The electroluminescent material containing an organic luminescent substance

 

(57) Abstract:

The invention relates to electroluminescent materials containing organic fluorescent substance. Describes a new electroluminescent material consisting of e an injecting layer, an active luminescent layer based on chelate complex metal 2B or 3A group of the Periodic system, hole-transport layer and the hole-an injecting layer. As the luminescent layer contains a complex of a derivative of 8-mercaptoquinoline General formula I, where n = 2-3, M = Zn, CD, Ga; R1-R6independently from each other H, methyl; R3, R4independently of one another phenyl, unsubstituted or substituted stands, tert.bootrom; R3-R5independently from each other, a methoxy group, ethoxypropan, dimethylaminopropyl, diethylaminopropyl, nitrile. The technical result - the creation of electroluminescent material with radiation in the green region of the spectrum, less sensitivity to moisture and increased thermostability. 2 C.p. f-crystals, 1 PL.

The invention relates to electroluminescent material containing an organic fluorescent substance.

Known electroluminescent is chinoline (q) aluminum (Alq3) [C. W. Tang, S. A. Van Slike, Appl.Phys.Letter v. 51, pp. 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, In2O3- SnO2(ITO), as well 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 with a mass ratio of 10:1), an active luminescent layer, hole-transport layer containing N,N'-diphenyl-N,N'-(3-were)-1,1'-biphenyl-4,4'-diamine (TPD) and hole-an injecting layer (anode) (In2O3- SnO2), which contains as an active luminescent layer chelate complexes of 8-oksihinolina (q) with metals 2B or 3A group of the Periodic system (M= Al, Be, Zn, Mg) (q3) [N Tokito, Materials for organic electroluminescent elements on the basis of metal complexes, 6th Seminar of Organic electroluminescent elements from basic knowledge to practical technologies. Institute of technology, Saitama, G. Hirasawa; Y. Hamada et al. Organic electroluminescent devices with 8-Hydroxyquinoline derivative-metal complexes as an emitter, Japanese Journal of Applied Physics, Part 2, vol.32, no.4 A, 1 April 1993, pp.L514-L515]th color (max= 503-567 nm) depending on the choice of metal (Al, Be, Zn, Mg), which is proportional to the current density in the range of 1-103mA/cm2and spectra of photo - and electroluminescence are almost identical. For complexes of zinc emission maximum is in the yellow area. The lack of materials on the basis of Mq3is the high sensitivity to moisture and oxygen, which makes it difficult to work with them both at manufacturing and operating devices (high demands on tightness). Although 8-oksikhinolinata have a high temperature resistance (in particular Alq3has a melting point of 360oC), but the morphology of the hole-transport layer, consisting of TPD varies even at room temperature due to a low glass transition temperature (<60 oC). 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, less sensitivity to moisture and increased thermostability.

The problem is solved the active luminescent layer, containing chelate derived 8-mercaptoquinoline with metal 2B or 3A of the Periodic system, with the General formula

< / BR>
where n=2-3, M=Zn, Cd, Ga, R1-R6independently from each other H, methyl; R3, R4independently of one another phenyl, unsubstituted or substituted stands, tert. bootrom, R3-R5independently from each other, a methoxy group, ethoxypropan, dimethylaminopropyl, diethylaminopropyl, nitrile, hole-transport layer and the hole-an injecting layer.

Group R1-R6in the derived 8-mercaptoquinoline not change 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 luminescent properties.

Introduction mercaptopropyl instead of actigraphy leads to the shift of the radiation in the short wavelength region. In addition, mercaptopropyl is less hydrophilic than oxygraph.

