TW200829680A - Organic electroluminescent compounds and display device containing the same - Google Patents

Abstract

The present invention relates to an organic electroluminescent compound and a display device using the same. The electroluminescent compound according to the present invention has good luminous efficiency and excellent lifetime of the material, so that an OLED device having very good operation lifetime can be prepared.

Description

[Technical Field] The present invention relates to an electroluminescent compound represented by the following Chemical Formula 1 and a display device comprising the same. [Chemical Formula 1]

The center to R3 is independently a phenyl or c10 to c20 fused polycyclic aromatic ring, and the phenyl or C1G to C2G of 1 to R3 is more fused to a polycyclic aromatic ring (^ to c20 alkane) a group, (^ to c20 alkoxy group, halogen, c5 to c7 cycloalkyl group, phenyl group or substituted by a condensed polycyclic aromatic group. [Prior Art] Development of organic electroluminescence with high efficiency and long life ( The most important factor in electroluminescent EL devices is the development of high-efficiency electroluminescent materials. In the case of blue light, if the wavelength of the light is slightly shifted to a long wavelength, it is advantageous in terms of luminous efficiency. Due to this unsatisfactory pure blue color, the material is not easily applied to high-quality displays. In addition, there are problems of color purity, efficiency and thermal stability. In terms of blue materials, from Idemitsu-Kosan Co., Ltd. A variety of materials have been developed and commercialized since the development of DPVBi (Compound a) disclosed in European Patent Publication No. 1063869. Until now, Idemitsu-Kosan's disyryl compound system has been known to have the highest Efficiency, its It has a power efficiency of 6 lumens per watt 200829680 (lm/W) and an effective device life of over 30,000 hours. However, when applied to a full-color display, the color purity is reduced by the driving time, so the life is only thousands of hours. [Compound a]

The dinaphthyl fluorene compound (compound b) disclosed by Kodak, U.S. Patent No. 6,465,115, is a compound of a Hole Transport Layer (HTL) substance, which has also been used as a blue power. Luminescent compound. However, these compounds still have problems to be solved in terms of luminous efficiency and color purity. [compound b]

Recently, LG Chem has disclosed an electroluminescent derivative (compound c) within a similar range of compound b in WO2006/25700. However, compound c has limitations in terms of luminous efficiency and color purity. [Compound C] 200829680

At the same time, in the case of green fluorescent materials, a widely used system has been developed in which a coumarine derivative (compound d, C545T), a quinacridone derivative (quinacridone derivative) (Compound e), diphenyl tetracene (DPT) (compound f) or the like is incorporated as a dopant in a concentration of from a few percent to no more than 20 percent. In the tris-(8-hydroxyquinoline) aluminum, Alq) (host material). However, the conventional electroluminescent material exhibits a superior performance in terms of initial light-emitting efficiency in practical use, but has a significant problem in life and a significant initial efficiency. Therefore, these materials have limitations when used on high performance panels for larger screens. It is reported that this is because the cationic material of Alq used as a host material has a short lifetime. In order to overcome this problem, it is urgent to develop a host material having amphoteric properties which are stable to both cationic materials and anionic materials. [compound d]

[compound e] 200829680

[compound f]

SUMMARY OF THE INVENTION The object of the present invention is to overcome the above problems and to provide an electroluminescent material having a host material property which is superior to the properties of a conventional material, and the host material is used in an electroluminescent material. Used as a solvent or energy carrier. Further, another object of the present invention is to provide a blue or green electroluminescent material having improved luminous efficiency and extended device life, and an organic electroluminescent device comprising the same. The present invention relates to an organic electroluminescent compound represented by Chemical Formula 1: [Chemical Formula 1]

Wherein R! to R3 are independently phenyl or C10 to C20 fused polycyclic aromatic rings, and the phenyl or C1G to C2G of R! to R3 is more viscous polycyclic aromatic ring via Q to C20 An alkyl group, a C! to C20 alkoxy group, a halogen, a 0:5 to C7 cycloalkyl group, a phenyl group or a fused polycyclic aromatic group; and a display device using the compound. 8 200829680 Feed life The electroluminescent compound of the present invention has high luminous efficiency and extremely long material, so that an OLED device having an extremely long service life can be prepared. [Embodiment] Other and further objects and advantages of the present invention will become more fully apparent from the following description. The present invention relates to an organic electroluminescent compound represented by Chemical Formula 1: [Chemical Formula 1]

