TW201122080A - Organic material and organic electroluminescence devices adopting the same. - Google Patents

Abstract

The invention relates to an organic material and organic electroluminescence devices adopting the same. The general structural formula of the material is shown as the following, wherein Ar is a residue selected from polycyclic aromatic hydrocarbon having 6 to 30 carbon atoms. Ar.sub.1 and Ar.sub.2 are respectively selected from hydrogen, an aromatic group having 6 to 24 carbon atoms, and heterocyclic aryl having 6 to 24 carbon atoms; n is an integer selected from 2 to 3. The organic material of the invention can be taken as an electron transport layer in an organic electroluminescence device.

Description

201122080 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a novel organic organic material, and an organic electroluminescent device using the novel organic material is a field of organic electroluminescence display technology. [Prior Art] Tian Jin, with the development of multimedia technology and the advent of the information society, is increasingly demanding the demand for flat panel display. The organic electroluminescent display has a series of advantages such as autonomous illumination, low voltage DC drive, full curing, wide viewing angle, and rich color painting. The response speed is 1 times that of the liquid crystal display, and the manufacturing cost is lower than the equivalent resolution. Liquid crystal displays, therefore, organic electroluminescent displays have broad application prospects. The study of organic electroluminescent displays (also known as organic light-emitting diodes, 〇LEDs) began in the 1960s, pope et al. (p〇pe M, Kallmann Liver and Magnante R. J., chem. Phys., 1963). , 38, 2042) For the first time, Lu reported the electroluminescence of onion single crystals, which unveiled the prelude of organic solid electroluminescence. In 1987, the researchers of Kodak Company of the United States (CW Tang 'SA Vansiyke, Appi. PhyS· Lett., 1987, 51, 913) proposed a two-layer structure based on the work of the predecessors. The design idea is to select a triarylamine compound with good film-forming properties and an aluminum complex of 8_light quinolate (A1q〇 as a hole transport layer and a light-emitting layer (both electron transport layer), respectively, to obtain high quantum Efficiency (1%), high efficiency (1.5 lm/W), stillness (&gt;i〇0〇cd/m2), and low electro-luminescence (<1〇v) organic electroluminescence. 990, RH 201122080, Cavendish Laboratory, University of Cambridge

Friend et al. (Burroughes:, by the way D d c 士咖 A R,

Friend R H' Nature' 199〇' 347 ' 539) is a new type of polymer light-emitting device made of (4) stupid ethylene (a new light-emitting device) Electroluminescent devices. These two breakthroughs have led to the potential of organic electroluminescent devices as a new generation of flat panel display devices. The organic electroluminescent device consists of two opposing electrodes and an organic medium between the electrodes. The organic medium layer includes a hole injection layer, a special transmission layer, a light-emitting layer, an electron transport layer, a charge blocking layer, etc. It is generally believed that the 0LED device tends to have more holes than electrons, resulting in two carriers at the composite interface. The imbalance reduces the brightness and efficiency of the device. At the same time, the excess holes easily enter the electron transport layer 'even the cathode' to accelerate the aging of the device and reduce the lifetime of the OLED. Therefore, increasing the injection and transmission of electrons has become a widespread concern in the industry. And research topics. In addition to efficient and stable cathodes, a hole blocking layer, electron transport is usually provided between the light-emitting layer and the cathode. The layer and the electron injecting layer respectively function to block hole-limited excitons in the light-emitting region, transport electrons, and inject electrons. The electron-transporting material conventionally used in organic electroluminescent devices is Alqs, but the electron mobility of Alqa is compared. Low (about 1〇-6cm2/Vs). In order to improve the electron transport performance of organic electroluminescent devices, researchers have done a lot of exploratory research work. Yang Yang et al. used nanoscale carbonic acid in organic electroluminescent devices. Hammer as an electron transport and injection material improves the luminous efficiency of the device (Advanced Functional Materials, 2007, 17, 1 966 - 1 973). LG Chemical Co., Ltd. reported that it will be stupid imidazole, 201122080 benzopyrazine or benzoxazaki彳卜人 this &amp;&amp; sitting D object as an electron transport material for organic electricity

The electroluminescent device (Chinese Patent Application No. 20_0041587.4, publication No. CN 1013Ώ5071Α) improves the electron injecting performance of the device due to the crying, reduces the starting voltage, and synthesizes the derivative ammonium salt of the triterpenoid ( Referred to as FFF-Blm4) (J. Am. Chem. Soc. &gt; 2008 - 1 30 (1 1 )&gt; 3282-3283)

As the material of the electron injecting layer, I丄L ^ greatly improved the electron injection and transmission of the device, and improved the electroluminescence tree block. The special effect drought, Cao Yu et al. also used air and various chemicals.

The gold-burning &amp; ancient 47 a ” 间 间 间 效 电子 电子 电子 电子 电子 电子 电子 电子 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 提高 。 。 。 。 。 。 。 。 。 。 。 Development of stable and efficient electron transport materials and / or electronics, human materials, thereby reducing the brightening voltage, improving device efficiency Long device life, has important practical application value. The ideal electron transport material should have the following characteristics. It has a reversible electrochemical reduction reaction; the 〇 energy level is suitable for the job. The mine has high mobility; the film formation is good; the Tg is high; In terms of the structure of the material, it is necessary to make the sub-configuration close to the plane, increase the h interaction between the knives during the molecular stacking, and at the same time require that the molecular structure cannot be planar, to prevent the film formation performance due to molecular crystallization; The unit 'has good electron accepting ability; the molecular weight is sufficient to ensure that it has a high thermal stability, and the amount is not too large to facilitate vacuum evaporation to form a film. [Summary of the Invention] It is a typical electron-deficient system, which has a good acceptability of electrons with a compound containing pyridine group 201122080. The planarity of the ruthenium hydrocarbon is better. The larger the condensed ring system, the better the planarity. The more eight forms an electronic channel. But too large _ / knife ^ track stack and not ... large thick (four) system is easy to make the crystals formed and not easy to form a film, so the present invention is connected to the filaments, in the empty door; on the basis? The stupid ring and the lack of electricity are formed in a three-dimensional manner to increase the film forming property. Considering the difficulty of vacuum steaming and the molecular weight of the solid electron transporting material, the molecular weight does not exceed _. The present invention is based on the above considerations. The invention develops a new type of organic material which has good number stability and light. The local electron mobility can be used as a kind of material with strong electron transport capability in organic electroluminescence. The invention provides an organic material whose structural formula is as follows: Δη 迤

^ and ^ The residues ethane and b of the condensed aromatic aryl group having 6 to 30 carbon atoms are each independently selected from a hydrogen atom, a heterocyclic group having a carbon number of &amp; a fragrant group and a carbon number of 6 to 24. Integer. n is selected from 2 to, and the present invention also provides the use of the electron transporting material in the above organic material. In the present invention as an organic electroluminescent device, the present invention also provides an organic electroluminescent device having an electrode disposed between the pair of electrodes: the above organic material in the medium. The organic light emission 201122080 Embodiment The structural formula of the organic material of the present invention is as follows:

N

Ar-

Wherein, red is selected from the residues of the anthracene aromatic hydrocarbons of the carbon atoms An and An, respectively, which are independently '&quot; to 3 ;; the fragrant group, the number of carbon atoms is "the wind atom, the aryl group having 6 to 24 carbon atoms" The heterocyclic aryl group of the integer 24, which is selected from the group consisting of 2 to 3, is as follows:

^ 4;2 A 4? (2)

(4)

(6)

Wherein, Ar is selected from the group consisting of carbon atoms (7) Tibetan horses 6 to 30

An and An independently select the residue of each hydrocarbon in each case.

^ % 9 wind atom, carbon atom I π in the number 6 to 24 aryl 7 201122080 fragrant group, a heterocyclic aryl group having 6 to 24 carbon atoms; n is selected from an integer of 2 to 3. In order to more clearly illustrate the present invention, the preferred structures of the types of compounds to which the present invention pertains are specifically drawn below: (1) When η = 2, some of the major electron transporting materials are structured as follows:

2-7 2-8

8 201122080

2-9

2-10

2-11

2-12

2-13

2-14

2-15

2-16

2-17

2-18 9 201122080

2-24

2-26

2-29

2-30 ίο 201122080

(2) When n=3, the typical electron transport material structure is as follows:

11 201122080

The invention is also related to a device. Novel organic electroluminescence with higher performance The organic electroluminescence of the present invention: #哭电子传轮(四)1: The above novel compound

.../ Appropriate Qing and L_ level, with better electron injection capability and electronic value of electrons, and thus enhance the brightness and luminous efficiency of the light-emitting area. 0 #驱动电增强 i The organic electroluminescent U-piece of the present invention (4) The above novel compound can be selected from other suitable electron-transporting layers and hole-blocking layers, materials, and the device layer of the optimized device. Lei early privately should be /. It is said that the merger of the two /, to ensure that 1 effective transmission (four) when the defense against the "goods"

It is possible to obtain "...the accelerated cracking caused by the cathode, the stable and stable organic electroluminescent device. The organic thunder &amp;|, %nr electroluminescent device of the invention simultaneously selects the reductive substance matched by the above novel substance for...new i Injecting high-injection of high-electron electrons is enough to further reduce the main material of the electro-chemical compound, and the interfering agent can be dispersed to improve the stability of the device, and the interaction between the knives ^ ^ = the role of the scorpion On the other hand, the first layer and the electron injection transmission function... The material is selected to have an electron-transporting organic: Α buffer layer 'buffer organic material, which can be spatially divided into 12 201122080 luminescent layer and reducing dopant to form luminescence quenching. At the center of the second, the dopant diffuses and migrates to the light-emitting region. Therefore, the buffer layer is beneficial to the stability of the device. The electron-transfer material is used as a buffer to ensure that 15 driving voltages are guaranteed. Achieving practical requirements such as efficiency will not impose a new burden on the performance of the benefit piece.