We offer the electroluminescent material as a hole-transport layer contains a mixture of oligomers with the General formula

< / BR>
where n= 8-9, when the molecular weight is P>oC compared with TPD, which ensures the preservation of the morphology of the hole-transport layer even at elevated temperatures [Yakushenko I. K., Kaplunov M,, Shamayev S. N., Efimov, O. N., Nikolaev, C., Belov, M. J., Marchenko, E. P., A. Skvortsov,, Voronin, C. A. "a Method for obtaining a mixture of oligotrophication and 3-(4-biphenylyl)-4-(4-tertbutylphenyl)- 5-(4-dimethylaminophenyl)-1,2,4-triazole as materials for electroluminescent devices and electroluminescent device on the basis of their Application for the patent of the Russian Federation N 97118798/04 from 20.11.97, a positive decision from 2.06.98].

Example 1. Synthesis of 8-mercaptoquinoline.

Bis(8-hinokitiol)zinc(II), Zn(MQ)2< / BR>
< / BR>
In a flask with a capacity of 100 ml, equipped with a magnetic stirrer, addition funnel and reflux condenser, was placed a 4.03 g (0,022 mol) of sodium salt of 8-mercaptoquinoline and 35 ml of methanol. The mixture was heated in an argon atmosphere with stirring until the salt is completely dissolved (the temperature of the mixture to about 50oC). Then to the resulting solution was added dropwise a solution of 1.36 g (0.01 mol) of anhydrous zinc chloride in 20 ml of methanol. After the addition of zinc salts, the reaction mixture was heated to 55-60oC for 20 min, cooled to room temperature and Rabaul the major MgSO4. Received at 3.35 g of the complex. The yield of 87.0% of theoretical (counting on zinc chloride). TPL=292-293oC.

Elemental analysis.

Found, %: C 55,80; H 3,21; N 7,52; S 16,62; Zn 17,05.

Brutto-formula C18H12N2S2Zn.

Calculated, %: C 56,10; H 3,11; N 7,27; S 16,61; Zn 16,91.

IR-spectrum (KBr tablet) given in the table.

Bis(8-hinokitiol) cadmium (II), Cd(MQ)2< / BR>
< / BR>
In a flask with a capacity of 100 ml, equipped with a magnetic stirrer, addition funnel and reflux condenser, was placed a 4.03 g (0,022 mol) of sodium salt of 8-mercaptoquinoline and 35 ml of methanol. The mixture was heated with stirring in an argon atmosphere until the salt is completely dissolved (the solution temperature of about 50oC), then was added dropwise a solution of 3,44 g (0.01 mol) cadmium dibromide tetrahydrate in 15 ml of methanol. She rolled a yellow precipitate. The mixture was stirred for 20 min at 55-60oC, then cooled to room temperature and diluted with an equal volume of water. The precipitate was filtered, washed with methanol (2x20 ml), water (2x20 ml), dried in vacuum over bezw. MgSO4. Received 3,93 g complex. Exit 91% of theoretical (counting on salt cadmium). TPL= 382-384oC.

Elemental analysis.

Calculated, %: C 49,95; H Was 2.76; N 6,48; S 14,80; Cd 25,99.

The IR spectrum of Cd(MQ)2(KBr tablet) given in the table. The similarity with the IR spectrum of Zn(MQ)2confirms the same composition of the organic part of these molecules.

Tris (8-hinokitiol) gallium (III), Ga(MQ)3< / BR>
< / BR>
In a flask with a capacity of 100 ml, equipped with a magnetic stirrer, addition funnel and reflux condenser, was placed 4,58 g (0,025 mol) of sodium salt of 8-mercaptoquinoline dissolved in 100 ml of 50% aqueous ethanol. The mixture was heated to 35-40oC and added dropwise 2.8 g (to 0.007 mol) of gallium nitrate octahydrate dissolved in 15 ml of water. Then the mixture was stirred for 1 hour at a temperature of 50-55oC. then the mixture was cooled to room temperature, the precipitate was filtered, washed his consistently ether (30 ml), methanol (20 ml), water (2x20 ml), dried in vacuum over bezw. MgSO4. Received 3,63 g complex. Output 94,3% of theoretical (counting on the gallium nitrate). TPL= 271-272oC.