Wherein R! to R3 are independently phenyl or C10 to Cm fused polycyclic aromatic p R! to R3 phenyl or C1 () to C2G fused polycyclic aromatic ring can be passed through ^ ^ 1 king L2 brothel group, (3丨 to C2 decyloxy, halogen, C5 to C? cycloalkyl, phenyl or substituted by a dog-producing aromatic group; and a display device using the compound. The electroluminescent material mentioned in the present invention comprises any material used as an organic substance in an organic electroluminescent device, the organic electroluminescent device comprising a first electrode, a second electrode and a clip An organic substance between the first and second electrodes; and narrowly, it means an electroluminescent host material suitable for use as an electroluminescent medium in the electroluminescent layer. In the compound represented by Chemical Formula 1 of the present invention , Ri to R3 are independently selected from the group consisting of phenyl, naphthyl, anthryl, fluorenyl, phenanthryl, fluorancenyl, fluorenyl, fluorenyl (perylenyl) Or tetraphenyl (naphthacenyl); and phenyl, naphthyl, anthracenyl, fluorenyl, phenanthryl, 200829680 fluorenyl, The thiol group, the fluorenyl group and the tetracylphenyl group may be optionally substituted by q to c2 decanemei C2 decyloxy, a halogen atom, a C5 to C? cycloalkyl group, a phenyl group or a fused polycyclic group. The organic electroluminescent compound represented by i: expressed by two formulas, but the equation does not limit the scope of the invention:

10 200829680

11 200829680

The present invention also provides an organic electroluminescent device comprising: a first electrode; a second electrode; and one or more organic layers sandwiched between the first electrode and the second electrode, wherein the organic layer comprises a Or a plurality of compounds represented by Chemical Formula 1: [Chemical Formula 1] 12 200829680

"Ri to R3 are independently phenyl or Ci 〇 to c2 〇 fused polycyclic aromatic ring, and the side of R1 to R3 is stupid or Cio to C2 〇 fused polycyclic aromatic ring is more c Substituted to h 丨匕 2 〇 土, 匸 1 to 〇 2 〇 alkoxy, halogen, Cs to C 7 cycloalkyl, stupid or fused polycyclic aromatic group. Organic electroluminescence of the invention The (electroluminescent, EL) device is characterized in that the organic layer contains an EL region containing one or more EL dopants and one or more compounds represented by the chemical formula (1) as an EL host material. The EL dopant of the organic EL device is not particularly limited 'may be, for example, a compound represented by one of Chemical Formulas 2 to 4: [Chemical Formula 2]

[Chemical Formula 3]

:n—m—N:

13 200829680 In Chemical Formula 3 and Chemical Formula 4, ΑΓι and Αγ2 are independently mdenofluorene, Wfl and ene) or (spir〇_fl earned), and are represented by the following chemical formula:

Wherein Rn to R16 are independently selected from the group consisting of: to a C2 alkyl group and a phenyl or naphthyl group having or without a Cl to Cs alkyl substituent; and the Ah to Ar6 series are independently selected from the group consisting of 〇5 to ^芳a family or polycyclic aromatic ring; wherein _ is the same as 2' Al>3 is the same as Ar5, and Ar4 is the same as Αγ6;

Α and Β are independently represented by a chemical bond, or t or ... · ring i^Ris is an independent steroid ring or is a two or "aromatic ring _ _ _ _ _ _ _ _ _ _ _ _ The bond or the branch of & 3 to 26 is independently a gas or aromatic group; and the = fang = relic ring, or its towel (4) _ system _ chemical formula 3 per cloth and ^ 4? /1 The compound of the formula is specifically, for example, a compound represented by one of the following chemical formulas: 200829680:

15 200829680

16 200829680

17 200829680

18 200829680

19 200829680

20 200829680

21 200829680

Wherein R19 to R22 are a methyl group or an ethyl group. The green EL compounds may be represented, for example, by one of Chemical Formulas 5 to 7.

Compound: [Chemical Formula 5]

22 200829680 [Chemical Formula 7]

In Chemical Formula 6 and Chemical Formula 7 φ„ ^, 仏7 and the system are independent of the multi-ring ring in which the two-group ring system is fused, one or one eve of a square eve, and the 1129 to I2 are independent. Each of the aromatic rings of the group R to R32 may be substituted by a c2G alkyl group to a compound of the formula 6 and the formula 7, and may specifically be, for example, a compound represented by one of the following chemical formulas:

23 200829680

24 200829680

25 200829680

The present invention is further described by way of example only, and is not intended to limit the scope of the invention in any way. [Preparation Example] Preparation of Compound represented by Chemical Formula 1 26 200829680

