Electroluminescent material containing organic luminescent substance

FIELD: luminescent materials.

SUBSTANCE: invention provides novel electroluminescent material comprised of injecting layer, metal chelate complex-based active luminescent layer, hole-transition layer and hole-injecting layer. Luminescent substance is selected from oxyquinolate metallocomplexes of zinc 8-hydroxy-2-methoxyquinolate and zinc 8-hydroxy-2-methylquinolate. Electroluminescent material shows emission in green spectrum region.

EFFECT: increased heat resistance and widened choice of stable green-emitting materials.

2 cl, 3 ex

 

The invention relates to electroluminescent materials containing organic fluorescent substance.

Known electroluminescent material (ELM), containing a luminescent layer evaporated layer of organic compounds - 8- aluminum [C.W.Tang, S.A.Van Slike Appl.Phys.Letter 51, 913-915 (1987)]. At the same time as the hole-an injecting layer (anode) is applied transparent low-resistance layer based on a mixed oxide of indium and tin, In2About3-SnO2(ITO), and as electron - an injecting layer (cathode) - alloy Mg-Ag.

The closest to the technical nature of the present device is ELM, consisting of electron-an injecting layer (cathode) (alloy Mg-In 10:1), an active luminescent layer, hole-transport layer of N,N'-diphenyl-N,N'-(3-were)-1,1'-biphenyl-4,4'-diamine (TPD) and hole-an injecting layer (anode) (In2O3-SnO2), and an active luminescent layer contains a fluorescent substance - chelate complexes of various metals (particularly zinc) with 8-oksikhinolinata ligands [T.Sano, Y.Nishio et al. Design of conjugated molecular materials for optoelectronics. J. of Materials Chemistry, 2000, v.10, p.157-160]. The structure on the basis of such a layered material has a photo - and electroluminescence from green to yellow (λmax=503-567 nm ) depending on the choice of metal (Al, Be, Zn, Mg), which p is portionally current density in the range of 1-10 mA/cm 2and spectra of photo - and electroluminescence are almost identical. 8- zinc emission maximum is in the yellow area. The lack of materials on the basis of oxyhydrates and TPD is the high sensitivity to moisture and oxygen, which makes it difficult to work with them as in the manufacture and in the operation of the devices (high demands on tightness), and low temperature resistance. Although the resistance of oxyhydrates high enough (in particular, Alg3has a melting point of 360°s), but the morphology of the hole-transport layer, consisting of TPD varies even at room temperature due to a low glass transition temperature (<60°). Heating during operation of the device leads to a change in the electrical transport properties of the layer and, as a consequence, the loss of the electroluminescence device, i.e. the loss of life of the device.

The present invention is the creation of electroluminescent material with radiation in the green region of the spectrum and high temperature performance.

The problem is solved by the fact that according to the invention the electroluminescent material consisting of e an injecting layer, an active luminescent layer-based fluorescent substance, a hole-transport layer and the hole-an injecting layer, ka is este fluorescent substance contains one of the first synthesized oxichinolina metal complexes of 8-hydroxy-2-methoxyquinoline zinc (I) or 8-hydroxy-2-methylinosine zinc (II):

Replacement of a hydrogen atom in the 2-position by methoxy or metal group do not alter the ability of a substance to the electroluminescence, but affect its solubility in organic solvents and allow small shift of the maximum wavelength of the photo - and electroluminescence, that is, to fine-tune electroluminescent properties.

As the hole-transport layer material may contain, for example, TPD. We offer the electroluminescent material as a hole-transport layer preferably contains a mixture of oligomers of triphenylamine with the General formula

where n=8-9, when the molecular-mass distribution: Mn=2332, Mw=3586 characterized by high glass transition temperature 185°that ensures the preservation of the morphology of the hole-transport layer even at elevated temperatures [Yakushenko I.K., Kaplunov MG, Shamayev, S.N., Efimov O.N., Nikolaeva, GV, Belov, M., Marchenko, H.E., starlings A.G., Voronin, VA "a Method of obtaining a mixture of oligoadenylates, the method of obtaining 3-(4-biphenylyl)-4-(4-tertbutylphenyl)-5-(4-dimethylamino-phenyl)-1,2,4-triazole and the electroluminescent device," the Patent of the Russian Federation N2131411 from 10.06.99].

The invention is illustrated by the following examples.

Example 1. Synthesis of 8-hydroxy-2-methoxyquinoline the Inca

The scheme for synthesis of:

1. 8-hydroxyquinolin-1-oxide (III)

To a solution of 100 g (0,69 M) 8-hydroxyquinoline solution in a mixture of 140 ml of glacial acetic acid and 300 ml of water was added 160 g of 30%hydrogen peroxide. The mixture is then boiled under reflux for 3 hours, cooled, extracted with chloroform (4×200 ml). The organic extract was successively washed with 5%hydrochloric acid, water. After drying over anhydrous magnesium sulfate the solvent was removed at atmospheric pressure. The residue was recrystallized from benzene. Received 42.8 g of product with TPL=138°C. the Yield of 38.6% of theoretical.