Elemental analysis.

Found, %: C 58,10; H To 3.73; N 7,29; S 17,34; Ga 13,12.

Brutto-formula C27H18N3S3Ga.

Calculated, %: C 58,90; H 3,28; N Of 7.64; S 17,46; Ga 12,68.

IR-spectrum (KBr tablet) are listed in the table is the strong absorption bands, which is consistent with the increase in the number mercaptoquinoline groups of this molecule.

Example 2. Synthesis of a mixture of oligomers of triphenylamine for hole-transport layer.

The scheme of synthesis of a mixture of oligomers of triphenylamine (I)

< / BR>
1) Synthesis of monomer.

4-Methyldiphenylamine was obtained according to known methods.

The mixture 66,68 g (30,6 mol) 4-iodine-toluene, 43,94 g (0.26 mol) of diphenylamine, 41,4 g (0.30 mol) of anhydrous K2CO3and 2.0 g of copper powder was heated in 75 ml of nitrobenzene to a boil with continuous stirring boiled under reflux for 24 hours By cooling the reaction mass was filtered, the precipitate washed with 100 ml of benzene. The combined filtrate by distillation under reduced pressure to remove the benzene, nitrobenzene, the remains of a 4-iodotoluene, and the residue was distilled in vacuum, collecting the fraction boiling at 180-200oC / 3 mm RT. Art. cooling substance was secretarypantyhose. It was purified by chromatographytandem on a short column with Al2O3eluent benzene : hexane (1: 1), with subsequent crystallization from 90% aqueous acetic acid. Got to 47.2 g of pure substances. Output 70.1 percent of theoretical. So pl. 68,0oC (so pl. 68,8oC ).

oC, was added in small portions during 2 hours 55 g (0.22 mol) of deoxyribose with continuous stirring. Initial temperature (-10oC) supported the entire period of addition of the reagent and forth, until the termination of allocation of gaseous HBr (only 2.5-3 hours), after which the mixture was heated to room temperature and left for 24 h Then the reaction mixture was treated with 20% aqueous NaOH solution (to pH 8-9 aqueous phase). Separated organic layer was separated by washing with 5% aqueous acetic acid, then water, then drove the solvent under reduced pressure. The resulting crystalline residue was purified on a short column with Al2O3, the eluent benzamycin (1: 4 vol.), followed by recrystallization from 90% aqueous acetic acid. Got to 38.2 g of the product. The yield of 82.6% of theoretical. So pl. 107oC.

Elemental analysis.

Found, %: C 57,37; H 3,69; Br 37,22.

C19H15NBr2.

Calculated, %: C 57,71; H 3,62; Br 38,31.

3) Synthesis of oligomers.

Oligomerization of the monomer [4,4'-dibromo-(4"-methyl)triphenylamine] were conducted according to a modified method [1].

Oligo(4,4'-(4"-methyl)triphenylamine (promoterami), (I).

oC. Received 15,95 g of the crude product. It was dissolved in 60 ml of benzene, was filtered from the insoluble residue was poured into 350 ml of hexane. Fallen yellow precipitate was filtered, dried in vacuum at 50oC. Received 6,35 g of the product. The yield of the pure product 39% of theoretical. So pl. 183-187oC.

r0,24)n.

Calculated, %: C 82,29; H The 5.45; N Of 5.05; Br 7,20.

For gross formula (C19H15N)8Br2. Molecular weight distribution: Mn= 1812, Mw= 2802, the polydispersity (Mn/Mw= 1.55V. The glass transition temperature (measured on a differential scanning calorimeter DTAS-1300) is equal to 175oC.

4) Dibromononane of oligomer (I).

Oligo(4,4'-(4"-methyl)triphenylamine (dimethylsiloxane) (II).