Among them, "aliquat 336" is a quaternary ammonium chloride 336; "THF" is tetrahydrofuran; "AcOH" is acetic acid; and "n_BuLi" is a n-butyl group. Preparation of Compound 12 In a mixed solution of toluene/ethanol (2:1 v/v), 9-bromoanthracene (58.3 mM) and a side acid derivative (Compound 11, 70·0 mM) were dissolved. Mohr) and tetrakis(triphenylphosphine)palladium (palladium) (Pd(PPh3)4) (5.8 mmol). After adding a 2 molar concentration (M) aqueous sodium carbonate solution, the resulting mixture was stirred at 120 ° C under reflux for 5 hours. Then, the temperature was lowered to 25 ° C, and the reaction was quenched by adding distilled water. Subsequently, it was extracted with ethyl acetate, dried under reduced pressure, and finally recrystallized from tetrahydrofuran and methanol to give Compound (12). Preparation of Compound (13) The compound (12) obtained as above (46.0 27 200829680 house Moule) and N-/sodium succinimide (N_br〇mosuccinimide) were dissolved in dioxane under a nitrogen atmosphere ( 50·6 millimoles). After ^; the obtained solution was mixed for 5 hours under $C. The reaction was quenched by the addition of distilled water, extracted with a gas-fired product, dried under reduced pressure, and finally recrystallized from tetrahydromethane and decyl alcohol to give compound (13). 1^X1) In the carefully purified THF, the compound (13) obtained above was dissolved (39.0 mmol). The resulting solution was cooled to -78, and n-butyllithium (1·6 Μ) was slowly added thereto. Already burned) (46 8 millimoles). After the mixture was stirred for 1 hour, ~, 4,4,5,5-tetramethyl-i,3,2-dioxaborolane (78·0 house mole) was added. The temperature was slowly raised to 25 ° C and the mixture was stirred for 1 day. After quenching the reaction by adding distilled water, the mixture was extracted with ethyl acetate and dried under reduced pressure. Finally, it is recrystallized from tetrahydrofuran and methanol to give compound (2). Preparation of ik^X3); dissolution of 2-gas-9,10-蒽酉-kun in a book (2-(:111〇1*〇-9,10-3111:1^91^11〇116) (29· 7 millimolar), compound (2) (35. 5 millimolar), tetrakis(triphenylphosphine)palladium(3)) (Pd(PPh3)4) (3.0 millimolar) and Aliquat 336 (3.0 millimolar) ). After a 2 M aqueous potassium carbonate solution was added thereto, the resulting mixture was stirred under reflux for 3 hours. Then, the temperature was lowered to 25 ° C, and the reaction was quenched by adding distilled water. It was extracted with ethyl acetate and dried under reduced pressure. Finally, it is recrystallized from decyl alcohol and tetrahydrofuran to give compound (3). The charge of ^^(6) was prepared by adding tetrahydrofuran to the bromine compound (Compound 4 or 5) (54.3 mmol), and at 25. (: The mixture was stirred for 1 minute to reach a complete dissolved state. After cooling 28 200829680 to -72 ° C, n-butyllithium (2.5 Μ dissolved in hexane) was slowly added dropwise (65·1 毫) After 1 hour, the compound (3) (21.7 mmol) was added thereto, and the temperature was slowly raised to 25. (: After the reaction mixture was stirred for 26 hours, saturatedness was added thereto. The aqueous ammonium solution was vaporized, and the resulting mixture was stirred for 1 hour, filtered under reduced pressure, and the organic layer was separated, followed by evaporation to give compound (6). Compound (6) was dissolved in acetic acid to dissolve the compound (6) obtained above. (21.7 mmol), potassium iodide (KI) ((86·8 mmol) and sodium monohydrate (NaH2P〇2.H2〇) (130.2 mmol), and the solution was stirred under reflux for 21 hours. After the solution was cooled to 25, water was added and stirred, and then the resulting solid was decanted. The solid obtained was washed successively with decyl alcohol, ethyl acetate and tetrahydrofuran to give the title compound as a pale ivory solid. (1).

