TW587093B - Electro-luminescent device and new luminescent compounds and doping agents - Google Patents

Abstract

The invention relates to an electroluminescent device, in which the luminescent layer contains a luminescent compound and a compound of the general formula I as doping agent, wherein B is an unsaturated carbocyclic or heterocyclic 4-8-link ring, which can also contain an alicyclic bridge, the rings D and E are five- or six-link rings, which each can contain one more hetero-atom N, O and S, the radicals R are one or more substituents H or straight-chain or branched C1-C6-alkyl, X and Y are carbon or nitrogen, R1, R2 and R9 are H or straight-chain or branched C1-C6-alkyl, R3 and R8 are hydrogen, straight-chain or branched C1-C6-alkyl, hydroxy, -OR16, -COOR16, N,N-dialkylamino, acetylamino or halogen, wherein R16 is hydrogen, or straight-chain or branched C1-C6-alkyl, R1 and R2 or R2 and R3 and/or R8 and R9 together can form an alicyclic, heterocyclic or aromatic ring, and A1 and A2, which can be the same or different, are cyan, nitro or -COOR16. The compounds I are partly new. Together with the luminescent compound, the doping agents have a red or white color, depending on the concentration, with excellent quantum efficiency.

Description

A7 --------- -B7 V. Invention (-The present invention relates to an organic, special, red light-emitting electroluminescent device, exactly a device with a light-emitting layer, the light-emitting layer contains at least one A luminescent compound or an additional dopant and a novel compound. Organic electroluminescent devices have been familiar to us for quite some time. In the simplest case, they consist of a glass substrate and a transparent indium tin oxide (ITO) coating. A hole transporting layer, a subsequent light emitting layer, and a metal electrode with low electron emission (see Figure 1). In this case, electrons are injected in a short direction of the metal electrode (cathode), which is usually made of Ca or Mg Made by co-evaporation or continuous evaporation (for example, with A1 or Ag), and holes (hole electrons) are injected from the end into the organic multilayer composite material by transparent IT contact (anode). These are reorganized here And form a singlet exciton. After a short time, the singlet exciton changes from light to the ground state under emission. In this case, the organic interlayer connection is formed by a light-emitting layer (which is a light-emitting compound and also Subconductor) and hole transport layer. In the hole transport layer, N, N′-biphenyl-N, N, -bis- (m-tolylbenzidine (TPD) and N, N , -Biphenyl-N, N, -bis- (1 • fluorenyl) · benzidine (ΐ-NρΒ) type as a hole transporting substance. The addition of an electron transporting layer often leads to an increase in the quantum efficiency of the electroluminescent device and / or The starting voltage is reduced (see Figure 2). At the same time, the light-emitting layer may have an extremely thin design. Easy to use. Independent of its transport characteristics "light-emitting substance, the light-emitting wavelength can be precisely adjusted over the entire visible spectral range. In addition, if at least two are tuned separately Each hole-transporting layer used (see Figure 3), the performance of the electroluminescent device is improved (the quantum efficiency is increased and the electroluminescence starting voltage is reduced). _ In some cases, an additional application may be made between the light-emitting layer and the metal electrode. Electric-5- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 587093 A7 B7 V. Description of the invention (2 sub-transport layers (as shown in Figure 2). In recent years, it has been deposited on transparent IT by vapor deposition. 〇 and thin hole injection between the hole transport layer Layer, for example, CuPC (copper phthalocyanine) (see Fig. 4) to improve the performance of the light emitting device. In particular, the so-called ", burst molecules" are used in the second hole transport layer because it has a low ionization voltage. These are high molecular organic compounds based on triphenylamine units. Recently, a novel hole transporting substance is described in German Patent Application No. 19,541,113, which shows excellent layering in addition to excellent hole transporting properties. Performance, thermal stability and low recrystallization tendency. For the manufacture of full-color electroluminescent devices, it is necessary to use red, green and blue light-emitting electroluminescent materials with high electroluminescence quantum efficiency and color purity. Thallium- (8-quinyl p-quinuclyl) -aluminum (Aiq3) is used as a better light-emitting substance in the light-emitting layer (CW · Tang, SA · van Slyke: Appl Phys · Let · 51, 1987, 913). The metal chelate complexing agent itself emits green light in the interlayer bonding. Among them, beryllium or gallium can also be used in the complex as a blonde blue electroluminescent device by using 1,3,4-oxadiazole (〇xidiaz Derivatives of 〇1) or obtained with diphenylethylfluorenyl arylene. The red luminescent radiation is obtained in particular by 4-dicyanomethylene substituted with 2-alkyl-6-N, N-dialkylamine phenethylfluorene. 4 Η -exo 1; Not only can 2-methyl-6- (4-N, N-dimethylaminophenethylfluorenyl) -4-dicyanomethylene-4 基 .ρbiran (DCM) be used (US patent application Case No. 4,769,292), and dikisylcyclobutanedione dye can be used as the second powdery acid dye. The disadvantage of using DCM as a dopant for A1Q3 is that the emitted light appears to the human eye. -6- This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 587093 A7 ______ B7 V. Description of the invention (3) Too orange, and because the DCM dye has agglomeration in A1Q3, the efficiency of the emitted light is not high enough for many applications, so the light emitting diode will not additionally work with sufficient long-term stability. DCM has gradually become familiar as a laser dye (U.S. Patent Application No. 3,8 52,683) and can be derived from additional dyes, which represent a form of conjugated polyfluorene with donor / acceptor design combination. By changing the donor substituent in the dye molecule, for example, replacing the 4-N, N-dimethylaminophenylphenyl group in DCM with a fairly strong donor julolide-based dye (DCJ dye), long wave The absorption band shifts, and the emission band also shifts red relative to the DCM. When DCJ is used in an electroluminescent compound, the visible color impression also corresponds to a stronger red. However, in this case, the weight is 0 / with respect to A1q3>. The dopant application area also maintains an unfavorable tendency to aggregate, so that these materials are too inefficient in the electroluminescent device. In addition, when using DCJ, it should be pointed out that the compound has poor evaporation properties. "The high decomposition rate during the evaporation process first causes problems in the production of such light-emitting layers. Compared to DCJ or DCM, although the introduction of a bulky third butyl substituent at the 2-position of the pyran ring of a corresponding DCM-like dye as described in US Patent Application No. 5,935,720 reduces the aggregation of dyes such as DCJT and DCJTB Tendency, but for the substance to be suitable for full-color applications, this tendency cannot be sufficiently suppressed. With the exception of the effects already mentioned, the disadvantage of using all dopant / A1Q3 systems is the visible impure impression (color tone) of the emitted light, which is usually only perceived by the human eye as a distinct orange-red to red. The reason is that there are obviously two common vehicle directions, which are the characteristics of this dye. On the one hand, these " D / A dyed paper standards are applicable to Chinese National Standards (CNS) A4 specifications (210 X 297 mm) 587093 A7 B7. 5. Description of the invention (4 materials) is the main conjugate direction. The self-donor substituent of the sex chain!) Points to the acceptor fa A (cyano group in the 4-position of the p-pyranyl ring). A meso substituent (which may be a phenyl or substituted phenyl ring) or a positive inducing substituent (which may be an alkyl or branched alkyl) from the same position points to the acceptor in the 4-position of the pyran ring Substituents. This intersection and conjugation has provided wide absorption and emission bands and impure tones of the emitted light. Get closer, X.T.i, Tao, S. Miyata, H. Sasser

