TWI354012B - Aromatic electroluminescent compounds with high ef - Google Patents

Description

139. The invention relates to an electroluminescent compound comprising a fused ring and an electroluminescent device using the same. [Prior Art] Recently, the rapid arrival of the information age has made the importance of displays used as a connection between humans and electronic information devices. As a novel flat panel display technology, organic light-emitting devices (〇Led) have been actively researched around the world. This is because OLEDs are self-illuminating types, have excellent display properties, and are easy to manufacture due to their simple device structure. And it can be used to make ultra-thin and ultra-light display states. An OLED device generally includes a thin layer composed of a plurality of different organic compounds between a cathode made of a metal and an anode. The electrons and holes injected through the cathode and the anode respectively pass through an electron injection layer and an electron. The transfer layer, a hole injection layer and a hole transfer layer reach an electroluminescent layer, thereby forming an exciton, and the formed excitons change in a steady state to emit light. At this time, since the nature of the OLed device largely depends on the nature of the organic luminescent compound used, the luminescent material is actively studied. The luminescent material is functionally divided into a host material and a dopant material, and it is well known that an electroluminescent layer having a device structure having an optimum electroluminescence property is produced by incorporating a dopant into a host material. Recently, there is an urgent need to develop an organic electroluminescence (EL) device having high performance and long life, and in view of the EL property level required for a medium or large OLED panel, it is particularly urgent to develop a material far superior to the existing electroluminescent material. . In this regard, the development of the subject material is one of the problems to be solved. At this time, it is used as an energy and solid solvent in the organic EL device, and the master material should have a property of f: its purity should be high and it should have ΐΐϊίΐΐ to allow vapor deposition. In addition, it should have "glass first, turn k / m degree and thermal decomposition temperature in order to obtain thermal stability; it needs to have a high 1354012 electrochemical stability (four) growth life; its county in the film should deal with other adjacent layers The material has extremely bauxite > every day #日日^#, and move between. (4) It has the power of the private silk, the same material should have a layer of various main materials and its typical examples include her own as she is fsan Ltd. Obtained diphenylvinyl-biphenyl (DpyBi) and dinaphthyl fine N obtained from her nan Kodak company,

There is still much room for improvement in terms of color purity. ..........—$〇P

DPVBi has a glass transition temperature of less than 1 〇〇. There is a problem of thermal stability, and in order to improve the problem, DPVPAN and DPVPBAN ' in which the ruthenium and the ruthenium are respectively introduced into the biphenyl group of DPVBl have been developed to increase the glass transition temperature to 105. Above °C, thereby improving the thermal stability, however, the color purity and luminous efficacy have not yet reached a satisfactory level.

1354012 In addition, by observing the DNA film formed on ITO by vapor deposition using scanning probe microscopy, it was found that there was a phenomenon that the film had low stability in the DNA and thus was easily crystallized. It is known that this phenomenon has an adverse effect on the life of the device, and in order to improve the disadvantage of DN A, inDNA and tBDNA in which a thiol group or a tert-butyl group is introduced into the second position of the DNA have been developed to destroy The symmetry of the molecules improves the stability of the film, but the color purity and electroluminescence efficiency have not yet reached a satisfactory level.

SUMMARY OF INVENTION Technical Problem

The electroluminescence of the luminescent compound and the provision of a color coordinate with a low degree of crystallinity. Further, the object-oriented organic electroluminescent luminescent device of the present invention is provided with a condensed ring. The present invention is described in detail below. The present invention relates to a chemical formula "54012 luminescent compound and an organic light-emitting diode (OLED) using the same as an electroluminescent material. The organic electroluminescent compound of the present invention is used as another layer in addition to the luminescent layer. Chemical formula 1 7ri

Ar2 R4 is a single ring-fused fused wire; Ari and fine oxygen or a C& face has two "hetero-oxyl groups, as the case may be in the middle, and the chemical formula 7 represents: clothes and specifically by the following chemical formula 2 to Chemical Formula 7

Ri3 Today "1 R

R12 Ar2 R4 chemical formula λ 9 ζ s > 1354012 R 13

.R2 r3 Chemical Formula 4

Rl2

R2 r3 chemical formula 5

Chemical formula 7 ίο 丄丄2

And the C system is the same as defined in 式τι, Μ, Ri, R2, R3 §, r Γ/1, and 1, and &1 to R13 are independently one or two or Has a branched alkyl group or a group and -C6_C3. An aryl group or a heteroaryl group 3 to 1 to 3; and the silk and the alkoxy group, the aryl group