Literature data [I.Murase Y.Demura, Mem. Fac. Sci. Kyushu Univ., Ser. C4, N3 (1961); Chem/ Abstr.58, 3390b (1963)]: TPL=138 C.

2. Methosulfate 8-hydroxy-1-methoxyquinoline (IV)

To 57,0 g (0.35 M) 8-hydroxyquinolin-1-oxide (III) was added under stirring 44.4 g (0.35 M) dimethylsulfate, after which the mixture was heated on a boiling water bath for 2 hours. By the end of this period the mixture was gomogenizirovannykh. Upon cooling the reaction mass was stirred until the beginning of crystallization, was added 200 ml of dry diethyl ether, dried in vacuum. Got 91 g of crude product, which was used further without additional purification. A yield of about 90% of theoretical.

3. 8-hydroxy-2-methoxyaniline (V)

To a solution of sodium methylate received the CSOs by dissolving 22 g (0,96 M) of sodium in 380 ml of anhydrous methanol and cooled to 0-2° C was added dropwise a solution of 91 g (0,32 M) methosulfate 8-hydroxy-1-methoxyquinoline (IV) in 270 ml of dry methanol. After the addition of all of the reagent mixture was stirred at the same temperature for another 2 hours, then left for a day at room temperature. To the reaction mass was added 600 ml of water, kept the methanol and water solution to neutralize acetic acid to pH 7. The precipitate was extracted with benzene, the extract was dried over anhydrous magnesium sulfate, treated with silica gel (15-20 g)was filtered and from the filtrate drove the solvent, the residue was recrystallized from hexane. Got to 44.7 g of the product, TPL=50,5°C. the Yield 82.0% of theoretical.

Literature data [Vimco, Iagreement, Upoading, "Methods of obtaining chemicals and drugs", vol. 14, M. area. 1966. P.88-89]: TPL=a 50.5-51°C.

4. 8-hydroxy-2-methoxyquinoline zinc (I)

The synthesis was carried out in an inert atmosphere (argon). To a solution of 4.45 g (25.4 mM) 8-hydroxy-2-methoxyaniline (V) in 30 ml of methanol was added at room temperature and stirring, a solution of 1.43 g (25.4 mM) of potassium hydroxide in 12 ml of methanol. The mixture was stirred for another 5 min, and then thereto was added dropwise a solution of 1.73 g (12.7 mM) of anhydrous zinc chloride in 15 ml of methanol. In the process of adding the formed yellow precipitate. The reaction mass was stirred for another 15 min, drove the methanol under reduced pressure, to the residue was added 100 ml of water. The precipitate was filtered off, washed on the filter with water, dried in vacuum. Got to 5.93 g of yellow powder. It was dissolved in 80 ml of dry pyridine at 50-55°C, was filtered from the insoluble components, the filtrate was diluted with an equal volume of hexane. The precipitate was filtered and then washed on the filter with benzene, diethyl ether, hexane. Dried in vacuum over pjatiokisi phosphorus. Got 4,82 g complex. Exit 92% of theoretical.

Elemental analysis. Found,%: 59,42; N. Of 3.85; N 6,46; Zn (as ZnO) 20,20. Brutto-formula C20H16N2O4Zn. Calculated, %: 58,06; N 3,90; N 6,77; Zn (as ZnO) 19,67.

IR-spectrum (KBr tablet, the frequency of maximum absorption, cm-1): 3435.5; 3127 SL; 3088 SL; 3048 CL; CL 3024; 2990 SL; 2945 SL; 2924 SL; 2852 cf; 1610 cf; 1590 SL; 1578 cf; 1509 cf; 1473 OSL; 1466; 1441 cf; 1430 SL; 1390 cf; 1341; 1316 cf; 1293; 1273 SL; 1220 SL; 1185 SL; 1170 SL; 1150 cf; 1106; 1074 SL; 1065 CL; 1040 cf; 1020 OSL; 976 SL; SR 874; 826; 796 cf; 748; 703 cf; 615 SL; 586 OSL; 572 OSL; 562 SL; 536 OSL; 520 SL; 424 SL. Qualitative indicate the relative intensities of absorption bands: OSL is very weak, SL - weak, Wed - medium, s - strong, OS - very strong, square - shoulder.

The presence of bands of stretching vibrations of C-H in the region 3000-3100 cm1and bands of vibrations of double bond C=C in the field 1500-1600 cm-1under the submits the presence of paired links the carbon-carbon bonds.