(Sasabe), G.J. Zhang, T. Wada, μ. Jiang (Apply · Physics Letters 78, 2001, 279-281)

It is based on A1Q3, and 3- (dicyanomethylene) _5,5 · dimethyl-bu (4-N, N-dimethylaminostyryl) cyclohexane (DCDDC) is used in the light-emitting layer. As a dopant instead of DCM-based dyes, a fairly pure and stronger light emission can be obtained. Since there is only one possible conjugate direction in this type of dye, the absorption and emission bands are very narrow. However, in (1% doping, the above substances have reached their maximum electroluminescence quantum efficiency relative to A1Q3, because higher doping increasingly results in the formation of aggregates. The optimal concentration of these dopant systems relative to A 丨 Q3 is between < 丨 The weight% range is too low, so that due to insufficient transmission energy, the inherent luminescence of MW distorts the color impression of the emitted light. As a result, the red tone is not pure, so that the initial display advantages of these dyes compared to the DCM type Most of it is lost ... The task of the present invention is to manufacture an organic electroluminescent device with improved quantum efficiency and improved long-term stability, and thus develop a new light-emitting compound for light emission and a common light-emitting compound (especially A%) Used: New dopant. Ben _ Another purpose of producing clear - the use of new types of can 1

587093 A7

Wherein R16 is hydrogen or straight or branched alkyl, heterocyclic or

In the case where Ri and or R2 and Rs and / or and R9 together form an alicyclic aromatic ring, and B is an unsaturated ring of 5 or 6 bonds and a ring of 0 bonds, two of the 1,3-positions Each ring atom may form an alicyclic bridge with each other, and the radical is one or more substituents, and the substituents may be the same or different, and may be a straight or branched alkyl group; A1 and A2 may be the same. Or different, is cyano, nitro or -c0Ri6, where Ru is hydrogen or a linear or branched alkyl. Preferred groups R i to R9 are lower alkyl (c〗 _ cd, in the sense, representing methyl, isopropyl, or third butyl, respectively. Another preferred design type relates to a type which contains the general formula Iπ or Device using a compound of general formula 1 V as a dopant, ^

Wherein, ⑼ to ^ 5 are hydrogen, linear or branched Ci_C0 alkyl, preferably methyl and other groups having the above meaning. R1G and R! 5 can be formed as needed-an alicyclic bridge, for example, in dye 2 or 4, see also Table 1 below.