^/, k-C丨-C2〇 is a straight chain or a branched alkyl group, an aryl group and a halogen group. w In the above Chemical Formula 1 to Chemical Formula 7, the oxime 2 may independently be a phenyl group, a local group, a phenyl group, a naphthyl group, an anthracenyl group, and an anthracenyl group, and the R? to R4 and Ru to 13 independently include hydrogen, A Base, ethyl, propyl, isopropyl, butyl, isobutyl, _, yl, hexyl, ethylhexyl, heptyl, octyl, isooctyl, decyl, decyl, dodecyl, Hexadecyl, cyclopentyl, cyclohexyl, strepto, tolyl, biphenyl, benzyl, naphthyl, anthracenyl and fluorenyl. The organic electroluminescent compound of the present invention may be, but not limited to, the following compounds:

11 1354012

Rl σ

[Examples] Preparation Example 1 Preparation of CYHDNA 12 1354012

In a round bottom flask, put 70 ml of dichlorodecane and 15.8 g (118.8 mmol) of vaporized aluminum, then 8.0 g (54.0 mmol) of isobenzofuran-1,3_dione and 8.8 mL (64.8 111111〇) 1) 1,2,3,4-tetrahydronaphthalene was dissolved in 80 〇1111^ two-gas methane and slowly added to the flask containing aluminum chloride. After stirring at 25 ° C for 24 hours, the reaction mixture was slowly added to a mixed solution of 30 mL of 35% chlorous acid and 150 mL of ice water and mixed for another 20 minutes. The reaction mixture was extracted with 200 mL of ethyl acetate, crystallized again, and then dried to give 10.6 g (37.8 mmol) of compound [1-1].

10.6 g (37.8 mmol) of compound [1-1], 50.4 g (378.1 mmol) of chlorinated and 1 U g (189.0 mmol) of sodium chloride were placed and stirred at 130 ° C for 4 hours under reflux. The reaction product was cooled to 25 ° C, then added and dissolved in 60 mL of tetrahydrofuran and 30 ml of water was added to complete the reaction. After the end of the reaction, the reaction product was triturated with 10 〇 rainbow gas and dried under reduced pressure to obtain 3 g (11.4 mmol) of compound [1-2].

After dissolving 8.5 g (40.9 mmol) of 2-indan in 50 mL of tetrahydrogenethane, 4.3 mL (45.7 mmol) of n-butyllithium (2.5 Μ solution in n-hexane) was added at _72 °C. It was slowly added to 50 mL of tetrahydrofuran in which 2-bromonaphthalene was dissolved, followed by stirring for 2 hours, followed by the addition of 3.0 g (1.44 mmol) of the compound [1-2], and stirred at room temperature for 24 hours. After the reaction was completed by slowly adding 50 mL of distilled water, the reaction mixture was extracted with 250 mL of 13^54012 tetrahydrofuran and dried under reduced pressure to obtain 3.5 g ( 6.8 Mnol) of compound [1-3]. 3.5 g (6.8 mmol) of compound [1-3], 4.5 g (27.1 mmol) of potassium iodide and 5.8 g (54.0 mmol) of sodium hydrophosphinate were dissolved in 30 mL of acetic acid and 10 ml of dichloromethane. The mixture was mixed and stirred under reflux for 24 hours. After the reaction product was cooled to 25 ° C and 20 mL of water was slowly added thereto to complete the reaction, the reaction product was extracted with 200 mL of dichloromethane, recrystallized and dried to obtain 2.8 g (5.8 mmol) of compound CYHDNA. The total yield is 11〇/0. NMR (200MHz, CDC13): 6 = 1.60 (m, 4H), 2.85 (m, 4H), 7.32 (m, 6H), 7.40 (t, 2H), 7.54 (d, 2H), 7.67-7.73 (m, 8H), 7.89(d, 2H) MS/FAB: 484.22 (measured value), 484.63 (calculated value) Preparation Example 2