(IV) Organic electroluminescence 11-pieces The above-mentioned novel compound doping = is a quinoid layer in the connection layer, and preferably the Ν/ρ connection layer connects two or two priming units as a charge generation layer. The current efficiency of the state in which the solid-state single 7L is superimposed is twice the current efficiency of a single light-emitting device, and the driving power is less than or equal to n times the single light-emitting device, and the power efficiency of the device of the present invention is also improved. In addition, the material of the invention has a higher glass transition temperature and a higher stability; the material has a lower molecular weight and a lower film deposition temperature, which is favorable for forming a uniform and dense film by thermal evaporation, and the preparation process is relatively simple. . The present invention also proposes an organic electroluminescent device comprising a pair of electrodes and an organic luminescent medium disposed between the pair of electrodes, the organic light-emitting substance 71 comprising a novel material selected from the above-mentioned general formula. The luminescent medium in the above organic device of the present invention comprises a light-emitting layer and an electron-transport layer functional layer, and the above novel material of the present invention is used in the above-mentioned electron-transporting functional layer. The electron transport functional layer further comprises another electron transporting material selected from the group consisting of a compound, a metal chelate compound, a trisalt compound, and rice. a compound, a phenanthroline compound or a stimulating compound. The above-mentioned oxime compound, metal chelate compound, triazole compound, imi 13 201122080 - phenanthroline compound or steroid compound includes: 2-(4_ ' ^ ) 5 (4~biphenyl)-1 , 3, 4-oxadiazole, tris(8-hydroxyquinoline) Shao 3 (4 ears buried base) phenyl _5_(4_butylphenyltriazole, 4, 7-diphenyl~]] , 10-phenanthroline, 2, 9-dimethyl-4, 7-diphenyl_1'1〇=嘻, 2-phenyl-9,10-naphthalene. v Two electron transport The electron transport functional layer of the material is also doped with an alkali metal, an alkali metal lanthanum, an oxide, an alkali metal complex, an alkali metal nitride, and a metal salt. The dopant is selected from the group consisting of a clock, a nitriding, and a nitriding. Clock, gasification clock, acid recording, oxidation clock 8 by 嗤 嗤 钟 clock, carbonate cone, degassing and unloading, town gasification clock, sodium fluoride, sodium gasification, fluorination planer, chlorination planer, bismuth oxide The above-mentioned dopant name Φ J2. a* Electron transporting work The doping concentration in this layer is U~4W, based on the weight of the host material. The electron injection and transfer function of the luminescent medium in the organic device of the present invention described above. The drawers are ready for the first layer and the power layer Electron injection and transport function 3 The novel compound of the present invention described above further comprises a dopant selected from the group consisting of metallurgical inspection, metal oxide, alkali metal complex, alkali metal nitride, Metal salt is tested. 1 The above-mentioned dopant is selected from the group consisting of bell, bismuth, gasification clock, gasification clock, oxidized chemistry, 8, 啥 啥 钟 clock, cesium carbonate, 气 gasification clock, which gasification clock sodium fluoride, chlorine Sodium hydride, fluorinated planer, gasification planer, yttrium oxide. The thickness of the above electron injection and transport functional layer is 2nm~4〇nm, thickness is 5nin 25mn 'Doping ratio of doping in the electron injection and transmission functional layer is weight percentage 49%, preferably doping: impurity S percentage 14 201122080 is more than 0.5% to 30%. In the above organic electroluminescent device of the present invention, a buffer layer is further included between the electron injecting and transporting functional layer and the light emitting layer. The material of the buffer layer is selected from the above novel compounds of the present invention, or is selected from the group consisting of an oxazole compound, a metal complex, a diazole compound, an imidazole compound, a quinoline compound, a porphyrin compound, and a diazonium compound. Diazophenan Compound.

The material of the above buffer layer is preferably selected from the above compounds of the above 2_ι to 2_38 and 3-1 to 3-3 of the present invention, or selected from 2__(4-tert-butylphenyl)-5-(4-diphenyl)-1,3. 4-oxadiazole, tris(8-hydroxyquinoline)aluminum, 3-(4-diphenyl)-4-phenyl-5-(4-butylphenyl)-, 2,4-triazole, 4, 7_Diphenyl-ι'ιο-phenanthroline, 2,9-dimethyl-4-7-diphenyl_11〇_phenanthroline, and 2-phenyl-9, 10- Naphthoquinone. The buffer layer has a thickness of 2 nm to 20 nm. In the above organic electroluminescence device of the present invention, the organic light-emitting medium contains at least two light-emitting units, and a connection layer is provided between the light-emitting units, and the above-mentioned connection layer contains the above-described novel compound of the present invention. The above connecting layer is further doped with a dopant selected from the group consisting of an alkali metal, an alkali metal oxide, a metal hydride, a metal nitride, and a metal salt. The dopant is preferably self-clocked, planed, nitrided by 'fluorine (tetra), Qian Zhong, oxidized, 8-hydroxyquinoline lithium, cesium carbonate, potassium borohydride 'sodium hydride lithium, sodium fluoride, sodium chloride, fluorinated Absolute, bismuth chloride, oxidation surface. Materials Synthesis Method Examples: Various pyridyl boronic acids, phenylpyridylboronic acids, 15 201122080 pyridylphenylboronic acid, various brominated, wild scorpion a/odor oxime, brominated naphthalene, anthracene used in the present invention The basic heart of brewing, Benzo, dibenzopyrene and so on is easy to buy, and the long-term recording and long-term recording in the chemical product market is more common in various organic pyridyl boric acid ^.^aa. The various bromines used in the present invention can be easily purchased in the domestic chemical product market from the base chemical materials such as 咬 蒽醌, 蒽醌, benzo, 酝, and 本 〜. Bromoanthracene, brominated hydrazine, various base groups and bite-based boric acid can be synthesized by common organic methods. j j «曰 Examples The following describes the synthesis of some of the main compounds in the present invention. Synthesis of Compound 2-1 of Synthesis Example 1 (1) First step reaction

A 500-mL three-necked flask was magnetically stirred. After argon replacement, 2-峨-5-mo, pyridinium I3.4g (purity 99%, 0.0473 mol) and THF 200 ml were added in that order. N-butyllithium i9 ml (concentration 2·5 M, 0. 0475 mol) was added dropwise at -83 ° C, and then 蒽醌 4·8 g (purity 99%, 〇 _ 023 m 〇 1) was immediately added. After the addition was completed, the solution was naturally warmed to room temperature and the solution was bright yellow. Add 2 ml of water to hydrolyze, extract 'Evaporation dry solvent' with ethyl acetate, add 3 〇〇ml of acetic acid, 18 g of KI and 18 g of sodium hypophosphite, reflux, react for 1 hour, cool down, and evaporate dry acetic acid, 16 201122080 The product was washed with water to give 5.05 g of a yellow compound, a purity of 87.42%, and a yield of 39.19%. (2) The second step reaction

Under the protection of N2 gas, 9,10-di(5__Pyridin-2-yl)phosphonium 6. Og (molecular weight 490, purity 87.42%, 0. 0106 mol), phenylboronic acid 3.克 (5. Purity AR, 0. 〇 486 mol), A stupid 86 ml ''ethanol 60 ml, water 72 rol. The above materials were heated to reflux, and _ benzene succinic acid (1 g each time) was added. After 4 hours, the reaction was stopped, allowed to cool, and the mixture was poured. The back cake was boiled with toluene hot, and the catalyst was removed. The catalyst was distilled off, and the water/THF of the solid was boiled, and the mixture was filtered off with cold and repeated twice. Obtained as a white-gray compound 2-1, purity 99-1%, yield 77.97%. Product mass spectrum (MS) (m/e): 484; Elemental analysis (c^2): Theoretical value C: 89.23%, H:4.99%, N: 5.78%; h^c: 89 i'〇%, Η : 5. 08%, N: 5·82%. Synthesis of Compound 2 - 3 of Synthesis Example 2 The same procedure as in Example 1 was carried out to select 2 - moth 4 - odor 0 to 0, benzene acid, and the same two-step reaction gave a pale yellow compound 2-3. 17 201122080 Product MS (m/e): 484; Elemental analysis (C36H24N 〇: Theory C: 89.23%, H: 4.99%, N: 5.78%; found C: 89.21%, H: 5. 05%, N : 5. 74%. Synthesis of compound 2 - 5 of Synthesis Example 3 (1) First step reaction