In its most simple case, according to Figure i, the organic electroluminescence device is composed of a layered composite material. The composite material consists of a metal electrode i (cathode), a release organic light-emitting compound (especially A1Q3) and contains At least one organic mixing box, "light-emitting layer 2, a hole-transporting layer 3 containing an organic hole-transporting compound, a transparent conductive anode 4, and a glass or similar transparent shell (composed of a carrier 5. In a different In the arrangement of the electroluminescent device, the performance of the device can reach the best. For example, according to FIG. 2, it has an additional electron transport layer 6. According to FIG. 3, it has two hole transport layers 3 & There is another layer between the conductive transparent layer 4 and the hole-transporting layer 3, for example, a thin CuPC layer. The compound of formula I or formula II is also advantageously present as a dopant in a mixture with other dopants, etc. Other dopants can be selected from the group consisting of 2-alkyl N, N-monoalkylamine styryl_ or juloridine-substituted dicyanomethylene-4 -fluorene -pyran (equivalent to the pyran ring 3rd butyl substituted pyran) and 3 (—cyan Methylene) -5,5-dimethyl] · (4 · ν, ν · dimethylaminophenylethylethyl) cyclohexane group, especially 丨, 2- or i, 3_ substitution Dihydroxycyclobutanone dye. The common use of several dopants can be carried out, for example, by co-evaporation. The organic light-emitting compound is preferably selected from tris (8-hydroxyfluorinyl) aluminum (A1Q3), 1, 3,4-% monoazole derivatives and diphenylethylfluorenyl-aryl derivatives, of which (A1Q3) is particularly preferred. It has been determined that, based on the weight of the organic light-emitting compound A1Q3, it has recently been used in organic light-emitting devices as > 1% to 8% by weight (preferably > 1% to 5% by weight, particularly good 1.5% to 3% by weight) in a concentration range of singly or in combination, ____- 12- This paper pump scale is applicable to China Standard (CNS) Α4 size (210X 297 mm)

Binding and thread ψ: 587093 A7 B7 V. Description of the invention () where B is an unsaturated carbocyclic ring with 4, 5, 7 or 8 bonds, and the carbocyclic ring is replaced by hydrogen and / or C i-C 6 alkyl And in the case of a 5-bonded ring, 'the ring carries at least one C! -C6 alkyl group; or B may be an unsaturated carbocyclic ring of 6 bonds, the carbocyclic ring consisting of one or more straight Chain or branch C! · C 6 alkyl radical substitution, where two ring atoms in the 1, 3 position can form an alicyclic bridge with each other; or B is a type substituted by one or more Ci-C6 alkyl groups An unsaturated carbocyclic ring of 6 bonds; or B is an unsaturated heterocyclic ring system of 4.8, having 0, N, or S as a heteroatom, the ring system consisting of hydrogen and / or one or more C i- C 6 alkyl substituted; and rings D and E are rings of 5 or 6 bonds. The ring may each contain one or more heteroatoms selected from N, 0 and S, and at least one of the two rings is required to contain Another heteroatom; and the group R is one or more substituents; the substituents may be the same or different, and are hydrogen or a linear or branched C i -C 6 alkyl; X and Y are carbon or nitrogen;

Ri, R] and R9 may be the same or different, and are hydrogen or a linear or branched c6c6 alkyl group; R3 and may be the same or different and are hydrogen, a straight chain, or a branched ^ -cardiacyl group, technical group, -ORi6, -COORi6, N, N-dialkylamino, acetamido, or halogen, where R10 is hydrogen or straight or branched (^-(: 6 alkyl,

Ri and R2 or R2 and R3 and / or R9 may together form an alicyclic ring, heterocyclic ring, or a square group, and A! And A2 may be the same or different. This paper size applies to China National Standard (CNS) A4 (210X297 mm)

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587093

Description of the invention (Poly- (N-ethynyl) (PVK) or a molecular composition suitable for the purpose of polycarbonate, wherein the hole-transporting substance is a hole-transporting adhesive or an absolute coupling agent (such as carbonate The ratio of) can be changed in a wide range. The weeping dragon weeping 秘-secret π, the head is prepared in an agent and inert rolling at I: while stirring at a warm temperature, according to conventional methods in the agent or solvent mixture ( For example, dichloromethane) to prepare a solution for producing PVK / TPD, and then coat the electrotransparent substrate 1 with a spin coating device in such a way that the hole transport layer 3 is inert gas (for example) under vacuum Drying 1: Drying at 25 ° C to 40 ° C with a dry layer thickness of 50 to 80 nanometers. It should be noted that 'depending on the state of the art, it can also be made from N, N · -diphenyl-! ^ By vacuum metallization.氺, _bis- (3 • methylphenylbiphenyl · 4,4 ·· diamine (tpd) or n, n, hn, h (1i &) i _ (^ npb) hole transport layer 3 Apply to a conductive support.