9-bromo-anthracene (15 gram, 58·3 mmol), benzene dissolved in a mixed solution of compound (300) in toluene (300 ml) and ethanol (5 ml) Boronic acid (chemical mouth 200) (8.5 g '70.0 mmol) and tetrakis(triphenylphosphine) palladium (pd(pph3)4) 29 200829680 (6.7 g, 5.8 mmol). After a 2 M aqueous sodium carbonate solution (145 ml) was added thereto, the mixture was stirred at 120 ° C under reflux for 5 hours. Then, the temperature was lowered to 25 ° C, and the reaction was quenched by adding distilled water (150 ml). Subsequent extraction with ethyl acetate (200 mL), EtOAc (EtOAc:EtOAc) 47.21 millimoles). Compound (400), dissolved in dichloromethane (360 ml) under nitrogen atmosphere, compound (300) (11 · 7 g, 46·0 Amol) and N-sodium sulphate ( N-bromosuccinimide ) (9·0 g, 50.6 mmol). The resulting solution was then stirred at 25 ° C for 5 hours. The reaction was quenched by the addition of distilled water (300 ml). After extraction with dichloromethane (2 mL), it was dried under reduced pressure, and finally recrystallized from tetrahydrofuran (2 mL) and decyl alcohol (2 mL) to give the title compound (4 〇〇) ( Ϊ́3·〇克, 39.0 millimoles). Compound (500) 3 ' was dissolved in carefully purified tetrahydrofuran (2 mL) to dissolve compound (4 〇〇) (13 g, 39.0 mmol). The resulting solution was cooled to, and n-butyllithium (1·6 Μ in hexane) (29·3 ml, 46.8 mmol) was slowly added thereto. After stirring the mixture for 1 hour, 2_isopropoxy-4,4,5, anthracenyl ",3,2-dioxaborolane (15.9 ml, 78·0 mmol) was added. The temperature was slowly raised to 25 ° C, and the mixture was stirred for 1 day. After quenching the reaction by adding steamed water (m.), the mixture was extracted with ethyl acetate (fine hexane) and dried under reduced pressure. Recrystallization from tetrazole (20 ml) and methanol (200 ml) to give the title compound (5 〇〇) 200829680 (13·5 g, 35·5 mmol). Solvent in toluene (300 ml) / glutamic acid 2-虱·9,1〇-蒽醌 (7.2 g, 29.7 mmol), compound (500) (135 voucher, ancient #ττ, / • see 35·5 pens), four (tripty phosphine) palladium (0) (Pd(PPh3)4) (3.5 g, 3 〇台宜和,ΛΛ1·凡,υ笔耳耳) and Aliquat 336 ( 1.4 ml, 3, 〇 millimolar. After adding 2M aqueous solution of cesium carbonate (15 〇 ml), the resulting mixture 3 (4) was stirred under the condition of (4). Then, the temperature was lowered to hunger, and steamed water was added by adding (100 ml) The reaction was quenched. Finally, it was extracted with ethyl acetate (2 mL) and dried under reduced pressure. I was recrystallized from methanol (q. Target compound (1)·〇克, 21.7 mmol.) Compound (7〇0) is prepared for 2-bromonaphthalene (2-bn>m〇naphthalene) (11.2 g, 54·3 mmol) Add tetrahydrofuran (250 ml), and stir the mixture for 1 min at 25 °C to achieve complete dissolution. After cooling to -72 ° C, slowly add n-butyllithium (2.5 Μ in hexane) (26·0 ml, 65·1 mmol). After 1 hour, compound (600) (10.0 g '21.7 mmol) was added thereto, and the temperature was slowly raised to 25 ° C. After the reaction mixture was added for 26 hours, a saturated aqueous solution of ammonium sulfate was added thereto, and the resulting mixture was stirred for 1 hour, filtered under reduced pressure, and the organic layer was separated, then evaporated to give the title compound (700) ( 15.6 g, 21 · 7 Mol.) Compound (101) is dissolved in acetic acid (250 ml) to dissolve the compound (700) (15 6 g, 21.7 mmol, potassium iodide (ΚΙ) (14. 4 g, 86.8 mmol) and sodium monohydrate 31 200829680 (NaH2P02, H20) (13·8 g, ι 30·2 mmol), The solution was stirred for 21 hours under reflux. After cooling the solution to 25, water (4 mL) was added and stirred, and then the resulting solid was filtered. The obtained solid was washed successively with methanol (3 ml), ethyl acetate (100 ml) and THF (50 ml) to give the title compound (1 〇1) (10·0 g , 68%). 4 Nuclear Magnetic Resonance (NMR) (Deuterochloroform (CDC13), 200 MHz) δ = 7·22 (m, 1H), 7.32-7.35 (m, 12H), 7.48-7.54 (m, 5H) ), 7.67-7.73 (m, 13H), 7·89 (m, 3H) MS/FAB: 682 (measured), 682.85 (calc.) [Preparation Examples 2 to 36] Table 1 was prepared according to the procedure described in Preparation Example 1. The organic EL compound shown. The NMR data of each compound are shown in Table 2. [Table 1]