Using 10 g (50.5 mmol) of naphthoquinone (2,3_Q-furosyl-N-1,3-dione and 9·5 g (60.5 mmol) of 1- benzene, 12.5 g (35.2 mmol) was obtained in a similar manner to the preparation of Example 1. Compound [2-1] Preparation of PHDNN 1354012 12.5 g (35.2 mmol) of compound p-ι], 46.9 g (351.9 mmol) of vaporized aluminum and 10.3 g (175.9 mmol) of sodium sulphate were used to prepare Example 1 In the same manner, 3 6 g (10.6 mmol) of compound [2-2] was obtained using 8.0 g (38.6 mmol) of 2-carbaphthalene, 3.9 mL (42.7 mmol) of n-butyllithium (2.5 Μ solution in n-hexane) And 3.6 g (10. 6 mmol) of compound [2-2], 3,8 g (64 mmol) of compound 〇3] was obtained in a similar manner to the preparation of Example 1. Using 3.8 g (6.4 mmol) of compound [2- 3], 4.2 g (25.3 mmol) of potassium telluride and 5.4 g (50.9 mmol) of calcium phosphinate, obtained in the manner of Example 1 to obtain 2 9 g (5 2 mmol) of compound p-4] 〇2·9 g (5.2 mmol) of compound [2-4] and 0.7 g (6.0 mmol) of phenylboronic acid were dissolved in a mixture of 30 mL of hydrazine and 15 ml of ethanol and added with 〇·2 g (i.7 mmol) of hydrazine ( Two bases of Kirin (〇) [Pd(PPh3)4] and 2.3 mL of 2 Μ aqueous sodium carbonate solution, then stirred under reflux for 5 hours. The product was cooled to room temperature and 15 times of water was slowly added thereto. After the reaction was completed, the reaction mixture was extracted with 300 mL of hexane and dried under reduced pressure to obtain 2.6 g (4.7 mmol) of compound PHDNN. 9%. ' !H NMR (200MHz, CDC13): δ=7.22-7.32(ιη, 9Η), 7.48(d, 2Η), 7.54(d, 3H), 7.67-7.73(m, llH),*7.89 (d, 3H) ' ' MS/FAB: 556.22 (measured value), 556.69 (calculated) Preparation Example 3 Preparation of NDNN except 2.9 g (5.2 mmol) of compound [2·4] and 1.1 g (6.4) In the same manner as in Preparation Example 2, 3.0 g (4.9 mmol) of compound NDNN was obtained in a total yield of 9%. !H NMR (200 MHz, CDC13): 5 = 7.32 (m, 8 Η) , 7.54(d, 4Η), 7.67-7.73(m, 14H), 7.89(d, 4H) ' ' 1354012 MS/FAB: 606.23 (measured value), 606.75 (calculated value) Preparation Example 4 Preparation of PDNBA

In a round bottom flask (10 ml), 1.7 g (70.1 mmol) of Mg was placed, and then a small amount of I2 tablets and 10 ml of tetrahydroanhydride were placed. 11 g (42.5 mmol) of 9-filled phenanthrene was dissolved in 1 mL of tetrahydrofuran and slowly added to a magnesium-filled flask of 〇 ° C, followed by stirring at 25 ° C for 30 minutes. 9.9 g (43.4 mmol) of 5-bromoisobenzofuran bauxite dimide and 12.7 g (95.6 mmol) of vaporized aluminum were placed in the flask and stirred for 24 hours. After the reaction solution was slowly added to 150 mL of 1 N aqueous hydrogen acid solution and stirred for 3 minutes, the reaction solution was extracted with 200 mL of dichloromethane and dried under reduced pressure to obtain 11.4 g (28.2 mmol) of compound [4. ]. 2.6 g (6.8 mmol) of compound was obtained in the same manner as in the preparation of Example 2 using 11.4 g (28.2 mmol) of compound [4-1], 37.9 g (284.4 mmol) of aluminum chloride and 8.3 g (142.2 mmol) of sodium hydride. [4-2]. Using 5.1 g (24.6 mmol) of 2-bromonaphthalene, 2.5 mL (27.3 mmol) of n-butyl oxime (2.5 Μ solution in 1354012 n-hexane) and 2.6 g (6.8 mmol) of compound [4-2], In a manner of 2, 2.2 g (3.7 mmol) of a di-based compound was obtained. 1.95 g (3.2 mmol) of compound was obtained in the same manner as in the preparation of Example 3 using 2.2 g (3.7 mmol) of the base compound, 2.5 g (14.8 mmol) of potassium molybdate and 3.1 g (29.6 mmol) of sodium hydrogenphosphinate. -3]. Using 1.95 g (3.2 mmol) of compound [4-3], 470.7 mg (3.9 mmol) of phenylboronic acid, 0.2 g (1.7 mmol) of hydrazine (triphenylphosphine), (9) [pd(pph3)4] and 2 3 2 μg of aqueous sodium carbonate solution was used to obtain U6 g (2.3 mmol) of compound PDNBA in the same manner as in Preparation Example 3, with a total yield of 5%. lU NMR (200MHz, CDC13): δ=7.22-7.32 (ΐϊΐ, 9Η), 7.48-7.54(m, 7Η), 7.73(d, 1H), 7.82-7.89(d, 2H), 8.93(d, 2H) ' MS/FAB: 506_2 (measured value), 506.63 (calculated value) Preparation of NDNDBA