After Pi4, in Xiangzhi, the dye according to the present invention was used alone as a luminescent compound or as a dopant alone or in the form of a mixture with different dopants using co-emitting technology and a luminescent compound (for example, a1qj was applied to On this layer, based on the weight of the light-emitting compound A1Q3, the concentration of the dopant or a mixture of the dopants may be in a concentration range of 1% to 8% by weight, preferably in a range of 1.5% to 3% by weight Depending on the application of the electroluminescent device, when using a mixture of dopants, the concentration of different dopants can be varied over a wide range, for example, 0.1% by weight based on the total weight of all dopants. And 50% by weight. Finally, without intermediate ventilation, a metal cathode 1 is applied to co-evaporation of Mg / Ag generally at a ratio of 10: 1, but preferably by evaporation of lithium benzoate and Ai (0.7 Nano-lithium benzoate and 100-nm A1). However, -17 paper sizes are also applicable to China National Standard (CNS) A4 (21 × 297 mm) 587093 A7

Other metals (for example, silver, magnesium metals or alloys. Calcium or indium), alloys or other proportions are used in the light-emitting layer 2 as a mixture of two compounds (equivalent dopants). II ISJ I now think of options), can also obtain the extremely 弇 μ 1Λ, L obtained red light-emitting electroluminescence device, until you see 'these new dopants are not yet for these purposes So come. When a new dopant or a mixture thereof is co-evaporated and manufactured with a different dopant (for example, a dye according to U.S. Patent Application No. 4,769,292), such as a substituted dicyclylcyclobutadiene difluoride = Emission 'can also obtain extremely effective red light emitting devices. The dyes produced according to the present invention are particularly used for dopants used in luminescent combinations. The synthetic steps for preparing the dyes have been familiar to us for a long time and are widely cited by Lemke (Lemke, R .: Chem. Ber 103, 1970, 1894-1899; Lemke, R .: DE-A-2,345,189; Lemke, R .: Synthesis 1974, 359-361).

In the case of synthesizing the dyes 7, 8, 11, 1, 19, and 20 according to Table 1, the starting materials required for a new dye or dopant having the structure of Formula I or 11 (for example, 1-4 Juloridine ) Is manufactured according to H. Katayama, M. Ohkoshi: Synthesis 1982, 692-693 under reducing conditions by sodium borohydride in THF from 8-hydroxyquinoline, monochloroacetic acid. Then, according to the familiar formazan fermentation step, the corresponding 9-formamyl-1 -humulolidin (Organikum, Organic-Chemical Basic Practicum, 13th Edition, VEB

Deutscher Verlag der Wissenschaften Publishing House, Berlin 1974). -18-This paper size applies to China National Standard (CNS) A4 (210X297 mm)

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587093 A7 B7 V. Description of the invention (15) Preparation of 9-formamidine · i, 7 ·: The method of thiojulolide is also familiar to us and has been disclosed in US Patent Application No. ^^^^. Hetero-bridged 1-methyl-ethylenone (eg, 5-methyl '· 2Η_pyran_3 (6ίί_) ketone) is based on SK Skinnemoen, κ Endehai ( Undheim) :, Acta Chemica Scandinavica B 34, 198〇, 295 297 is produced in a two-stage process from di_ (2 · propynyl) _fluorene through the dipropionyl ether reaction stage and subsequently through intramolecular ring closure. Corresponding to 5-methyl-2Η-1-thiopyran-3 (6-oxanone is similarly produced by intramolecular ring closure of diacetone sulfide. The preferred dyes of the present invention are the compounds listed in Table 丨 below. They Some of them are familiar to us for non-linear optical applications (NLQ) and are published in German Patent No. 68919889 D2, for example, dyes}. Very high electric field strength is generated by electron delocalization at the atomic scale (For example, generally used with lasers) Affects the non-linear polarization vector and sensitive measurement benefits in hyperpolarized compounds, and facilitates the full use of absorption and reflection in laser radiation and various effects and applications (Jinkel ( Pockels) effect, coherent anti-Stokes Raman scattering, two-photon absorption, and emission spectrum; optical switching (Kerr effect and the like) that produces new (higher) frequency optics Device (frequency doubling, total and difference). However, since these NL0 applications are mainly based on absorption performance, and fluorescence performance is not affected ‘so’ it ’s less obvious that these familiar compounds are used in emission applications, such as in organic light-emitting devices. ____- 19- This paper size applies to Chinese National Standards (CNS) A4 specifications (210X 297 public love) 587093 A7 B7 V. Description of the invention (16)