500 ml three-necked bottle was mixed with magnetic force. After argon replacement, 8.26 g of 2-iodo-5-bromopyridine (purity of 99%, 0.0288 mol) and 3.58 g of phenylboronic acid (purity of 98%, 0.0292 mol) were added. Pd( PPh3) 4 1.79g (AR, 〇·〇〇155mol) 'Sodium carbonate aqueous solution 175ml (concentration 2M), benzene 175ml, ethanol 175ml. 5%。 The yield was 94.43%. The product was purified by a column. (2) The second step reaction

The 5 00 ml three-neck bottle was magnetically stirred, and after nitrogen substitution, 201122080 2-phenyl-5-bromoacridine 6 75 g (purity 95 45%, 〇 〇 274 m 〇 1), THF 11 mol. 6克(纯度纯度99%, 0.0124摩尔) was added after -7 (Tc was added dropwise 13 ml of n-butyllithium (concentration: 2 5 M, 〇. 0325 m 〇 1). After the addition, 加 2. 6 g (purity 99%, 0.0124 mol). Naturally warm to room temperature, the solution is bright yellow. Add 200ml of water to hydrolyze 'extract with ethyl acetate, and evaporate the solvent. Add 220ml of acetic acid, 22g of KI and sub-linalic acid, reflux. React for 1 hour, cool down, cool filter The yield is 2. 8g of pale yellow product. It is boiled for 1 hour with water of ιν 10 / / THF φ, and it is filtered off with a few times to obtain 2 · 1 g of pale white compound 2-5. The yield was 20.48%. Product MS (m/e): 484. Elemental analysis (C36HuN2): Theory C: 89. 23%, Η: 4.99% 'N: 5.78%; found C: 89 30%, Η: 5. 01%, Ν: 5. 69%. The synthesis of the compound 2-7 of Synthesis Example 4 was carried out using 2-phenylindole, 3,5-bromopyridine as the same as in Example 3. Step reaction 'to give pale yellow compound 2-7. Product MS (m/e): 560; • Elemental analysis (C42M2): Theoretical value c: 89. 97%, Η: &quot;5. 03%, N: 5· 00%; measured value C: 89. 91%, Η: 5. 06%, Ν: 5. 03%. Synthesis Example 5 compound 2-9 Awake, 2-phenyl-4-di-D-bite, the same reaction as in Example 3 was obtained to give a pale yellow compound product MS (m/e): 560; Elemental analysis (C42H28N2): Theory C: 89 97% ' H : 5. ' N : 5. 00% ; Found C : 89. 98%, Η : 5. 05%, N : 4. 97%. Synthesis of compound 6-11 for synthesis of compound 2 , 6 - 2 (3 _ ° vs. 0 base) awake, 2 - hard-5 - bromine 0 than bite 'by the same reaction as 19 201122080 Example 1 'to obtain yellow compound 2-i 1 ^ product MS (m/ e): 638, elemental analysis (C46H): theoretical value C: 86.49%, Η: 4. 73% 'N: 8·77%; measured value c: 86. 40%, Η: 4. 79%, Ν: 8. 81%. Synthesis of compound 2-13 of Synthesis Example 7 2,6--the base was used to brew '2-moth-5-bromoindole, and the same reaction as in Example 3 was obtained to give a pale yellow compound 2- 13. Product MS (m/e): 636; Elemental Analysis (C48H): Theory: C: 90.53%, H: 5.07%, N: 4.40%; found C: 90.50%, H: 5.12%, N: 4.38 %. Synthesis of Compound 2-15 of Synthesis Example 8 Benzopyrene&apos;-phenyl-2-bromopyridine was used in the same manner as in the second step of Example 3 to give yellow compound 2-15. Product MS (m/e): 534 ; Elemental analysis (C4 «H26N2): Theory: C: 89.86%, Η: 4.90%, N: 5.24%; found C: 89.80%, Η: 4.91%, Ν: 5.29 %. Synthesis of Compound 2-18 of Synthesis Example 9 Benzoindole, 2-iodo-5-bromopyridine was used, and the same compounding procedure as in Example 3 was used to give yellow compound 2-18. Product MS (m/e): 534; Elemental analysis (C4 〇 H26N2): Theory C: 89.86%, H: 4.90%, N: 5_24%; Measured C: 89.85%, H: 4.82%, N: 5,33%. Synthesis of Compound 2-19 of Synthesis Example 10 A yellow compound 2-19 was obtained by the same reaction as in Example 3, using one and brewing, 2 - moth-5 -bromo ratio. Product MS (m/e): 584; Elemental analysis (C44H28N2): Theory C: 90. 38%, Η: 4. 83%, N ·· 4. 79 %; found C: 90. 34%, Η : 4. 90%, Ν: 4. 76%. 20 201122080 Synthesis of compound 2-21 of Synthesis Example 11 Dibenzopyrene, 2-substituted-5-bromo was used. The same reaction as in Example 1 was carried out to give a yellow compound 2-21. Product MS (m/e): 584; Elemental analysis (C44H28N2): Theory C: 90.38%, H: 4.83%, N: 4.79 %; found C: 90. 46%, Η: 4. 70%, N : 4. 84%. Synthesis of Compound 2-23 of Synthesis Example 12 Using phenanthrenequinone, 2-iodo-5-bromopyridine, the same reaction as in Example 1 gave yellow compound 2-23. Product MS (m/e): 484; Elemental Analysis (CaH): Theory: C: 89.23%, H: 4.99%, N: 5.78%; Found C: 89.40%, H: 4.85%, N: 5.75%. Synthesis of Synthesis Example 13 Compound 2 - 2 5

Under the protection of N2 gas, 3,9-di-bromoindole 4.32g (purity 95% ' 〇. 〇im〇i), 6-phenylpyridine-3-boronic acid 5. lg (in a 500 mL three-necked flask) The purity of 98% ' 〇. 〇 25mol), gasified palladium ruthenium. 21g (purity AR, 0. 0012mol), diphenylphosphine 0 · 63g (purity AR, 0. 0024mol), potassium carbonate 5. 3g (purity AR ' 0. 0486mol) 'Toluene 86m, ethanol, 60m, water, 72ie, the above materials were heated to reflux. After 4 hours, the reaction was stopped. The mixture was allowed to cool, and the filter cake was filtered. The catalyst was removed by hot boiling. The catalyst was removed, and the benzene was distilled off. The solid was boiled with 1/1 Torr of water/THF, and then filtered, and then evaporated. The yield was 75.1%, and the yield was 75.26%. 21 201122080 Product MS (m/e): 558; Elemental analysis (C42H26N2): Theory C: 90.29%, Η: 4.69%, N: 5.01%; found C: 90.11%, Η: 4·88%, Ν : 5. 01%. Synthesis of Compound 2-28 of Synthesis Example 14 Using 3,9-di-bromoindole, 5-phenylpyridine-3-boronic acid, the same reaction as in Example 13 gave yellow compound 2-28. Product MS (m/e): 558 ; Elemental analysis (C42H26N2): Theory C: 90. 29%, Η: 4. 69%, N: 5. 01%; found C: 90.11%, Η: 4. 88%, Ν: 5. 01%. Synthesis Example 1 Synthesis of Compound 2 - 31 @6-di-bromo-bromo, 6-phenylpyridine-3-boronic acid was used, and the same procedure as in Example 13 to give a yellow compound 2-31. Product MS (m/e): 534; Elemental analysis (C4 〇 H26N2): Theory C: 89.86%, Η: 4.90%, Ν: 5. 24%; found C: 90. 01%, Η: 4. 86%, Ν: 5. 13%. Synthesis of Compound No. 3-33 of Synthesis Example 16 Using the same procedure as in Example 13 using 6,12-di-bromo-bromo, 5-phenylpyridine-3-boronic acid, a yellow compound 2-2-3 was obtained. Product MS (m/e): 534; Elemental Analysis (CoL): Theory C: 89.86%, H: 4.90%, N: 5. 24%; found C: 89. 80%, Η: 4·93 %, N : 5. 27%. Synthesis of Compound 2-35 of Synthesis Example 17 Using 1,6-di-bromoindole, 4-phenylpyridine-2-boronic acid, the same reaction as in Example 13 afforded yellow compound 2 - 3 5 . Product MS (m / e): 508; elemental analysis (C - O: theory C: 89.74%, Η: 4.76%, Ν: 5. 51%; found C: 89.81%, Η: 4. 70 %, Ν : 5 · 49%. Synthesis Example 1 Synthesis of Compound 2 - 3 7 22 201122080 The same reaction as in Example 13 was carried out using 1 '6-di-bromoindole, 2-phenylpyridine-4-boronic acid. 'Yellow compound 2-37. Product MS (m/e): 508; Elemental analysis (C38H24N2): Theory C: 89. 74%, Η: 4. 76% ' Ν : 5. 51 妒; measured value C : 89. ' Η : 4. 81%, Ν : 5. 49%. Synthesis of compound 3-1 of compound 19 is selected from 2, 9, 10-tribromo fluorene, 6-phenylpyridine-2-boronic acid, The same reaction of Example 13 was carried out to give a pale-yellow compound 3-1. Product MS (m/e): 637; Elemental analysis (C47H3lN3): Theory C: 88.51%, H: 4.90%, N: 6.59%; Found C: 88. 49%, Η: 4, 95%, N: 6.56%. The synthesis of compound 3-3 of Synthesis Example 20 was carried out using 2,9,10-dibromoindole ' 6 -phenyl 0 than cross-3 - shed acid, the same reaction as in Example 13 to give a pale-yellow compound 3-3. Product MS (m/e): 637; Elemental analysis (C47H31N3): Theory C: 88.51%, H: 4.90%, N : 6. 59%; measured value C: 88. 55%, Η: 4.93%, N: 6. 52%. Embodiments of Organic Electroluminescent Device: The basic structure in the organic electroluminescent device proposed by the present invention includes: a substrate, a pair of electrodes, and an organic medium disposed between the electrodes, including an empty electron transport layer, an electron injection hole injection layer, a hole transport layer, a light emitting layer, a layer, a barrier layer, etc. may be glass or a flexible base a flexible base body is a transparent substrate, and the sheet is made of one of a polyester type and a polyamidide compound;