Using 1.95 g (3.2 mmol) of the compound prepared in Preparation Example 4, 0.664 g (3.9 m-naphthalene boronic acid, 0. (1.7 saponin 1) oxime (triphenyl squara [Pd(PPh3) 4], 2.3 ml) 2 Μ sodium carbonate aqueous solution and a mixed solution of 3 Torr and 15 'J were used to obtain u & NDNDBA in the same manner as in Preparation Example 2, the total yield was 5%. ° 1H NMR_MHZ, CDCl3): δ =7.22·7·32(ιη 48 6Η), 7.67-7.89(m, 10H), 8.12(d, 2H), 8.93(d, 2H) MS/FAB: 556.22 (measured value), 556.69 (calculated value) 17 1354012 Example 1 Manufacture of an OLED device using the compound of the present invention An OLED device having a structure using the electroluminescent material of the present invention was first fabricated. First, a film of a transparent electrode oxidized copper tin itq obtained from the OBEL peripheral glass ( 15 Ω / 匚]), the film has been washed by ultrasonic waves using trichloroethylene, propylene, ethanol and distilled water in sequence, and then stored in isopropyl alcohol. Then, the ITO substrate is placed in a vapor deposition apparatus. On the substrate holder, and then placed in a unit of the vapor deposition apparatus, 4,4,,4"-tris(N,N-(2-naphthyl)-phenylamine having the following structure Triphenylamine (2-TNATA) and venting until the vacuum in the chamber reaches 10 6 Torr' and then applying a current to the unit to evaporate 2-TNATA 'to vapor-deposit on the ITO substrate to have 6 A hole injection layer of thickness.

The hole transfer layer of thickness. Subsequently, another unit of the vapor deposition apparatus was placed with N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4,diamine (npb) having the following structure. And then applying a current to the cell to burst NBP, thereby vapor deposition on the hole injection layer having 2〇1354012

After forming the hole injection layer and the hole transfer layer, an electroluminescent layer is vapor deposited thereon as described below. Putting a compound of the invention (for example, compound CYHDNA) into one unit of the vapor deposition apparatus, and placing a doped electroluminescent material having the following structure into another unit of the vapor deposition apparatus φ, A phosphorescent layer having a thickness of 35 nm was then vapor deposited on the hole transfer layer at a deposition rate of 1 〇〇:1.

Subsequently, three (8-hydroxyquinoline) (III) (Alq) having the following structure was deposited as an electron transfer layer at a thickness of 20 nm, and then lithium quinolate (Liq) having the following structure was deposited at a thickness of 1 to 2 nm. As an electron injecting layer, an A1 cathode was then deposited with a thickness of 150 run using another vapor deposition apparatus to fabricate an OLED. 19 1354012

Each of the materials used in the OLED device was purified by vacuum liter at 1 -6 Torr and then used as an electroluminescent material. ' ^ 丽 实例 Example 1 using a conventional electroluminescent material to fabricate an OLED device to form the electrical contact layer and the electricity in the manner of Example i

j 'puts the blue electroluminescent material kein (DNA) in the vapor deposition read-unit and puts another blue-electroluminescent material in the unit of the subtractive deposition The electroluminescent layer having a thickness of 35 nm was then vapor deposited on the transfer layer of the hole at a deposition rate of 1 Å. .