Table I • 20-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X297 mm) — NC CN A NC CN A Dye 1 Dye 2 VV Rabbit Feed 3 Feed 4 A7 B7 V. Description of the invention (17 ) NCy.CN NCyCN 5 料 5 Dye NC CN Λ NCn ^ CN X Dye 7 Dye 8 λ NCv ^ CN Dye 9 —Dye-io 587093 This paper size applies to China National Standard (CNS) A4 (210X297 mm)- 21-587093 A7 B7 V. Description of the invention (18) NC.CN NC CN V Dye 11 Dye 12 nc ^ cn Λ NCV ^ CN j Λ Dye 13 Dye 14 nc ^ n Λ ncv ^ n I Λ. Ί% 9 \ 1 Dye 15 Dye 16 ^ -22- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) Lian 587093 A7 B7 V. Description of the invention (19) NC CN Ϊ A. Dye 17 Dye 18 NCv ^ CN X NCV ^ CN X. FREE. One dye 19 dye 20 ^ v ^ CN X nc ^ n long · ^ 9. Dye 21 Dye 22 -23-This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public %) Pregnancy 4 Total A7

However, the present invention is not limited by these examples, which are used to explain the present invention in more detail. : M · X (general synthesis example): In order to prepare the dyes to be used according to the present invention, ηmmol molybdenum earrings are ^ methyl-acetamidone (isophorone, verbalone, 5 / methyl 2Η_pyran-3 (6Η) -one, methyl-2Η-thiopyran-3 (6Η) -one and the like), 66 g (10 $ mol) of malononitrile and 10 ml of three 0.15 g of piperidine in fluorenylmethanamine was placed in a 50 ml three-necked flask equipped with a thermometer and a magnetic stirrer and initially warmed at 25 C for 1 hour while stirring. Subsequently, the mixture was heated for another hr. The reaction mixture gradually turned brown. Now, while stirring, 10 millimoles corresponds to 9-methylpyrrolizidine (for example, 9-methylpyridyl-8-fluoro-1,1,7,7-tetramethyljuloridin, 9 _ Formamyl- !, 7-dithiojuloridine or ^ formamyl humulolide) Fractions are added to the thermal reaction mixture as a solid or in solution, and heated at 80 ° C for 1 hour. The reaction mixture changed color to dark reddish purple. The reaction process was observed by thin layer chromatography (silica gel: 60, flowable mixture: 1-butanol / ethanol / acetic acid / water 60/10/5/2). After generating various dyes of the desired quality, the reaction was terminated / cooled and the mixture was allowed to stand overnight. Subsequently, the microcrystals were vacuumed out and washed several times with methanol to remove the unreacted starting material portion, and at 60 t Dry in a vacuum drying chamber for 8 hours. The dye which does not crystallize immediately is crystallized by adding a precipitant to the reaction solution (e.g., methanol). Purification dyes are typically performed by recrystallization (for example, from methanol) and subsequent sublimation in high vacuum. -24- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 54Ϊ 587093 A7 _ — —__ B7 Fifth, issued ^ Mingming (2〇 " 'According to Figure 1, ITO (tin oxide Indium) 4 coated glass-breaking carrier 5 was spin-coated with N, N, diphenyl-N, NL bis- (3-methylbenzene in a ratio of 1: 丨 (weight ratio) in dichloromethane. A solution of a base) _benzidine and poly_ (n ^ ethylenecarbazole) is applied with a hole transport layer (Htl) 3. The layer is dried under an inert gas at a temperature between 25 t and 40 ° C, and the layer thickness is 50nm. After the 'light-emitting layer 2 was applied in a high vacuum (10.5 hPa) by co-evaporation of A1QS and purified dye 1 at a concentration of 15% by weight relative to A1 (^ On the obtained hole transport layer 3. Subsequently, a metal cathode 1 (0.7 nm fluorination via +100 nm A1) was applied by LiF & A1 evaporation. The steps used for the metal cathode can also be performed in a manner corresponding to Example 3. For detection Electroluminescence. A controlled voltage between 1 and 20 volts is applied between the ITO and the metal electrode. The device obtained by this method produces a hair with a height of 58 candelas per square meter at 12.6 volts. Luminous rate. The emitted light has no secondary emission of Alp in the range of about 53 nm, and it shows a very pure red hue. Example 3 According to Figure 1, a glass support coated with ιτο (indium tin oxide) 4 5, a hole consisting of N, N · -diphenyl-N, N'-bis- (3-methylphenylbiphenylaniline) was applied to a thickness of 50 nm by vapour deposition under krypton vacuum (10 hPa). On the transport layer (HTL) 3. Then, by co-evaporating AiQ3 and relative to A. At a concentration of 2% by weight of the purified dye 1, an electroluminescent layer 2 was applied on the hole transport layer 3 obtained in this way. The thickness of the applied electroluminescent layer 2 was 60 nm. Subsequently, a metal cathode was applied by evaporation of benzoic acid and A1. (3) Lithium nanobenzoate + 100 nm A1). -25- Surface paper silver scale SS Home Standard (CNS) A sample (21GX297 public love y A7