2 Preparation Example Compound No. Ri r2 Rs 1 101 Ό0 , , CO Ό 2 102 , €0 , CO , , CO 3 103 , 00 '*€0 ·, Λ 32 200829680 4 104 ''CO , , CO 00 5 105 , co , , CO 6 106 ''CO , , CO 0^*0 7 107 , , CO , CO 0-0 V s 8 108 ΌΟ , 00 •i 9 109 ''CO , , CO '.〇r° ° 10 110 , , CO ''CO ^00 r 11 111 , , 00 '00 a00 12 112 ''CO , ,CO .03⁄4 13 113 Ό 14 114 •, ^b Ό0 15 115 Ό Ό Ό 16 116 Ό Ό , O0 17 117 00 00 Ό 33 200829680 18 118 όο 00 , , € 0 19 119 Ό 20 120 - Ό 0 21 121 ρ-ο Ό 22 122 . Old bb Ό 23 123 0^0 s O^O \ \ Ό 24 124 . 〇r°° .(/° Ό 25 125 1 1 ''CO 26 126 〇c〇o 〇r°° Ό 27 127 • 'tfb,, €0 Ό 28 128, €0 ''CO 29 129 '' CO 30 130 -, ^o Ό0 00 34 200829680 31 131 , 'Φ〇''CO -<y〇32 132 , , 33 33 133 'CO , ΌΟ 34 134 , 'CO 35 135 ''CO Φο CO 36 136 ''CO φο - [Table 2] Compound No. 1 NMR (CDCI3, 200 MHz) MS/FAB Calculated 101 δ 7.22 (m, 1H), 7.32-7.35 (m, 12H), 7.48-7.54 (m, 5H), 7.67-7.73 (m, 13H), 7.89 (m, 3H) 682 682.85 102 <5 7.32 (m, 12H), 7.54 -7.57(m, 4H), 7.67-7.73(m, 16H), 7.88(m, 4H) 732 732.91 103 δ 1.67(s, 6H), 7.28-7.33(m, 12H), 7.54-7.77(m, 19H ), 7.84-7.90(m, 5H) 798 799.01 104 δ 7.32-7.38(m, 13H), 7.54-7.56(m, 4H), 7.67-7.73(m, 16H), 7.86(m, 3H) 733 732.91 105 5 7.22(m, 1H) 7.32-7.34(m, 12H), 7,48-7.54(m, 9H), 7.65-7.73(m, 13H), 7.88(m, 3H) 758 758.94 106 <5 7.21( m, 1H) 7.32_7.54(m, 20H), 7.67-7.73(m, 14H), 7.90(m, 3H) 759 759.94 107 δ 7.28-7.34(m, 15H), 7.48-7.54(m, 7H) , 7.68-7.74(m, 13H), 7.87(m, 3H) 758 758.94 108 6 7.24(m, 2H) 7.33-7.34(m, 14H), 7.48-7.54(m, 7H), 7.66-7.73(m, 16H), 7.89(m, 3H) 834 835.04 109 <5 7.30-7.33(m, 12H), 7.52-7.54(m, 8H), 7.67-7.74(m, 16H), 7.86(m, 3H) 808 809.00 110 δ 7.32-7.38 (nri, 15H), 7.54 (m, 4H), 7.67-7.75 (m, 17H), 7.88 (m, 4H) 810 809.00 111 ^ 7.28-7.32 (m, 14H), 7.54-7.56 ( m. 6H). 7.67-7.74(m, 16H), 7.91 (m, 4H) 808 809.00 112 <5 7.32-7.38 (m, 13H) , 7.52-7.55(m, 8H), 7.65-7.75(m, 16H), 7.87(m, 3H) 810 809.00 113 δ 1.68(s. 12H) 7.28-7.38(m, 13H), 7.48-7.77(m, 16H), 7.84-7.90(m, 5H) 814 815.05 114 δ 1.67(s, 12H) 7.28-7.35(m, 12H), 7.54-7.77(m, 18H), 7.84-7.90(m, 6H) 864 865.11 35 200829680 115 δ 7.22-7.32(m, 15H), 7.48-7.54(m, 7H), 7.65-7.75(m, 7H), 7.89(s, 1H) 582 582.73 116 δ 7.22(m, 2H) 7.32-7.35( m, 12H), 7.49-7.55 (m, 6H), 7.65-7.72 (m, 10H), 7.88 (s, 2H) 633 632.79 117 δ 7.21 (m, 1H) 7.32-7.40 (m. 14H), 7.45- 7.55(m, 5H). 7.63-7.67(m, 13H), 7.87(s, 1H) 683 682.85 118 δ 7.30-7.38(m, 14H), 7.54(m, 4H), 7.63-7.73(m, 16H) , 7.89(s, 2H) 732 732.91 119 5 7.22_7.32(m, 15H), 7.48-7.54(m. 15H), 7.67-7.73(m, 7H), 7.86(s, 1H) 734 734 9Γ 120 δ 7.20(m, 2H) 7.32(m, 12H), 7.46-7.56(m, 14H), 7.65-7.74(m, 10H), 7.89(m, 2H) 784 784,98 121 δ 7.20-7.38(m, 17H ), 7.44-7.54(m, 11H), 7.67-7.70(m. 9H), 7.89(s, 1H) 735 734.92 122 ά 7.22-7.34(m, 21H), 7.46-7.53(m, 11H). 7.66- 7.74(m, 13H), 7.85(s, 1H) 886 887.11 123 (5 7.28-7.32(m, 19H), 7. 5〇-7.54(m, 11H), 7.65-7.67(m, 7H), 7.88(s, 1H) 734 734 124 (5 7.20(m, 1H) 7.32-7.35(m. 12H), 7.46-7.54(m , 13H), 7.65-7.72(m, 13H), 7.90(m, 3H) 834 835.04 125 ά 7.32-7.44(m, 18H), 7.54(m, 4H), 7.67-7.70(m, 18H), 7.88( s, 4H) 886 885.10 126 d 7.28-7.32(m, 17H), 7.48-7.54(m, 9H), 7.67-7.73(m, 13H), 7.87(m, 3H) 834 835.04 127 5 1.67(s, 6H 7.22-7.33(m, 13H), 7.48-7.73(m, 17H), 7.84-7.90(m, 4H) 748 748.95 128 (5 1.68(s, 6H), 7.28-7.38(m, 12H), 7.55- 7.73(m, 19H), 7.84-7.90(m, 5H) 798 799.01 129 5 1.67(s, 12H) 7.21-7.38(m, 12H), 7.55-7.73(m, 18H), 7.85-7.91 (m, 6H) ) 864 865.11 130 5 1.67(s, 6H), 7.32-7.38(m, 13H), 7.54-7.74(m,19H). 7.84-7.93(m, 4H) 798 799.01 131 5 1.68(s, 6H) 7.23- 7.40(m, 13H), 7.48-7.60(m, 10H). 7.67-7.77(m, 11H), 7.85-7.90(m, 4H) 824 825.04 132 (5 1.67(s, 6H) 7.22-7.33(m, 13H), 7.48-7.73 (m, 17H), 7.84-7.90 (m > 4H) 748 748.95 133 δ 1.68 (s, 6H), 7.28-7.38 (m, 12H), 7.55-7.73 (m. 19H), 7.84 -7.90(m, 5H) 798 799.01 134 <5 1.67(s, 12H) 7.21-7.38(m, 12H), 7.55-7 .73(m, 18H), 7.85-7.9l(m, 6H) 864 865.11 135 (5 1.67(s, 6H), 7.32-7.38(m, 13H)· 7.54-7.74(m,19H), 7.84-7.93 (m, 4H) 798 799.01 136 δ 1.68(s, 6H) 7.23-7.40(m, 13H), 7.48-7.60(m, 10H), 7.67~7.77(m, 11H), 7.85-7.90(m, 4H) 824 825.04