The electrode layer (anode layer), the machine material is generally ΙΤΟ, 23 201122080 copper, silver and other metals with higher work function, the optimal choice of ΙΤ 4 ΙΤ 0 'organic conductive polymer is preferably polythiophene / polyvinyl sulfonate (Simplified below, PED0T: PSS), polyaniline (hereinafter referred to as PANI) - the first electrode layer (cathode layer, metal layer), generally using lithium, magnesium, Qiao, recorded, Syrian, marriage and other work functions Lower metals or alloys thereof with copper, gold, silver, and electrode layers alternately formed with metal fluorides, the present invention is preferably a sequential Mg:Ag alloy layer, an Ag layer, and a sequential LiF layer, A1 layer.

The organic luminescent medium mainly comprises an organic electroluminescent layer (EML), generally using a small molecular material, and may be a fluorescent material such as a metal organic complex (such as

Alq3, Gaq3, Al(Saph-q) or Ga(Saph-q)) compounds, the small molecule material may be doped with a dye, and the doping concentration is "?2" Wt% of the small molecule material, and the dye is generally For a material of aromatic fused ring (such as rubrene), coumarin (such as DMQA, C545T) or dipyran (such as DCJTB, DCM), the luminescent layer material can also be carbazole. a compound such as 4,4 _N' N - hexa-17 azole-biphenyl (CBP), polyvinyl carbazole (ρνκ),

The material may be doped with a phosphorescent dye, nr(ppy)3) 'bis(2-phenyl such as tris(2-phenyl)pyridyl)pyridinium)(acetamidineacetone)iridium (Ir(ppy)2(acac) , octaethyl porphyrin platinum (pt〇Ep), etc.; the above device structure may further include a hole injection layer and a hole transport layer 'Hole injection layer (HIL) matrix material may be copper phthalocyanine (CuPc) , 4,4 4 -tris(N-3-methylphenyl-N_phenyl-amino)_triphenylamine (m MTDATA), 4'4 4" -tris(N-2-Caichi-N _Phenyl-gas-based)-triphenylamine (2-TNATA) The material of the hole transporting layer may be selected from the group consisting of ruthenium, osmium, bis-(p-naphthyl)-N, 24 201122080 〜amine (ΝΡΒ), TPD and the like. The material used in the present invention is Ν'-diphenyl-1, fluorene- phenyl- 4,4, electron injecting and transporting functional layer materials in the device. Several materials used in the present invention are as follows.

ΕΤ-11 ΕΤ-22 Several embodiments will be given below and the present invention will be specifically explained with reference to the accompanying drawings.

Technical solution. It should be noted that the following examples are only intended to aid the understanding of the invention and are not intended to limit the invention. Benefits Design: In order to facilitate the comparison of the transmission properties of these electron transport materials, the present invention is a tenth-simple electroluminescent device (substrate/anode/hole transport layer (HTL)/organic light-emitting layer (EML)/electron transport layer (etl) / cathode), the luminescent layer uses 9 10 - (2-Nyliden) 蒽 (shed) as an example of luminescent materials (that is, the main material # ' is not a luminescent material, the purpose is not to pursue high efficiency, but to verify these materials Practical possibilities). 25 201122080 Example 1: Device structure: IT〇/NPB (40 nm)/ADN (30 nm) / Compound 2-1 (20 nm) / LiF (〇.5 nm) / Al (150 nm) Glass coated with ΙΤ0 transparent conductive layer The plate is sonicated in commercial detergent, rinsed in deionized water, ultrasonically degreased in acetone:ethanol mixed solvent, baked in a clean environment to completely remove water, cleaned with ultraviolet light and ozone' and bombarded with low energy cation beam The glass substrate with the anode is placed in a vacuum chamber, and evacuated to lxl (T5~9xl (T3pa, vacuum evaporation of ΝρΒ on the anode film as _ hole transport layer, evaporation rate is 〇 Lnm / s, the thickness of the vapor deposition film is 5 〇 nm; ADN is vacuum-evaporated on the hole transport layer as a light-emitting layer of the device, the steaming rate is 0. lnm / s 'the total film thickness of the vapor deposition is 3 〇 nm; The compound 2-1 of the present invention is vacuum-dried over the luminescent layer as an electron transport layer of the device, and the evaporation rate is 〇. lnm/s, and the total thickness of the deposited film is 2 〇 (10); vacuum evaporation on the electron transport layer The LiF of the thickness 〇511111 is an electron injection layer, and finally the thermal evaporation coating metal A1 is a cathode with a thickness of l5 〇 nm. Example 2: Device structure: IT〇/NPB (4〇nm)/ADN (30 nm) / compound 2-3 (30 nm) / LiF (0.5 nm) / Al (150 nm) The above device was prepared in the same manner as in Example 1. The difference is that the electron transport layer adopts the compound 2_3 of the present invention and has a thickness of 3 〇 nm. LiF having a thickness of 0.5 nm is deposited as an electron injection layer, and finally the hot steam cover metal is a cathode having a thickness of 150 nm. Comparative Example 1: 26 201122080 Device structure: IT 〇 / NPB (40 run) / ADN (30 nm) / Alq3 (20 nm) / LiF (0.5 nm) / Al (150 nm) The above device was prepared in the same manner as in Example 1, except that the electron transport layer was made of A1q3, thickness. 20 nm 〇 Comparative Example 2: Device structure: ITO/NPB (40 nm) / ADN (30 nm) / Alq3 (30 nm) / LiF (0.5 nm) / Al (150 nm) φ The above device was prepared in the same manner as in Example 1, except that The electron transport layer was Alq3 and had a thickness of 30 nm. Comparative Example 3: Device structure: ITO/NPB (40mn) / ADN (30mn) / ET - 11 (20mn) / LiF (0.5 nm) / Al (150 nm) According to Example 1 The above device was prepared in the same manner, except that the electron transport layer material was ET-11 and the thickness was 2 〇 nm.