The DNA ruthenium / ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium 20 CS ) 1354012 • Example 2 • The electroluminescent properties of the fabricated OLED device were measured at 500 cd/m 2 and 2,000 cd/m 2 , respectively, and the organic electroluminescent compounds of the invention produced in Example 1 and Comparative Example 1 were prepared. The electroluminescent efficacy of OLED devices of conventional electroluminescent compounds is shown in Table 1 below. Especially in the blue electroluminescent material, the measurement is based on the brightness at about 2,000 cd/m2, which is important because of the electroluminescence properties in the low-luminance region and the brightness applied to the panel. Table 1 Numbered electroluminescent material 1 Electroluminescent material 2 EL peak (nm) Electroluminescence (cd - light efficiency 1/A) Color coordinate electroluminescence efficiency / Y @500 cd/m2 @2000 cd/m2 XY 1 CYHDNA 茈460.488 5.23 4.77 0.162 0.212 22.5 2 PHDNA 茈464.492 6.23 5.66 0.165 0.223 25.4 3 NDNN 茈464.492 6.12 5.60 0.165 0.225 24.9 4 PDNDBA 茈464.496 6.69 5.92 0.164 0.237 25.0 5 NDNDBA 茈466.498 6.70 5.81 0.164 0.235 24.7 Comparative Example 1 DNA 茈456.484 4.45 3.62 0.160 0.200 22.3 As shown in Table 1, the "electroluminescence efficacy / Y" value showing a tendency similar to quantum efficiency is used as a reference, when Comparative Example 1 (ie, containing conventional conventional electroluminescent material DNA) The OLED device using the organic electroluminescent compound of the present invention exhibits a higher "electroluminescence efficiency / gamma" value when compared with an OLED device using the organic electroluminescent compound of the present invention. [Industrial Applicability] The organic electroluminescent compound according to the present invention has an advantage in that an OLED device having a high driving life of 21 1354012' can be manufactured because it has a preferred material electroluminescence efficiency and excellent material lifetime properties. . The organic electroluminescent compound of the present invention is also characterized by an excellent EL property which is improved when it is used as a light-emitting layer and other layers. It will be appreciated by those skilled in the art that the <RTI ID=0.0>&lt;/RTI&gt; </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; Those skilled in the art will also appreciate that such equivalents do not depart from the spirit and scope of the invention as set forth in the appended claims. [Simple diagram description] [Main component symbol description]

twenty two

Claims (1)

1354012 Month mmm\ No. 096117959 Patent Application. Chinese Patent Application Substitution Replacement (丨〇〇.1月〇月2丨曰) Patent Application Range: ^ 1. An organic electroluminescent compound selected from the chemical formula 4 to Chemical formula 7: [Chemical Formula 4] [Chemical Formula 5] Rl3 [Chemical Formula 6] Rl3 23 1354012 Patent application for the 0% U 7959 patent replacement for the Chinese patent application (October 21, 100) ΓChemical formula 7] Month f Replacement page a Q-Qo aryl group; the heart is independently a hydrogen, a Ci_c2 〇 straight chain or a branched or alkoxy group and a C6_C3 () aryl or heteroaryl group and a halogen group; Ru to R] 3 independently / also monohydrogen, _ c "C2Gi chain or branched alkyl or alkoxy group and a Q-Qjo aryl or heteroaryl group and - halogen group; η series 1 to 3; The alkyl group and the alkoxy group, the aryl group and the heteroaryl group are optionally substituted by a Ci_c2() linear or branched alkyl group, an aryl group and a dentate group. An organic electroluminescent compound, wherein the oxime | and the Ar2 are independently selected from the group consisting of phenyl, anthracenylphenyl, biphenyl 'naphthyl, ketone, and fluorenyl. 3. The organic electrochemistry of claim 1. a luminescent compound, wherein the oxime to ruthenium and to Rl3 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylhexyl, heptyl , octyl, isooctyl, decyl, decyl, dodecyl, hexadecyl, phenyl, phenyl, biphenyl, benzyl, naphthyl, anthracenyl and decyl. The organic electroluminescent compound of claim 1 is selected The following compounds: 24 1354012 t </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; 6. An electroluminescent device comprising an organic electroluminescent compound as claimed between enthalpy 4 and an anode. Said in any of the 25