[Examples 1 to 13] Fabrication of a ruthenium LED device by using the compound of the present invention An OLED device was fabricated by using the electroluminescent material of the present invention. First, a transparent electrode indium tin oxide (ITO) film (15 Ω / obtained from glass OL (manufactured by Samsimg-Coniing)) was continuously used using triethylene glycol, acetone, ethanol, and steamed water. □ (face gamma, electric square and C square resistance))) performing ultrasonic rinsing, and storing it in isopropyl alcohol before use, then mounting the ITO substrate on the substrate of the vacuum vapor deposition apparatus to lose the vacuum gas phase The cell is placed in one of the deposition devices and is represented by the following 36. The temperature is 36 200829680 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine 4,4',4''-Tris-(N-(naphthylen,2-yl)-N-phenylamine)triph enylamine,2-TNATA), and then venting it until the vacuum in the chamber reaches 10_6 Torr (torr) A current is applied to the cell to evaporate 2-TNATA to vapor deposit a 60 nm thick hole injection layer (HIL) on the IT0 substrate.

Then, N,N'-biguanidinyl)-N,N'-diphenyl-4,4'.diamine (N, N,N'-diphenyl) is added to another unit of the vacuum vapor deposition apparatus. N'-bis(a-naphthyl)-N,N'-diphenyl-4, 4'-diamine, NPB), and applying a current to the unit to evaporate NPB, thereby vapor deposition on the hole injection layer A layer of 20 nm thick hole transfer layer was deposited.

After the hole injecting layer and the hole transferring layer are formed, an electroluminescent layer is vapor deposited thereon in the following manner. In one unit of the vacuum vapor deposition apparatus, a compound of the present invention (e.g., compound 121) is added, and in another unit, perylene having the structure shown in Fig. 37 200829680 is added as a doping material. The 35 nm thick electroluminescent layer was vapor deposited on the hole transfer layer by evaporating the two materials at different rates and using a doping of 2 mol% to 5 mol% of germanium.

Next, vapor deposition of a thickness of 20 nm is represented by the following chemical formula (8-hydroxy 啥 Lin)! (III) (tris (8-hydroxyquinoline) aluminum (III), Alq) as an electron transfer layer, and vapor deposition of a thickness of 1 nm to 2 nm by the following chemical formula (lithium quinolate, Liq) acts as an electron injection layer. Subsequently, a 150 nm thick aluminum (A1) cathode was vapor-deposited by using another vapor deposition apparatus to fabricate an OLED.

Each of the materials used in the OLED device was purified by sublimation at 10 Torr. [Examples 14 to 26] An OLED device 38 was produced by using the compound of the present invention. 200829680 A hole injection layer and a hole transfer layer were formed as in Example 1, and an EL was vapor-deposited thereon in the following manner. Floor. In one unit of the vacuum vapor deposition apparatus, a compound of the present invention (e.g., compound 121) is added, and coumarin 545T (Coumarine 545T, C545T) having the structure shown below is added to another unit. The 35 nm thick EL layer was vapor deposited on the hole transfer layer by evaporating the two materials at different rates and by doping 2 to 5 mol% of C545T.