Current efficiency cd/AX y at a voltage V of 1000 cd/m at 1000 cd/m2 Example 1 Compound 2-l (20 nm) 8.14 0.97 0.1997 0 2525 Example 2 Compound 2-3 (30 nm) 9.95 1.02 0.1858 〇2620 Comparative Example 1 Α1φ(20ηπ〇10. 76 0.82 0.1927 0 Comparative Example 2 Alq3(30nm) 11.58 0.78 0.1951 0. 2611 Comparative Example 3 ET-11(20nm) 8.16 0.90 0.1920 J. 2565 It can be seen from Table 1. When the electron transport layer is used in the electron transport layer 27 201122080 2-1 or compound 2-3, the voltage at the time of the storage and de-si λλ λ reaches 1 000 cd/m 2 is lower. Lumen efficiency, double early and external quantum efficiency are higher, and the color coordinate $ is red-shifted. The lightning value of Example 2 is increased by 1 Onm ', but the thickness of the obtained layer is increased. The effect of the performance of the J heart s is smaller. While the electron transport layer of the comparative example 2 is also increased by 1 〇 nm, the driving voltage of the device is also increased. The driving voltage is significantly increased and the efficiency is also lowered. In Comparative Example 3, (4) was used as the electron transport layer, and the driving voltage was high as compared with Example 1, and the efficiency was low. It is shown that the novel organic material of the present invention can be preferably used as an electron transport layer in an organic electroluminescence device. Embodiment 3: Device structure: ITO/NPB (40mn) / ADN (30 nm): 7% TBP / compound 2 9 (30 nm) / LiF / A1 The IT substrate was processed in the same manner as in Example 1, and the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer were sequentially deposited in the vapor deposition chamber. The cathode structure, the chamber pressure during the evaporation process is less than 5.0×10 3pa. In this embodiment, the organic layer is first vapor-deposited with 4〇nm thick Νρβ as a hole transport layer; evaporation by double source co-steaming method 3〇nm thick ADN and 2,5'8,1 tetra-tert-butyl fluorene (TBPe) as the luminescent layer, the ratio of TBPe in ADN by rate control is 7%; the compound 2-9 of steaming 20nm as electron The transport layer; 0.5 nm of LiF as an electron injection layer and 15 〇nm of A1 as a cathode. Example 4: Device structure: ITO/NPB (40 nm) / ADN (30mn): 7% TBP / compound 2-9 (20 nm) /Alq3(l〇nm)/LiF/Al 28 201122080 The above device was prepared in the same manner as in Example 3 except that the 20 nm layer was sequentially vapor-deposited on the light-emitting layer. Alq3 of 2-9 and 10 nm was used as an electron transport layer; finally, LiF of 0.5 nm was vapor-deposited as an electron injection layer and A1 of i50 nm was used as a cathode. Example 5: Device structure: ITO/NPB (40 nm) / ADN (30 nm): 7% TBP / compound 2-9 (20 nm) / compound 3-1 (10 nm) / LiF / Al The above device was prepared in the same manner as in Example 3. The difference was that the compound 2-9 and the 10 nm compound 3-1 which were successively vaporized on the light-emitting layer were successively used as an electron transport layer; finally, Li F of 0.5 nm was vapor-bonded as an electron injection layer and A1 of 150 nm was used as a cathode. Comparative Example 4: Device structure: ITO/NPB (40 nm) / ADN (30 nm): 7% TBPe/Alq3 (30 nm) / LiF / Al The above device was prepared in the same manner as in Example 3 except that an evaporation of 30 nm was performed on the light-emitting layer. Alqs is used as the electron transport layer; finally, LiF of .5 nm is vapor-deposited as the electron injecting layer and A1 of ΐ5〇η!Π is used as the cathode. Comparative Example 5: Device structure: ITO/NPB (40 nm) / ADN (30 nm): 7% TBPe/ET-12 (30 nm) / LiF / Al The above device was prepared in the same manner as in Example 3 except that it was steamed on the light-emitting layer. 30 nm of ET-12 was plated as an electron transport layer; finally, 5 nm of LiF was used as an electron injection layer and A5 〇nm A1 was used as a cathode. 29 201122080 Table 2 Brightness at 8 V (cd/m2) Efficiency at 8 V (cd/A) Current density at 8 V (A/mz) Example 3 Compound 2-9 (30 nm) 15,320 7.3 2, 099 Example 4 Compound 2-9 (20 nm) / AlQ3 (10 nra) 11, 350 6.4 1,773 Example 5 Compound 2-9 (20 nm) / Compound 3-1 (10 nm) 15, 660 7.2 2, 175 Comparative Example 4 Alqa OOnm) 10,070 6.0 1 , 678 Comparative Example 5 ET-12 13, 850 6.8 2,036 From Table 2 'Example 3 using the compound 2 - 9 of the present invention as an electron transport layer', high brightness and efficiency were obtained in the blue doped layer system. The electron transporting layers of Examples 4 to 5 have a two-layer structure, and the difference is that the two layers of electron transporting materials are different. From the viewpoint of the devices, Examples 4 to 5 still obtain higher brightness and efficiency. In Examples 3 to 5, the brightness, efficiency, and current density were greatly improved as compared with the device of Comparative Example 4 having only the Alqs electron transport layer. It is indicated that the compounds of the present invention can be matched to other electron transport materials such as Alqa to achieve higher device performance. Example 6: Device structure: IT〇/NPB (4〇nm)/PADN (30nm): 1% C545T/compound 2-13 (30 nm) / Mg: Ag/Ag The above device was prepared in the same manner as in Example 3, and the difference was made. The luminescent layer of the present embodiment is a dual source co-evaporated 3 〇 nm thick pAM and 2, 3, 6, tetrahydro-1' 1' 7' 7, 4-tetramethyl-1H, 5H, uh_1 〇 _ ( 2_benzothiazolyl) quinolizin (C545T), the rate of C545T in pADN is 1/〇, and 3〇nm of compound 2_13 is evaporated on the luminescent layer as electron transport 30 201122080 A method of vapor deposition of 1 〇Οηπι of Mg: Ag as a cathode with a ratio of 10:1 'finally covers 5 nm of Ag as a protective layer. Example 7: Device structure: IT0/NPB (40 nn /: PADN (30 mnh 1% C545T / compound 2-13 (20 nm) / 3-3 (l 〇 nm) / Mg: Ag / Ag in the manner of Example 6 The above device was prepared, except that the compound 2-13 and the 1 nm compound 3-3 were sequentially vaporized on the light-emitting layer as φ as an electron transport layer; and 1.0 nm of Mg: Ag was vapor-deposited by a dual source co-evaporation method. The cathode has a ratio of 10:1, and finally covers 50ηιπ of Ag as a protective layer. Comparative Example 6: Device structure: ITO/NPB (40 nm)/PADN (30 nm): 1% C545T/Alci3 (30 nm)/Mg: Ag /Ag The above device was prepared in the same manner as in Example 6, except that 30 nm of Alqa was vapor-deposited on the light-emitting layer as an electron transport layer; 10 nm of Mg was vaporized by a dual source co-evaporation method: Ag was used as a cathode, and the ratio was 1 : 1. Finally, cover _ 50 nm of Ag as a protective layer. Comparative Example 7 : Device structure: ITO/NPB (40 nm) / PADN (30 nm): 1% C545T / ET-11 (3〇Tim) / Mg : Ag / Ag The above device was prepared in the same manner as in Example 6, except that 30 nm of ET-11 was vapor-deposited on the light-emitting layer as an electron transport layer; and 100 nm of Mg:Ag was vapor-deposited by a two-source co-evaporation method, and the ratio was 1〇: 1 Finally, Ag covering 5Onm is used as a protective layer. 31 201122080 Table 3: Brightness at 8 V (cd/m2) Efficiency at 8. V (cd/ΑΊ Current density at 8 V Example 6 Compound 2-13 (30 nm) 25, 780 19.6 vA/m ; 1 οι η Example 7 Compound 2-13 (2Qnm) / compound 3-3 〇 0 nm) 27, 880 18.7 ly Ui ϋ 1,488 Comparative Example 6 Alq3 (30 nm) 20, 350 11.8 1 7〇C Comparative Example 7 ET-11 23, 890 17.9 1 &gt; 1 £ιϋ 1,334 From Table 3, the light-emitting layers of Examples 6-7 employ the common green light system PADN: C545T for the purpose of verifying the present invention. The application prospect of compounds as electron transport layers in green light. From the comparison of device results, the electron transport layer used can effectively reduce the driving voltage and improve the brightness and efficiency of the device, whether it is a two-layer structure or a single-layer structure. Examples 6-7 have a significant improvement in brightness, efficiency, and current density compared to Comparative Example 6. Example 8 Device Structure: ITO/NPB (4〇nm)/AlQ3(50(10))/Compound 2-21 :CsC〇3(20nm, 10%) /Al(i5〇nm) The IT〇 conductive glass substrate with a specific pattern will be used as the substrate. The film is ultrasonically cleaned in deionized water containing a cleaning solution, the temperature of the washing liquid is about 60 C', and then the cleaned substrate is baked and dried in an infrared baking lamp to be placed in the steaming mirror cavity to sequentially flow into the liquid layer. Οχ1〇-3ρ3。 The hole transport layer, the luminescent layer, the electron transport layer, the electron injection layer, the cathode structure, the chamber pressure during the steaming process is less than 5. Οχ1〇-3ρ3. 32 201122080 In the embodiment, 〇0 anode is first hot deposited by vapor deposition of 4 〇nm NPB as a hole transport layer; 50 nm thick 8 hydroxyquinoline aluminum (Alq3) is continuously evaporated as a light-emitting layer, and a total clock method is used. The electron injecting and transporting functional layer of the evaporated bond, wherein the compound CsCCh has a doping concentration of ίο% (% by weight) in the compound 2-21 of the present invention; finally, 15 〇nm of A1 is evaporated as a haze Example 9 • Device structure: ITO /NPB (40 nm) / Alq3 (50 nm) / Compound 2-25: CsF (20 nm, 10%) / Al (150 nm) The above structural device was prepared by the method of Example 8, except that the compound of the present invention 2-25 was used. The csf doped with 1% by weight is used as the electron injection and transport functional layer of the device. Example 10 Device structure: ITO/NPB (40 nm) / Alq3 (50 nm) / Compound 2-28: KBH (20 nm, 10%) / Al (150 nra) • The above structural device was prepared according to the method of Example 8 The 〇H doped with 〇% by weight in the compound 2-28 was used as the electron injection and transport functional layer of the device. Example 11 Device structure: ITO/NPB (40 nm) / Alq3 (30 nm) / Compound 2-18 (20 nm) / Compound 2-3: Li3N (20 nm, 10%) / Al (150 nm) Prepared according to the method of Example 8. The above structural device differs only in that the light-emitting layer is 30 nm of Alqp on which 2 nm of the compound 2-18 is first deposited as a buffer layer of the device' and then the doping 丨〇% (weight: 33, 2011,220,080) in the compound 2_3 is used. L i3 N acts as a device for the early, early, λ J electric thousand injection and transmission functional layer. Comparative Example 8 Device structure: ITO/NPB (4 〇 nm) / Ak3 (5 〇 nm) / LiF (〇 5 nnm) / Al (150 nm) According to the method of Example 8, 锄μ, +. : 4 structural device, the difference is that there is no electronic intrusion and transmission functional layer of the present invention in the device, and only the electron injection layer of L i F is used. Comparative Example 9 Benefits, structure, ITO/NPB (40 nm) / Alq3 (50 nm) / A1q3: KBH (20 nm, 10 ° / 〇) / Al (150 nm) According to the method of Example 8, the μ, +, from the ancient The above structural device is prepared, except that the electronic injection layer of the present invention is not included in the device, and the electron injection layer of AlqrKBH is used only for the functional layer of the king and the transfer wheel. Comparative Example 10 Device structure: ITO/NPB (40 nm) / Alq3 (50 nm) / ET_12: Li3N (20ηπι, 10%) / Al (150 nm) The above structural device was prepared according to the method of Example 8, except that there was no such device. In the electron injecting and transporting functional layer of the present invention, only the electron injecting layer of ET-12:Li3N is used. The device performance data of the above embodiment is shown in Table 4 below. Table 4:

Example 8 Compound 2-21: CsC〇3 (20 nm, 10%)/A1 Current Density A/m2 ----_ 2000 6.78 539.94

Current efficiency cd/A 3. 70 T70* (hours) @2000cd/m2 358 34 201122080 Example 9 Compound 2-25: CsF (20 nm, 10%) / A1 2000 6.86 628. 54 3.18 216 Example 10 Compound 2 28: ΚΒΗ (20 nm, 10%) / A1 2000 7.52 554. 56 3.61 455 Example 11 Compound 2-18 (20 nm) / Compound 2-3: LiaN (20 nm, 10%) / A1 2000 6.48 662. 71 3.02 558 Comparative Example 8 LiF (0.5 nnm) / Al (150 nm) 2000 6.58 645.16 3.10 120 Comparative Example 9 Alq3: KBH (20 nm, 10%) / Al (150 nm) 2000 7.55 692. 04 2.89 169 Comparative Example 10 ET-12: Li3N (20nm, 10%) / Al (150nm) 2000 7.21 653. 59 3.06 187

From Table 4, Examples 8 to 11 are NPB/Alq3 classical double-layer devices. Compounds 2-21, 2-25, and 2-28 are mixed with different dopants to compare their driving voltage, efficiency and stability. At a luminance of 2000 cd/m2, the driving voltage is distributed from 6.48 V to 7. 5.2 V, and the efficiency is up to 3.7 cd/A. The stability is attenuated to a 70% lifetime with a parallel to φ ratio and a lifetime of from 200 hours to 56 hours. In Example 11, a buffer layer was further interposed between the light-emitting layer and the doped electron transport injection layer to be a compound 2-18 of 20 nm. The addition of the buffer layer can separate the luminescent layer from the inorganic dopant, and can prevent the inorganic dopant from diffusing and migrating to the luminescent layer, thereby improving the lifetime of the device more effectively, and the time is 558 hours when the brightness is attenuated by 70%. Significantly higher than other examples and comparative examples. Comparative Example 8 is a conventional NPB/Alq3/LiF/Al bilayer device, which has no doping structure used in the present invention, since the total thickness of the organic layer of the device is thinner (20 nm less) than that of the implementation of 35 201122080, Examples 1 to 4, The drive voltage is lower at 6.58V, and the efficiency reaches 3.1 〇cd/A 'but the lifetime is only 120 hours. Comparative Example 9 is a commonly used A1 q3 'Comparative 10 is an ET-12 material. After the dopant is mixed, since the electron mobility of Alqa and BAlq is not as good as the organic material of the present invention, the driving voltage of the comparative example is high, The efficiency is low. Although the lifespan of Comparative Examples 9 and 10 was higher than that of Comparative Example 8, it was less than 2 % by more than the example, which was related to the lower glass transition temperature of A1Q3 and ET-12.

Example 12 Device Structure: ITO/m-MTDATA: F4-TCNQ (150 nm, 2%) / NPB (20mn) / MADN: TBPe (3 〇 nm, 5%) / Alq3 (l〇nni) / Compound 2-33 : CsF (10 nm, 5%) / Α 1 (150 nm) The above structure device was prepared according to the method of Example 1, and a hole injection layer was deposited on the surface of the 〇IT〇 anode, and the hole injection layer was 15 nm thick m-MTDATA, wherein The 2% doped F4_TCNQe is further deposited as a hole transport layer. The luminescent layer is a blue light body 2-methyl-9,10_bis(2-naphthyl)-fluorene (MADN) doped with 5% ratio of blue dye 2, 5, 8, tetra-tert-butyl flower (TBPe), luminescent layer The thickness is 3Gnm. The buffer layer between the light-emitting layer and the electron-transporting layer is 晟厣&amp; τ η * 嘈 嘈 thickness is l 〇 nm, and the deposited material is Μ. . The electronic, primary, and transport functional layers are co-distilled with compound (iv) and W, and the push concentration of W is 5% and the thickness is 1 〇. Finally, (4) a metal M having a thickness of 15 〇 nm is used as a cathode. 36 201122080 Example 1 3 Device structure: ITO/m-MTDATA: F4-TCNQ (150 nm, 2%) / NPB (20 nm) / MADN: TBPe (30 nin, 59 〇 / BCP (2nin) / compound 2-33: Li3N (10 nm, 25%) / Α 1 (150 nm) The above structural device was prepared in the same manner as in Example 12 except that the thickness of the buffer layer between the light-emitting layer and the electron transport injection layer was 2 nm 'deposited material was 2' 9_2 Methyl-4,7-diphenyl], 10-phenanthroline (BCP). The electron injecting and transporting functional layer is prepared by the co-evaporation process of the compound and the state, and the doping concentration of LhN is 25%. The thickness is 1 〇 nm. Example 14 Device structure: ITO/m-MTDATA: F4-TCNQ (15 〇 nm, 2%) / NPB (20 mn) / MADN: TBPe (30 nm, 5%) / PBD (20 nm) / compound calls 2-33: LiF (10 nm, 50%) / Al (i5 〇 nm) The above structural device was prepared according to the method of Example ' 2, except that the thickness of the buffer layer between the light-emitting layer and the electron-transporting layer was 2Gnm, the deposition material is 2-(4-diphenyl)-5-(4_tert-butylbenzene i,3,4-dioxin. The electron injection and transport functional layer adopts the compound &quot;3 and W Co-heating process preparation 'and UF doping concentration is 5〇%, thickness For ι〇(10). Comparative Example 11 Device structure: 37 201122080 ITO/m-MTDATA: F4-TCNQ (150 nm, 2%) / NPB (20 nm) / MADN: TBPe (30 nm, 5%) / Alq3 (20 nm) / LiF (〇5nm)/Al(150nm) The above structural device was prepared according to the method of Example 12, except that there was no doping layer for electron transport and implantation, but a thickness of 20 nm of Alq3 was directly deposited on the light-emitting layer as an electron transport layer. Finally, Li.5nm LiF was deposited as electron injection layer and 150nm AI was used as cathode. Comparative Example 12 Device structure: ITO/m-MTDATA: F4-TCNQ (150nm, 2%)/NPB (20nm)/MADN: TBPe (30nm , 5%) / Compound 2-33 (20 nm) / LiF (0.5 nm) / Al (150 nm) The above structural device was prepared according to the method of Example 12, except that there was no doping layer for electron transport and implantation, but light was emitted. On the layer, a compound of 2 to 3 μm thick was deposited as an electron transport layer, and finally LiF of 5 nm was deposited as an electron injection layer and A1 of 15 Onm was used as a cathode. Device performance of the above Examples 12-14 and Comparative Example 1 The data is shown in Table 5 below: Device Structure Brightness cd/m2 Voltage V Current Density A/m2 Current Efficiency cd/A x(5V) y(5V) Example 12 Alq3(10nm)/Chemical 2-33: CsF (10 nm, 5%) 5000 8.06 722. 07 6.92 0.1434 0.1901 Example 13 BCP (2 nm) / compound 2 - 33: Li 3 N (10 nra, 25%) 5000 8. 52 762. 84 6.55 0.1419 〇. 1892 38 201122080 Example 14 PBD (20 nn / compound 2-33 : LiF (lOmii, 50%) 5000 8.35 813.71 6. 14 0.1415 ---- ο. 1874 Comparative Example 11 Alq3 (20 nm) / LiF / Al 5000 9 85 915.39 5.46 0.1417 〇. 1879 Comparative Example 12 Compound 2-33 (20 nm) / LiF / Al 5000 5, 90 751.57 6.65 0.1417 ------ 0.1810 Examples 12 to 14 were mixed with compounds 2_33 in different proportions. The agent (concentration is 5% to 50%), and the buffer layer uses different materials with electron transport properties to obtain better performance. Compared with Comparative Example 11, the drive voltage has a lower driving voltage of up to 18V. The efficiency of the compound 2-23 doped device is also higher. Compared with the comparative example i of 5.46 cd/A, the efficiency of the doped device is increased by 0.5 to 1.5 cd/A, and the increase is up to 27%. At the same time, from the stability comparison, after the compound 2_33 is doped, the half-life lifetime (initial brightness MOOcd, 2) of the device is all extended, and the relative improvement of the comparative example 11 can reach 5_. The use of the buffer layer separates the inorganic dopant from the luminescent layer to avoid luminescence quenching, which is beneficial to the improvement of device stability. In addition, Comparative Example 12 employed undoped compound 2-33, which was compared with Examples 1 2 to 14, and the ratio of 1 9 mountain was not as low as A1 q3, so the driving voltage was very low, only 5 γ曰, ^ . 9V. However, the life of Comparative Example 12 was not as good as that of Examples 12 to 14' because the library was not doped. It can be seen that 'matching ETL and changing the like, th ^ ^ dopant material, well-designed doping ratio and thief structure can find a balance between driving voltage, efficiency and stability. , to obtain performance ^ 〇 TFTs, 0 ^ excellent, real, high-performance devices, the performance of the TiA 0LED products. 39 201122080 Example 1 5 Device structure: ITO/NPB (40 nm) / Alq3 (30 nm) / Compound 2-5 (20 nm) / Compound 2_5: Li3N (10 nm, 10%) / V2 〇 5 (10nni) / NPB (40nin /Alq3(30nni)/Compound 2-5 (20nm) /LiF(0.5 nm)/Al(150nm) The substrate is placed in a cleaning solution with a ITO conductive glass substrate with a specific pattern as the substrate. Ultrasonic cleaning in deionized water, the temperature of the washing liquid is about 60 ° C, then the cleaned substrate is baked with an infrared baking lamp, placed in the evaporation chamber, and the functional layers are deposited by thermal evaporation in sequence, during the evaporation process. The chamber pressure is lower than 5.0 xl (T3pa. In this embodiment, ΙΤ0 必阳, 丨, 1 is 7U flat 7L 1 first deposits 4 〇nm thickness of NPB' as a hole transport layer, and then on it $ X The thickness of Alq3 is 3〇nm' as the light-emitting layer, and then the electron transport layer of 2〇nm ^ degree is deposited, and the compound layer of the present invention is used, and then the connection layer is prepared on the first precursor. The vapor deposition (four) connection layer, The compound 2-5 and 1% by weight of the coffee were deposited in a co-steamed sea way, and the thick core (10)' was then deposited with a p-type tie layer, (10), thickness ^. and then connected: deposition preparation second The illuminating unit, the structure and the first illuminating unit. Finally, the thermal evaporation, the layer, the 电子/儿 〇 _ 5 nm thickness of the electron Λ '- covers the cathode metal layer A1, the thickness i5Qnm. Example 16 Device structure: 201122080 ITO/NPB (40 nm) / Alq3 (30 nin) / compound 2-35 (20 nm) / character 2 ~ 35: Li3N (10nm, 10%) / Vz 〇 5 (10 nm) / NPB (40nm) / Alq3 ( 30 nm) / Compound 2-35 (20 nm) / LiF (0.5 nm) / Al (150 nm) The above device structure was prepared in the same manner as in Example 15 except that the material used for the N-type layer in the electron transport layer and the tie layer was changed to Compound 2-35 ° Example 17 Device Structure: ITO/NPB (40 nm) / Alq3 (30 nm) / Compound 3-3 (20 nm) / Compound 2-13: Li 3N (1 Onm, 100 / 〇 / V2 〇 5U 〇rnn / NPB (40 nm) / Alq3 (3 (him) / compound 3_3 (20 nm) / LiF (0.5 nm) / Al &lt; 150 nm) The above device structure was prepared in the same manner as in Example 15, except that the electron transfer layer was The material was changed to compound 3-3, and the material used for the N-type layer in the tie layer was changed to compound 2-13. Comparative Example 8 Device structure: ITO/NPB (40 nm) / Alq3 (30 nm) / Alq3 (20 nm) / LiF ( 0.5 nm) / Al (150 nm) The preparation method is as described above. Comparative Example 1 3 ITO/NPB (40 nm) / Alq3 (30 nm) / Alq3 (20nni) / Alq3: Li3N (l 201122080

