution is spin-coated on the ITO conductive glass substrate and makes the individual layer composite function film, plate metal electrode then and promptly be prepared into the electroluminescent device of individual layer composite function film, this luminescent device can send green glow.The square resistance of electroluminescent device of the present invention requires in 10 Europe/below the mouth.The ito glass substrate need carry out clean before using.Luminescent device of the present invention is made of the electroluminescent organic material after composite, just can make luminescent device send versicolor light, even send white light.
The selection of the used carrier transmission material of electroluminescent device of the present invention can be electron transport material and hole mobile material two big classes, and electron transport material commonly used has OXD-7, PBD, TAZ etc., and its structure is as follows:
Hole mobile material commonly used has TPD, α-NPB, PVK etc., and its structure is as follows:
Only adopt a kind of compound as carrier transmission material in each luminescent device of the present invention, its effect hole mobile material preferably is TPD, PVK, carrier transmission material and luminescent material weight ratio are between 1: 0.55～1: 3, and best effect is between 1: 0.5～1: 2.Can also be gold-plated on the glass substrate 1 of the present invention, with gold-plated glass as substrate.
The polymer materials that the present invention can be used as carrier has polycarbonate, polymethyl methyl esters, (one, two, three or four) alkane ester, polystyrene, also can be two or more monomeric multipolymers or above-mentioned mixture of polymers, polymer support is after forming composite function film, the ratio of its weight and total mass is 10%～40%, and optimum proportion is between 15%～30%.
Organic solvent commonly used has toluene, dimethylbenzene, ethylene dichloride, chloroform etc.
The present invention makes its spin coating speed of rotation of electroluminescent device and is chosen in 1000～3000 rev/mins, and optimum revolution is at 15002500 rev/mins, and room temp is at 20～25 ℃.
But as metal electrodes such as the cathode material aluminium of electroluminescent device, magnesium silver alloys, calcium, lithium/aluminium, best results be calcium and magnesium/silver metal electrode.
Electroluminescent device of the present invention has following characteristics:
1, electroluminescent device of the present invention is the luminescent device of individual layer composite function film.
2, electroluminescent device making processes of the present invention is easy and simple to handle, has both kept the advantage of traditional method, has saved the complicated technology of high vacuum vapor deposition again, and is easy to regulation and control, economical with materials.
3, this electroluminescent device is simple in structure, does not need the multilayer evaporation.
4, this electroluminescent device institute is luminous can use composite electroluminescent organic material by glow color requirement design, then can obtain versicolor light, comprises white light.
Below be electroluminescent device embodiment of the present invention:
Embodiment one
Luminescent device 1 structure (Fig. 3): ITO/ compound 1+TPD+PC (2: 2: 1)/Al
ITO/ compound 2+TPD+PC (2: 2: 1)/Al
ITO/ compound 3+TPD+PC (2: 2: 1)/Al
ITO/ compound 4+TPD+PC (2: 2: 1)/Al
ITO/ compound 5+TPD+PC (2: 2: 1)/Al
All can send in the luminescent device 1 to oxine and close the similar green light of aluminium spectrum, radiative main peak is between 520526 nanometers.Luminosity 200～500cd/m
2
Embodiment two
ITO/ compound 2+PVK+PC (2: 2: 1)/Al
ITO/ compound 3+PVK+PC (2: 2: 1)/Al
ITO/ compound 4+PVK+PC (2: 2: 1)/Al
ITO/ compound 5+PVK+PC (2: 2: 1)/Al
All send in the luminescent device 2 to oxine and close the similar green light of aluminium spectrum, radiative main peak is between 523～530 nanometers.Luminosity 200～500cd/m
2
Embodiment three
This luminescent device is made of the electroluminescent organic material after composite, and its structure is as follows:
ITO/ compound 2+PVK+Eu (TTA)
2(PMBBP) phen/Al
Obtain white light, luminosity 150cd/m
2
Eu (TTA) wherein
2(PMBBP) phen has following structure:
Eu (TTA)
2(PMBBP) the phen compound is synthetic referring to people Synthetic Metals111-112 (2000) such as Weiguo Zhu, 445-447.
Claims (4)
1, a kind of electroluminescent organic material is characterized in that adopting on oxine closes 5 on the quinoline ring of aluminium and introduces group, made the derivative luminescent material that oxine closes aluminium, and this luminescent material has following structure:
Y representative in the said structure formula: O, S;
R representative: contain the alkyl of 1-12 carbon atom, cycloalkyl, thiazolinyl, alkynyl, aryl or
Aralkyl;
-COR
1,-COOR
1, R wherein
1=H, contain the alkyl of 1-6 carbon atom
And/or cycloalkyl and/or aromatic base.
2, according to the described luminescent material of claim 1, it is characterized in that it is that 5-alkoxyl-methyl-oxine closes aluminium that oxine closes in the aluminium derivative preferred luminescent material, this luminescent material has following structure:
R=-CH in the said structure formula
3
＝-C
2H
5
＝CH
2CH
2CH
3
＝-CH
2CH
2CH
2CH
3
3, according to the described luminescent material of claim 1, it is characterized in that oxine closes that another preferred luminescent material is that 5-alkyl sulfide methyl-oxine closes aluminium in the aluminium derivative, this luminescent material has following structure:
R=-CH in the said structure formula
3
＝-C
2H
5
＝-CH
2CH
2CH
3
＝-CH
2CH
2CH
2CH
3
4, according to claim 1 or 2 or 3 described luminescent materials, it is characterized in that it both can being that oxine closes the aluminium derivative, it can also be the mixture of two kinds or above electroluminescent organic material, promptly can be composite in addition to its kind and ratio by the glow color requirement, make new electroluminescent organic material.
5, according to the described luminescent material of claim 1, it is miscible in organic solvent to it is characterized in that the above-mentioned oxine of making can being closed aluminium derivative luminescent material and carrier transmission material and polymer support, stir into a homogeneous solution, then this solution is spin-coated on the substrate, then can be made into the electroluminescent device of individual layer composite function film.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021133824A CN1164712C (en) | 2002-02-22 | 2002-02-22 | Organic electroluminescence material and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021133824A CN1164712C (en) | 2002-02-22 | 2002-02-22 | Organic electroluminescence material and device |
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|---|---|
| CN1367223A CN1367223A (en) | 2002-09-04 |
| CN1164712C true CN1164712C (en) | 2004-09-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100503655C (en) * | 2003-06-02 | 2009-06-24 | 日本轻金属株式会社 | Luminescent organic-polymer/metal complex, luminescent organic-polymer/metal complex composition capable of forming film by wet process, and process for producing the same |
| TWI390006B (en) * | 2003-08-07 | 2013-03-21 | Nippon Steel Chemical Co | Organic EL materials with aluminum clamps |
| CN1325530C (en) * | 2004-08-26 | 2007-07-11 | 复旦大学 | Luminous polyurethane material and its synthesis method |
| CN101747887A (en) * | 2008-12-08 | 2010-06-23 | 中国科学院福建物质结构研究所 | Organometallic polymer white fluorescence luminescent material and preparation method thereof |
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