To a suspension of 4.13 g (to 0.17 mol) of metallic magnesium in 60 ml of dry THF was added in an argon atmosphere and with continuous stirring at 16.1 g (0.11 mol) of methyl iodide with such speed, that the reaction mixture was quietly seething (time adding about 0.5 hours). To the resulting mass was added 0.15 g of catalyst ([1,3-bis(diphenylphosphino)propane] Nickel(II)chloride) (dpppNiCl2) and a solution of 6.0 g (about of 0.003 mol) prosteradlo of oligomer (I) in 95 ml of THF. The reaction mixture was stirred at room temperature for 24 h, and then boiled under reflux for a further 2 hours By cooling the reaction mass was carefully poured into 1.5 liters of 2% hydrochloric acid. Fell precipitate a light yellow color. It was washed successively with 2% hydrochloric acid, water, ammonium hydroxide, water, C is whether in 60 ml of benzene and was chromatographically on a short column of silica gel (eluent benzene). The collected eluate was concentrated to a volume of about 40 ml and poured with stirring into 100 ml of hexane. Fell light yellow precipitate. It was filtered, washed with hexane, dried in vacuum at 50oC. Received 3,47 g of substance. The yield of the pure product 61.4% of theoretical. Melting point 206-210oC. the glass transition Temperature by the method of differential thermal analysis 185oC.

Elemental analysis.

Found, %: C 88,47; H 5,71; N Of 5.83.

For gross formula (C17,7H13,6N)n.

Calculated, %: C 88,56; H Between 6.08; N Are 5.36.

For gross formula (C19H15N)8(CH3)2. Molecular weight distribution: Mn= 2332 (about 9 units), Mw=3586, a polydispersity Mw/Mn=1,54. UV absorption spectrum (solution in chloroform) 313, 372 nm.

Example 3. Using 8-mercaptoquinoline zinc, Zn(MQ)2.

The maximum absorption for the deposited film 420 nm. The maximum photoluminescence (powder, stimulating emission 440 nm) at 525 nm, half-width of the spectrum of photoluminescence 58 nm. Quantum yield of photoluminescence measured for a solution in ethanol of about 3%.

For the manufacture of electroluminescent devices with the structure ITO/PTA/Zn(MQ layer and Mg:Ag - electron-an injecting layer, use a glass substrate with a transparent layer of a mixed oxide of indium and tin with resistance 20-25 Ohms/square, which by centrifuging from a solution in toluene put a layer of PTA thickness of 0.05 - 0.1 μm. Then by evaporation of Zn(MQ)2obtained in example 1, in a vacuum at a temperature of approximately 300oC and the base pressure 510-6mm RT.article put the active electroluminescent layer with a 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 510-6mm RT.article and sprayed metal electrode by evaporation of an alloy containing magnesium (90 wt.%) and silver (10 wt.%). The thickness of the metal electrode is about 0.1 μm.

The area of the illuminated surface of 4-5 mm2. Received ELU has the following parameters: brightness 121 CD/m2is achieved at a voltage of 14.1 B and a current density of 24 mA/cm2.

1. The electroluminescent material containing electron-an injecting layer, an active luminescent layer based on chelate complex metal 2B or 3A group of the Periodic system, hole-transport layer and hole-an injecting layer, characterized in that as LUMIN the Ga;

R1- R6- independently from each other H, methyl;

R3, R4- independently of each other phenyl, unsubstituted or substituted stands, tert.bootrom;

R3- R5- independently from each other, a methoxy group, ethoxypropan, dimethylaminopropyl, diethylaminopropyl, nitrile.

2. The electroluminescent material under item 1, characterized in that the luminescent layer contains a complex of 8-mercaptoquinoline zinc.

3. The electroluminescent material under item 1, characterized in that as the hole-transport layer contains a mixture of oligomers of triphenylamine formula

< / BR>
where n = 8 - 9

when the molecular-mass distribution: Mn = 2332, Mw = 3586.

 

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