Onm, 10%) / V2 〇 5 (10 nm) / NPB (40 nm) / Alq3 (30 nm) / Alq3 (20 nm) / LiFCO. 5 nra) / Al (150 nm) The above device structure was prepared in the same manner as in Example 15, and the difference was made. The material used in the N-type layer in the electron transport layer and the connection layer was changed to Alq3. Voltage of the stream at 2000 cd/m2 at 2000 cd/m2 V flow efficiency cd/A efficiency lm/W Example 15 13.0 6.1 1.2 Example 16 13.2 5.8 1.1 Example 17 12.8 6.4 ---------- 1.2 Comparative Example 8 6.6 3,1 1.2 Comparative Example 13 13.8 5.3 1.1 Comparative Example 8 is a single light-emitting unit device using a 20 nm thick AW material electron transport layer. Examples 15 to 17 and Comparative Example η are two devices in which the luminescence is superimposed, and the difference is that Alq3 is used as the electron transport layer and the N-type layer of the connection layer, and the compound of the '''. The implementations 5 to 17 adopt the present invention. From the performance comparison of the above table, it can be seen that the current efficiency is about - times higher than that of a single one using two light-emitting single structures. The current efficiency of the thief is as early as possible. The compound (1) and 2 of the present invention are electron transport layers, and the AM/D and $μ 2 13 are not only used as the N/P connecting layer "&quot; The current efficiencies of Examples 15 to 17 are also as follows: Layer: Body Comparative Example and Comparative Example 8, f Η 13. Although Examples 15 to 17 (4) 42 201122080, the magnitude of the increase in driving voltage Less than twice as large as Comparative Example 8, it can be seen that the N-type layer of the compound of the present invention as a connection layer has more efficient electron generation and injection ability, can significantly lower the driving voltage and improve efficiency. Example 18 Device structure: ITO/HAT (5 nm) /NPB(20nm)/Alq3:C545T(30nin, 1%)/Alq3

(20nm) / Compound 2-28: Li3N (20nm, 5%) / Mo 〇 3 (15nm) / NPB (20nm) / Alq3: C545T (30nm * 1%) / Alq3 (20 nm) / LiF (0. 5nm /Al (150 nm) The above device structure was prepared in the same manner as in Example 15, except that the hole injection layer HAT having a thickness of 5 nm was first deposited on the IT0, the thickness of the hole transport layer NPB was 20 nm, and the light-emitting layer was Alq3 doped C545T. The thickness of the luminescent layer is 30 nm, the concentration of the green dye is 1%, and the electron transport layer is changed to Aiq. The N-type layer in the connection layer is compound 2-28, and the 5% ratio of Li 3N is doped. The thickness of the N-type connection layer is 20 nm. 'P-type connection layer is m〇〇3, thickness 15 nm. Example 19 Device structure: ITO/HAT (5 nm) / NPB (20 nm) / Alq3: C545T (30 nm, 1%) / Alq3 (2 〇 nm) / compound 2-28: Li3N (15 nm, 20%) / m-MTDATA: F4-TCNQ (20 nm, 2 ° / 〇) / NPB (20 nm) / Al q3 : C545T (30 nm, l%) / Alq3 (20 nm) / LiF (0. 5 nm) / Al (150 nm) The above device structure was prepared in the same manner as in Example 18 except that the thickness of the N-type layer of the layer of 2011 20112080 was 15 nm, the doping ratio was 20%, and the p-type layer was m-MTDATA doped. The 2% ratio of F4-TCNQ' is 20 nm thick. Example 2 0 Device structure: ITO/HAT (5 nm) / NPB (20 nm) / Alq3: C545T (3 0nni, 1%)/Alq3 C2〇nm) / Compound 2-28: Li3N (5nm, 1〇%) / HAT (5nm) / NPB (20nm) / A 1 q3: C545T (3 0 nm, 1%) / Alq3 (20 nm) / LiF (〇. 5 nm) / Al (150 nm) The above device structure was prepared in the same manner as in Example 18 except that the thickness of the N-type layer of the connection layer was 5 nm, the doping ratio was 1%, and the p-type layer was HAT (hexanitrile hexaazatriphenylene, hexacyanohexaatritriene), thickness 5 nm. Example 21 Device structure: ITO/HAT (5 nm) / NPB (20 nm) / Alq3: C545T (30 nm, l ° / 〇) / Alq3 (20 nm ) / Compound 2-28: 70 %

Li3N (5 nm, 10%) / HAT (5 nm) / NPB (20 nra) / Alq3: C545T (30 nm, 1%) / Alq3 (20 nm) / LiF (〇. 5 nm) / A1 (150 nm) In the manner of Example 20. The above device structure was prepared except that the doping ratio of LisN in the N-type layer of the connection layer was. Comparative Example 14 44 201122080 Device structure: ITO/HAT(5nm)/NPB(20nm)/Alq3: C545T(3 0nm, l%)/Alq3(20nm)/LiF(0.5 nm)/A1(15Onm) The device structure described above was prepared in the manner of Example 18 except that the device had only one light-emitting unit and no connection layer. Comparative Example 1 5 Device Structure:

ITO/HAT (5 nm) / NPB (20 nm) / Alq3: C545T (30 nm, 1%) / Alq3 (2 0nni) / Alq3: Li (10 nm, 10%) / ΗΑΤ (1 Onm) / NPB (20 nm) / Alq3: C 545T (30 nm, 1%) / Alq3 (2 〇 nm) / LiF (0.5 nm) / Al (150 nm) The above device structure was prepared in the same manner as in Example 18 except that the N-type layer of the connection layer was Alq3 doped. Li in a ratio of 1% by weight, thickness i〇nm, and a P-type layer is a HAT having a thickness of 10 nm. • Comparative Example 1 6 Device Structure: ITO/HAT(5nm)/NPB(20nm)/Alq3:C545T(30nni) l°/〇)/Alq 3(20nm)/ET-ll:Li (10nm, l〇°/ 〇) / HAT (10 nm) / NPB (20 nm) / Alq3: C545T (30 nm, 1%) / Alq3 (20nra) / LiF (〇. 5nm) / Al (150nm) The above device structure was prepared in the same manner as in Example 18. The difference is that the N-type layer of the connection layer is ET-11 doped with a ratio of 1% by weight of u, the thickness is 10 nm, and the p-type layer is HAT having a thickness of 10 nm. 45 201122080 Voltage of the flow at 1000 cd/m2 at 1000 cd/m2 V flow efficiency cd/A efficiencies lm/W Example 18 8. 0 15.0 5. 89 Example 19 8.5 14.8 5.47 Example 20 7.5 16.2 6. 78 Example 21 9,2 14.5 4. 95 Comparative Example 14 4.2 8.0 5.9 Comparative Example 15 8.9 14.6 5.16 Comparative Example 16 8.8 14.8 5.21

Comparative Example 14 is a device of a single light-emitting unit, and Comparative Example 5 and Examples 18 to 21 are devices in which two light-emitting units are superimposed, except that the N-type tie layer material of Comparative Example 15 is Alq3, and Examples 18 to 21 The n 5 tie layer material was selected from the compound 2_28 of the present invention to match different p-type tie layers. The N-type connection layer of Comparative Example 16 was ET_u, and the driving voltage of the device was slightly lower than that of the embodiment, and the efficiency was slightly lower. It was demonstrated that the compound of the present invention has better transmission properties than the ET-11 material. From the comparison of the performance data in the above table, the connecting layer 2-28: 10%Li3N/HAT % έ A1 is the preferred structure of the array, and the embodiment 20 is compared with other parts' current efficiency and gn hands and grasping efficiency There have been great improvements in terms. And the light-emitting unit of the taxi you! 4 Example 14 comparison, Example 2 〇 drive voltage single

2 times the comparative voltage, carrier generation injection performance: Small The connection layer of Example 20 is shown to have excellent &amp; BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A is a graph showing the luminance-voltage of the light-emitting device 46 201122080 of Example 114 and Comparative Example 11-12; and Figure 2 is a graph showing the currents of the light-emitting devices of Examples 12-14 and Comparative Example u_12 A graph of density-voltage; FIG. 3 is a graph illustrating current efficiency-current density of light-emitting devices of Examples 12-14 and Comparative Examples π-12; and FIG. 4 is a view illustrating Examples 12-14 and Comparative Examples 11-12 A diagram of the lifetime of a light emitting device.

[Main component symbol description] None

47

Claims (1)

201122080 VII. Patent application scope: 1. An organic material, which is shown by the following formula 1: Wherein Ar is selected from the group consisting of residues of a fused ring aromatic hydrocarbon having 6 to 30 carbon atoms; and An and Αγ2 are each independently selected from a hydrogen atom, an aromatic group having 6 to 24 carbon atoms, and 6 to 24 carbon atoms. a heterocyclic aromatic group; n is selected from an integer of 2 to 3 ·. 2. The organic material as described in claim 1 of the patent scope, wherein 48 201122080 3. The organic material as described in claim 1 or 2, wherein 4. The organic material as described in claim 1 or 2, wherein the group attached to the Ar group is: 5. The organic material as described in claim 1 or 2, wherein the organic material is represented by the following structural formula: 49 201122080 2-21 2-23 50 201122080 material a galvanic galvanic corrosion and an organic luminescent medium disposed between the pair of electrodes; "negative, the organic luminescent medium is included in the material section of the __ box according to the scope of claims 1-5. 8. The organic electroluminescence of the above-mentioned organic light-emitting medium including the light-emitting layer and the electron-transporting functional layer, as claimed in item 7 of the patent application, the above-mentioned organic light-emitting device 51 201122080 The material described in the item is included in the transmission function layer. The organic electroluminescence device described in the above paragraph (4) of claim 7 further comprises another electron transporting material, which material is selected from: (4) a compound, a metal chelate compound, a trivalent compound, a compounding compound, a phenanthroline compound or an anthraquinone compound. The organic electroluminescent device according to claim 9, wherein the oxazole compound, metal chelate compound, triazole compound, imidazole compound, phenanthroline compound or anthraquinone compound is : 2_(4-tert-butylphenyl)-5-(4-biphenyl)4' 3,4-oxadiazole, tris(8-hydroxyquinoline)aluminum, 3-(4-linked stylyl)_4 _ Stupid _5_(4_ butyl stupid) 1,2, 4 one. Sit, 4,7 - a stupid base - l, i〇-phenanthrene, 2,9-dimethyl-4' 7-diphenyl-1,1 〇 phenanthroline, or 2 benzene Base _9, 1 〇 dinaphthoquinone. The organic electroluminescent device of claim 7, wherein the organic light-emitting medium comprises a light-emitting layer and an electron injecting and transporting functional layer, wherein the method of any one of claims 1 to 5 is The material is included in the above-mentioned electron injection and transfer function layer, and the electron injection and transmission work 3b layer further comprises a dopant. The dopant is selected from the group consisting of metal, metal oxide, alkali metal-alloy metal alkali nitrogen. And alkali metal salts. 12. The organic electroluminescent device according to claim 11, wherein the dopant is selected from the group consisting of lithium, lithium, lithium nitride, lithium fluoride, lithium cobalt oxide, oxidized hydride, lithium quinolate, Barium carbonate, potassium borohydride, lithium borohydride, sodium fluoride, sodium gasification, fluorination, gasification planing, and cerium oxide. 52 201122080 23. The scope of claim 5, wherein the electron injection and transmission electron injection and transmission electron layer of the above electron injection and transmission layer has a thickness of 2 nm to 40 nm. The doping ratio of _, = agent is a weight percentage U· Η 49/β, based on the material as claimed in the patent application. The thickness of the functional layer of the organic electroluminescent device of the organic electro illuminator as described in any one of items 1 to 5, as described in claim 13# ^, ^+· ^ ^ is ― change in the functional layer The doping ratio of the agent is the weight percentage of the material wire. For example, please refer to the item described in item ρ of the item Φ, and the Φ application for the patent method is the organic electroluminescent device spoon of the pregnant woman, in the above electronic Between the injection and transfer function layer and the light-emitting layer:: the punch layer 'the material of the buffer layer is selected from the patent application range 丄 or 2 _ ^, or selected from the group of compounds, metal complexes And a azole compound, an imidazole compound, a quinoline compound, a porphyrin compound, a guanidinium compound, and a phenanthroline compound. The material of the above-mentioned buffer layer of the organic electroluminescent device of the invention of claim 15 is selected from the above-mentioned spooning in the scope of claim 5. 'or selected from 2-(4-tert-butylphenyl)-5-(4-biphenyl) 3 oxadiazine, tris(8-hydroxyquinoline)aluminum, 3-(4-biphenylyl) -4-j base ~5~(4~ butylphenyl)-1,2,4-triazole, 4,7-diphenyl-l,l〇-phenanthroline, 2,9-di Base-4,7-diphenyl-1,1〇-phenanthroline, and 2-phenyl-9,1〇__naphthoquinone. The organic electroluminescent device 53 201122080 according to claim 15, wherein the buffer layer has a thickness of 2 n 2 nm. 18. The organic electroluminescent device according to claim 7, wherein the organic luminescent medium comprises at least two illuminating units, and a connecting layer is disposed between the illuminating units, as in any one of the five patent claims. The material described in the item is contained in the above connecting layer. 19. The organic electroluminescent device according to claim 18, wherein the connecting layer is further doped with an alkali metal, an alkali metal oxide, a metal halide, an alkali metal nitride, and an alkali metal. A dopant for the salt. 20. The organic electroluminescent device according to claim 19, wherein the above dopant is selected from the group consisting of lithium, ruthenium, nitridium chain, lithium fluoride, cobalt acid clock, lithium oxide, and 8-hydroxyquinoline. Lithium, barium sulphate, potassium borohydride, lithium borohydride, sodium fluoride, sodium vapor, barium fluoride, chlorinated planer, and cerium oxide. 54