In order to detect electroluminescence, a voltage between ITO and a metal electrode was applied between the ITO and the volt control voltage. The device obtained in this way produced a luminous rate of up to 600 candelas per square meter at 12.8 volts. The emitted light was about In the 530nm range, there is no A1Q3 and secondary emission, and the visual display shows a very pure red hue. According to Figure 2, a glass carrier coated with IT0 (indium tin oxide) 4 passes through the vacuum (10-5 hPa). Vapor deposition applied a 5-cavity transport layer (HTL) consisting of + '4,4_tri-(> ^ (1-fluorenyl) · N_phenyl_amino) -triphenylamine to a thickness of 5 5 nm 3. Then, by co-evaporating A1Q3 & purified dye i at a concentration of 1.5% by weight relative to A1Q3, the electroluminescent layer 2 is applied to the hole transporting layer 3 obtained in this way. The electroluminescent layer is applied The thickness of 2 is 30 nanometers. Now, 10 nanometers are applied as a ladle transport layer 6 by vapor deposition. Subsequently, a metal cathode U0 ·? Nanometer lithium fluoride is applied by LiF and A1 evaporation. + 100 nm A1). The steps used for the metal cathode can also be performed in the same manner as in Example 3. In order to detect electroluminescence, in ιτο and gold A controlled voltage between 1 and 15 volts is applied between the electrodes. The device obtained in this way produces a luminous rate of up to 900 candela / m2 at 14 volts. The emitted light has no AlQ3 first order in the range of about 53 nm Emission and visible pure red tint. On a piece of glass carrier 5 coated with ITO (Indium Tin Oxide) 4, a 5 nanometer thickness composed of CuPC was applied by vapor deposition on 鬲 2 (10 · 5 hPa). Injection layer, a 55 nm thick hole transport layer (HTL) 3b consisting of 4,4,, 4 ,,-tris-fluorenyl) · N-phenyl-amino) -triphenylamine -26- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

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Claims (1)