Example 2. Synthesis of 8-hydroxy-2-methylinosine zinc

The scheme for synthesis of:

1. 8-hydroxy-2-methylinosine zinc (II)

The synthesis was carried out in an inert atmosphere (argon). To a solution of 3.98 g (25 mmol) of 8-hydroxy-2-methylinosine in 15 ml of methanol was added at room temperature and stirring, a solution of 1.4 g (25 mmol) of potassium hydroxide in 12 ml of methanol. The mixture was stirred for another 10 min, and then thereto was added dropwise a solution of 1.70 g (12.5 mmol) of anhydrous zinc chloride in 10 ml of methanol. Formed yellow precipitate. After 20 min of the reaction mixture, the solvent was removed under reduced pressure, was added 50 ml of water, stirred and the precipitate was filtered. It was washed on the filter with water, dried in vacuum. Received of 4.66 g of yellow powder. It was dissolved in 75 ml of pyridine at 50-55°C, was filtered, the filtrate was cooled to room temperature and was added with stirring an equal volume of hexane. The precipitation was filtered, washed on the filter with diethyl ether, hexane, dried in vacuum over pjatiokisi phosphorus. Received 4.15 g of the complex (87.1% of theoretical).

Elemental analysis. Found, %: C 62,64; N. Of 4.57; N 7,76; Zn (as ZnO) 20,75. Brutto-formula C20H16N2O2Zn. Calculated, %: C 62,92; N 4,22; N 7,33; Zn (as ZnO) one-21.32.

IR-spectrum (KBr tablet). 3436; 3064 OSL; 3052 OSL; 3036 OSL; 2924 OSL; 2850 acting is l; 1954 SL; 1910 SL; 1630 OSL; 1606 cf; 1592 cf; 1568 OSL; 1507 OSL; 1463; 1450 OSL; 1428 cf; 1378 OS; 1340 OS; 1319 OSL; 1308 cf; 1283 cf; CL 1248; 1240 OSL; 1218 OSL; 1210 OSL; 1178 SL; 1142 CL; 1110.22; 1064 CL; 1045 OSL; 1034 SL; 1016 CL; 978 OSL; 956 SL; 925 SL; 876 SL; 869 OSL; 832 OS; 796 SL; 750 OS; 742 OSL; 705 SL; 673 OSL; 641 OSL; 600 cf; 592 OSL; 567 CL; 510 cf; 469 cf; 432 cf.

Example 3. The use of complexes I and II

The maximum absorption for cut film 375 nm for I and 386 nm for II. The maximum photoluminescence (excitation radiation 370 nm) film I at 514 nm for films II at 520 nm, half-width of the photoluminescence spectra of about 100 nm.

For the manufacture of electroluminescent devices with the structure ITO/HTL/EML/Mg:Ag, where ITO - hole-an injecting layer, HTL - hole-transport layer, EML - electroluminescent layer and Mg:Ag - electron-an injecting layer, use a glass substrate coated with a transparent layer of a mixed oxide of indium and tin with resistance 20-25 Ohms/square. On a substrate applied a hole-transport layer, consisting of TPD or MOUTH. When TPD is applied by evaporation in a vacuum, and MOUTH - by centrifuging from a solution in toluene. The thickness of the hole-transport layer 0.05-0.1 μm. Then by the evaporation of complex I, obtained according to example 1, or complex II, obtained according to example 2, in vacuum at a temperature of approximately 350°and a base pressure of 5·10-6mm Hg is applied activeselectionset layer thickness of 0.02-0.05 micron. The sample is placed in a vacuum installation VUP-4, pump out in a dynamic mode to vacuum 5·10-6mm Hg and sprayed metal electrode by evaporation of an alloy containing magnesium (90%), and silver (10%). The thickness of the metal electrode is about 0.1 μm. The area of the illuminated surface of 4-5 mm2. Received ELU emits blue-green light when a forward voltage. In particular, the device containing TPD and I, has the following parameters: brightness of 140 CD/m2is achieved at a voltage of 16 V and a current density of 24 mA/cm2(efficiency 4 CD/A).

1. The electroluminescent material consisting of e an injecting layer, an active luminescent layer-based fluorescent substance, a hole-transport layer and an injecting hole layer, characterized in that the fluorescent substance contains one of oxichinolina metal complexes of 8-hydroxy-2-methoxyquinoline zinc (I) or 8-hydroxy-2-methylinosine zinc (II)

2. The electroluminescent material according to claim 1, characterized in that it as a hole-transport layer contains a mixture of oligomers of triphenylamine with the General formula

where n=8-9, when the molecular weight distribution of Mn=2332, Mw=3586.



 

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