An electron transfer layer and an electron injection layer were vapor-deposited in the same manner as in Example 1, and a 150 nm thick A1 cathode was vapor-deposited by using another vapor deposition apparatus to fabricate an OLED. [Comparative Example 1] Fabrication of an OLED device using a conventional EL material A hole injection layer and a hole transfer layer were formed as in Example 1. In one unit of the true air phase deposition apparatus, dinaphthylanthracene (DNA) was added as a material of blue EL, and ruthenium was added as another blue EL material in another unit. An electroluminescent layer having a thickness of 35 nm was vapor-deposited on the hole transfer layer by using a vapor deposition rate of 100:1. 39 200829680

An electron transfer layer and an electron injection layer were vapor-deposited in the same manner as in Example 1, and a 150 nm thick A1 cathode was vapor-deposited by another vapor deposition apparatus to fabricate an OLED. [Comparative Example 2] Fabrication of OLED device using a conventional EL material As in Example 1, a hole injection layer and a hole transfer layer were formed. Alq was added as an EL host material to another unit of the vapor deposition apparatus, and C545T was added to the other unit. The two materials were evaporated at different rates, and a 30 nm thick EL layer was vapor-deposited by doping on the hole transfer layer. The doping concentration is preferably from 2 mol% to 5 mol% in terms of Alq.

An electron transfer layer and an electron injection layer were vapor-deposited in the same manner as in Example 1, and an OLED having a thickness of 150 nm was vapor-deposited by using another vapor deposition apparatus to fabricate an OLED. 200829680 [Comparative Example 3] Using a conventional EL material to fabricate an OLED device As in Example 1, a hole injection layer and a hole transfer layer were formed. In another unit of the vapor deposition apparatus, DNA was added as a blue EL material, and another unit was charged with C545T. The 30 nm thick EL layer was vapor deposited on the hole transfer layer by evaporating the two materials at different rates and using doping. The doping concentration is preferably 2 to 5 mol% in terms of Alq. [Comparative Example 4] Using a conventional EL material to fabricate an OLED device As in Example 1, a hole injection layer and a hole transfer layer were formed. A compound (A) having the structure shown below is added as a blue EL material to another unit of the vapor deposition apparatus, which is disclosed in U.S. Patent Publication No. 20060046097 A1, and C545T is added to another unit. . The EL layer having a thickness of 30 nm is vapor-deposited on the hole transfer layer by evaporating the two substances at different rates and using doping. The doping concentration is preferably from 2 mol% to 5 mol% in terms of Alq.

An electron transfer layer and an electron injection layer were vapor-deposited in the same manner as in Example 1, and a 150 nm thick A1 cathode was vapor-deposited by another vapor deposition apparatus to fabricate an OLED. 41 200829680