587093 Patent Application No. 091109898 B8 Chinese patent application scope replacement March 1983, m 9 < jc ό. I (1 ^ ^ \ ϊ- ί month β a | VI, patent application scope ^, " 丨 ι 1. A light emitting device comprising a hole transporting layer and a light emitting layer interposed between two conductive electrodes, wherein up to two electrodes are transparent, characterized in that the light emitting layer contains at least- A compound of general formula is used as a luminescent compound or a dopant used for a luminescent compound. /, Re A ^ R A A 2 BD-rR E E, wherein the ring B is a kind of unsaturated which has 0, Nils as heteroatoms Carbocyclic or heterocyclic 4 to 8-bonded rings, where in the case of 6 -8-bonded rings, carbon atoms can be bridged; where B is not a 4_H-pyran ring, two rings D and E Is a ring of 5 or 6 bonds, the ring contains-or more N, 0 and S heteroatoms, respectively; selected from the group R is one or more substituents, which may be the same or different, hydrogen or straight Chain or branch CVC6 alkyl; and X and Y are -carbon or nitrogen; Ri, R2 and R9 are the same or different And is hydrogen or linear or branched or halogen; R3 and R8 are the same or different, and are hydrogen, linear or branched Ci_C6 alkyl, the paper size is suitable for financial_Tukamaki (CNS) M specifications (detailed public) 587093 Guiji, -0R10, _C00Rl0, N, N-dialkylamino, acetamido, or halogen, where Ri6 is hydrogen or straight or branched alkyl; R1 and R2 or R2 and R3 and / or & 8 And & 9 may together form an alicyclic, heterocyclic or aromatic ring; and ', and ba 2 may be the same or different, and are cyano, nitro or _c〇〇Ri6, where R16 is fluorene or straight chain or branched Ci -C ^ alkyl. 2. The electroluminescent device according to item 丨 of the application, which is characterized in that it contains a compound of the general formula 11 as a dopant for the electroluminescent compound, X / ... ',, R II ′, R1, R2, 114 to] ^ 7 and 119 are the same or different, and are hydrogen or a linear or branched alkyl group, I and R8 may be the same or different, and are hydrogen, a linear or branched group, a fluorenyl group, -0R16, -COOR16, Ν, Ν · dialkylamino, acetamido, or autogenin 'wherein R10 is hydrogen or a linear or branched C1-C6 alkyl group, R1 and R 2 »or R2 and / or 1 ^ 8 and 9 can form an alicyclic, heterocyclic, or aromatic ring together, and B is an unsaturated ring of 5 or 6 bonds, where in the case of a ring of 6 bonds, two of the 1,3-positions Each ring atom can form an alicyclic bridge with each other, and the group r 587093 A8 B8 C8 ----------- 6. The scope of patent application is one or more substituents, which may be the same or different. And is hydrogen or a linear or branched alkyl group; Am and A2 may be the same or different and are cyano, nitro or -CO〇Ri6, wherein Ri6 is hydrogen or a linear or branched Cl-c6 alkyl group. 3. The electroluminescent device according to item 1 or 2 of the scope of the patent application, characterized in that the group R to% as a Cl-C0 alkyl group in its sense represents a fluorenyl group, an isopropyl group or a third butyl group. 4. The electroluminescent device according to item 1 or 2 of the scope of patent application, characterized in that the compound of formula I exists as a dopant in a mixture with other dopants. -6-N, N-: alkylaminophenethylfluorenyl- or juloridine substituted dicyanomethylene · ren H-pyran (equivalent to pyran substituted with a third butyl ring on the annan ring Group) and 3 _ (dicyanomethylene) -5,5-dimethyl-i- (4-N, N-dimethylaminophenylethylethyl) cyclohexyl, especially 丨, 2-or 丨, 3 _-substituted dihydroxycyclobutadione dyes. 5. According to the scope of patent application! Or item 2 of the electroluminescent device, characterized in that the organic light emitting compound is selected from the group consisting of Wife- (8 _ Jingji p Kulynji) Ming (Aiq3), 1, 3, 4-Ziji Jun derivatives and diphenyl Group consisting of vinyl-aryl derivatives. 6. The electroluminescent device according to item 丨 or 2 of the scope of patent application, which is characterized by the formula based on the weight of the luminescent northern compound A1Q3! The concentration of the dopant is in the range of more than 1% by weight to 8% by weight. 7. The electroluminescent device according to item 6 of the scope of patent application, characterized in that the concentration of the dopant of this formula is 15 weights based on the weight of the light-emitting compound A1Q3 -3- This paper size applies to Chinese national standards (CNS ) A4 specification (210 X 297 mm) 587093 AB c D, patent application range of% to 3% by weight S. The electroluminescent device according to item 6 of the patent application scope, which is characterized by its emission with A1Q3 Pure red light. 9. An electroluminescent device according to item 8 of the scope of patent application, characterized in that it has a luminous rate in the range of 580 to 2050 candela / m 2 at 10 to 12 volts, and a secondary emission without A1Q3 at 530 nm Emitting red light. 10. The electroluminescent device according to item i or 2 of the scope of the patent application, characterized in that the concentration of the dopant is in the range of 0.1 to 1% by weight based on the weight of the light-emitting compound A1Q3, and A1Q3 — Starts emitting white light. 11 · A compound of general formula I, 玎 where B is an unsaturated carbocyclic ring of 4, 7, or 8 bonds, which is substituted by hydrogen and / or C i-C 6 alkyl, and at least one CC 6 is downloaded in the case of a 5 bond ring Alkyl; or B may be an unsaturated carbocyclic ring of six bonds substituted by one or more straight or branched Cl_C6 alkyl groups, where two ring atoms at the 1,3-position may form a lipid with each other Ring bridge; or -4 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 587093 AB c D 6. Application scope of patent =, four kinds of unsaturated with 0, N or s as heteroatoms Heterocyclic system 4 to 8 ring 'The ring system is substituted by hydrogen and / or a plurality of Ci_c6 alkyl groups; wherein B is not a 4-H pyran ring; and rings D and E are 5 or 6 bonds A ring, which may each contain one or more heteroatoms selected from N, 0, and S, and specifies that at least one of the two rings contains another heteroatom; and the R group is one or more substituents The substituents may be the same or different, and are hydrogen or straight-chain or branched Cl_c6 alkyl; X and γ may be carbon or nitrogen; R2 and R9 may be the same or different, and are hydrogen or straight-chain or branched Branched c "c alkyl or autogenous; R3 and may be the same or different, and are hydrogen, straight or branched, via i, -0R16, -COOR16, N, N-dialkylamino, acetase di Or halogen, where R10 is hydrogen or straight or branched alkyl, Ri and R2 or R2 and R3 and / or Rs and R9 may together form an alicyclic, heterocyclic < aromatic ring, and Ai & A2 may be the same or different , Is cyano, nitro or -COORm, where R16 is hydrogen or a straight or branched Ci-C6 alkyl group. 12. The compound according to item 11 of the scope of patent application, where B is an unsaturated carbon with 6 bonds Ring, and may be substituted by one or more linear or branched C 1 -G 6 alkyl groups. Here, two ring atoms in the 1,3-position may form an alicyclic bridge with each other, -5- 587093 A8 B8 C8 D8 hole, Shen Qing patent scope 5 D and E is a 6-bonded carbocyclic ring, these ring systems are replaced by hydrogen and / or C i-C 6 pit group; and X and γ represent carbon . 13. The compound according to item 11 of the scope of patent application, characterized in that the groups R to trans 9 represent C1-C6 alkyl groups in the sense of methyl, isopropyl or third butyl, respectively. 14. A compound of the general formula γ, Among them, Ri, R2 and R9 can be the same or different, and are hydrogen or halogen or a straight bond or a branched Ci-C6 ^ group; ^ 4 may be the same or different, and are hydrogen or a linear or branched CVC6 alkyl group; R3 and R8 may be the same or different, and are hydrogen, a straight chain or a branched C "C6 ^ group, -GR16, -COOR16, N, N Diamine, acetamido or halogen, wherein Ri6 is hydrogen or straight or branched Cl-C6 alkyl; R17, Ri8, R! 9 and / or R2O may be the same or different, and are hydrogen or halogen Or a linear or branched alkyl group; or -------- 6- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 587093 A8 B8 C8 D8 Patent application scope Ri7 and R19 and / 4r18 * r2g can form alicyclic ring together; or Ri9 * R2O may form a heterocyclic ring with a nitrogen atom; and AiKA2 may be the same or different and is a cyano group, a nitro group, or _c00r ^, which is hydrogen or a linear or branched Clec6 alkyl group. Rt, R5 FV 15. The compound according to item 4 of the Shen Qiao patent scope, which is a compound of the general formula v > VI-V 丄 "R3 and Rs may be the same or different and are hydrogen or halogen; and r4, R5, r6 * r7 are the same, and they are hydrogen or methyl. 16.-A compound of the general formula VII, R Α1 \ χ · Α2 X, Ri ^^ 19 Ling 18 cold 20 VII is-a species with 0, N4S As a heteroatom unsaturation ring or hetero% is a 4-8 bond foot ring, in which one carbon atom of the 6.8 bond can form a bridge with each other; in the case, two 5 scales are suitable as home products ( CNS) A4 size (210X297 mm) 587093 8 8 8 8 A BCD Ri, R2 and R9 may be the same or different, and are hydrogen or halogen or straight or branched ^ -alkyl; R3 is hydrogen, straight or branched alkyl, meridian, -〇r16, -c00r16, N, N-dialkylamino, acetamido, or halogen, wherein it is hydrogen or a linear or branched CVC6 alkyl group; R8 is hydrogen; R17, Rh and / or Rw may be the same or Different, and is hydrogen or halo or straight or branched alkyl; or Ri7 * R19 and / or r18 and r2G may form an alicyclic ring together; or Ri9 and R20 may form a heterocyclic ring with a nitrogen atom; and A! &Amp; A2 may be the same or different, and is cyano, nitro or -CooRb, where Ri6 is hydrogen or a straight-chain or branched Ci-C ^ alkyl group. 17. The compound according to item 16 of the scope of patent application, wherein Ri, R2 and R9 may be the same or different and are hydrogen or methyl; R3 is hydrogen or halogen; R8 is halogen. 18. Compound according to item 16 of the scope of patent application, which is a compound of general formula νΠΙ The patent application parks R 丨 and R4r9 may be the same or different and are hydrogen or methyl, R3 is nitrogen or a prime; Rs is a prime; alkane is the same as or U; ^ same '' is hydrogen or straight chain or Branch Ci.c 11 clock, two 19 and / or R 2 ° can be the same or different, and is hydrogen or fluorine or straight chain or branch κ6 alkyl; ~, R17 and R19 and / or R18 and R20 can form an alicyclic ring together Or Ri9 and Chi 2O may form a heterocyclic ring with a nitrogen atom; and A 1 and A 2 are a gas group. 19. The compound according to item 17 of the scope of patent application, wherein r is nitrogen; Rl 2 and Rl 3 are methyl; R 3 is hydrogen or halogen; and Rs is fluorine. m The compound according to item 18 of the Chinese Patent Application, which is a chemical formula of the formula ιχ Compound 587093 A8 B8 C8 _ Patent application R12 * RU can be the same or different, and is a straight or branched Ci_C6 alkyl group 21. A compound of general formula X, earth 22 · —An electroluminescent device comprising a hole transfer layer and a fluorescent layer between two conductive electrodes, at least one of which is transparent, characterized in that the light-emitting layer contains at least one The compound in any one of the range "to the magic item is used as a fluorescent compound or a dopant. -10- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)