V

[Experimental Example 1] Blue EL properties of the obtained OLED device The ruthenium LEDs produced in the above Examples 1 to 13 and Comparative Example 1 each contained an organic EL compound of the present invention and a conventional electroluminescent compound at 500. The blue luminous efficiency of these 〇LEDs was measured one by one at cd/m2 and 2,000 cd/m2, and the results are shown in Table 3. [Table 3] No. Body material dopant doping concentration (mol%) Luminous efficiency (cd/A) Color coordinate @500 cd/m2 @2,000 cd/m2 Example 1 Compound 101 - 茈2.0 5.72 5.30 (0.16, 0.21 Example 2 Compound 102 茈 2.0 5.43 5.04 (0.16, 0.22) Example 3 Compound 103 茈 3.0 5.60 5.17 (0.16, 0.21) Example 4 Compound 107 茈 3.0 5.93 5.46 (0.16, 0.21) Example 5 Compound 109 茈 3.0 6.27 5.88 (0.16 , 0·22) Example 6 Compound 113 茈 5.0 5.36 4.97 (0.15, 0.18) Example 7 Compound 115 茈 3.0 5.26 4.80 (0.15, 0.17) Example 8 Compound 120 茈 3.0 5.54 5.12 (0.16, 0.20) Example 9 Compound 121 茈3.0 6.30 5.86 (0.15, 0.19) Example 10 Compound 122 茈 3.0 ----- 5.80 5.42 (0·16, 0·20) 42 200829680 1 Example 11 Compound 126 茈 3.0 6.03 5.63 (0.15, 0.19) Example 12 Compound 129 茈3.0 5.99 5.64 (0.15, 0·19) Example 13 Compound 136 茈 3.0 5.88 5.51 (0.15, 0.18) Comparative Example 1 DNA 茈 2.0 4.45 3.62 (0.16, 0.20) Table 1 shows the application of the material of the present invention to a blue EL device The result. As can be seen from Table 1, the luminous efficiency of the EL material of the present invention is 5.26 candelas per amp (cd/A) to 6.30 candelas per amp (cd/A) at low brightness (@500 cd/m2). The high-brightness (@2000 cd/m2) is 4.80 cd/A to 5.88 cd/A, and the EL material of Comparative Example 1 has a luminous efficiency of 4.45 cd/A and 3.6 cd at low luminance and high luminance, respectively. /A. Therefore, the EL device using the organic EL compound of the present invention has a luminous efficiency higher than that of the comparative example by 1.5 cd/A or more. In particular, each of the compounds of the present invention can increase the luminous efficiency by 2 cd/A or more at high luminance. Further, when the host material of the present invention is used, a certain degree of improvement in color purity can be observed. The results of the improvement of the color purity and the luminous efficiency shown above demonstrate that the EL material of the present invention has excellent properties. Fig. 1 shows the luminous efficiency-current density property of Comparative Example 1 using DNA: 茈 as a conventional EL material, and Figs. 2 and 3 shows the current of Example 9 using the compound (121) of the present invention as an EL material, respectively. Density-voltage properties and luminous efficiency - current density properties. The results shown in the figures demonstrate a significant improvement in performance. [Experimental Example 2] Green EL Properties of OLED Devices Prepared The OLEDs manufactured in Examples 14 to 26 and Comparative Example 1 each contained a 43 200829680 organic EL compound and a conventional electroluminescent compound at 5,000 cd/ The green light-emitting efficiencies of the OLEDs were measured one by one under the brightness of m2 and 20,000 cd/m2, and the results are shown in Table 4. [Table 4] No. Body material dopant doping concentration (mol%) Luminous efficiency (cd/A) Color coordinate @5,000 cd/m2 @20,000 cd/m2 Example 14 Compound 101 C545T 2.0 17.5 17.0 (0.28, 0.64) Example 15 Compound 102 C545T 2.0 17.2 16.8 (0.28, 0.64) Example 16 Compound 103 C545T 3.0 18.2 17.7 (0.28, 0.64) Example 17 Compound 107 C545T 3.0 18.5 17.9 (0.28, 0.64) Example 18 Compound 109 C545T 3.0 18.7 18.0 (0.27, 0.63) Example 19 Compound 113 C545T 5.0 17.2 16.8 (0.26, 0.64) Example 20 Compound 115 C545T 3.0 17.3 16.8 (0.26, 0.62) Example 21 Compound 120 C545T 3.0 19.2 18.4 (0.27, 0.64) Example 22 Compound 121 C545T 3.0 20.1 19.5 ( 0.27, 0.64) Example 23 Compound 122 C545T 3.0 17.9 16.7 (0.28, 0.65) Example 24 Compound 126 C545T 3.0 18.0 17.4 (0.27, 0.63) 44 200829680 Example 25 Compound 129 C545T 3.0 18.7 18.0 (0.28, 0.63) Example 26 Compound 136 C545T 3.0 18.6 17.9 (0.28, 0.63) Comparative Example 2 Alq C545T 2.0 10.3 9.1 (0.29, 0.65) Comparative Example 3 DNA C545T 2.0 15.8 14.0 (0.27, 0.61) Comparative Example 4 Compound A C545T 2.0 16.7 14.8 (0.25, 0.62) Table 4 shows the results of the properties of the green EL device to which the material of the present invention is applied. Similar to the blue EL device of Experimental Example 1, it was confirmed that it had excellent properties at low luminance and high luminance as compared with the conventional EL material. The efficiency was improved by 70% or more as compared with the Alq host material of Comparative Example 2, and the efficiency was improved by 40% or more as compared with the conventional host material of Comparative Example 3. This result indicates that the present invention significantly overcomes the limitations of conventional green EL materials. In particular, it is estimated that a significant increase in performance at high brightness will suffice for such compounds to be practically applied to larger screen or 2 inch handheld OLEDs that require excellent properties. There is no significant difference in the color coordinates. Therefore, the EL material according to the present invention which can simultaneously improve the luminous efficiency and maintain the same color purity is an epoch-making invention which is one level beyond the conventional material. Fig. 4 shows the luminous efficiency-luminance property of Comparative Example 2 using Alq: C545T as a conventional green EL material, and Fig. 5 shows the luminous efficiency of the green EL device of Example 22 using the compound (121) of the present invention as an EL material. - Current density properties. Fig. 6 shows the luminous efficiency-current density properties of Comparative Example 3 and Comparative Example 4 using a conventional EL material and a green EL device using the compound (121) of the present invention as an EL material. 45 200829680 The EL material of the present invention can be applied to both blue t 0 LEDs and green OLEDs and in terms of performance (4) excellent results κ results show excellent salient properties of EL materials. The material of the present invention having such characteristics can simplify the structure of the 〇led panel, thereby indirectly reducing the production cost of the OLED. These excellent features make the development of the OLED field possible with innovative results. Fig. 7 is a comparison of the color purity of the green EL device of the green EL device of Comparative Example 2 using the compound (121) of the present invention as an example of the EL material. The el material of the present invention exhibits good EL color properties and is not significantly different from conventional pure green EL materials. In the EL spectrum of the EL device of Example 22, it was confirmed that the characteristic green EL peak was at 520 nm. This indicates the fact that the organic EL compound of the present invention having a blue EL property has excellent electrical properties, which maximizes the characteristics of the beta dopant. The excellent life characteristics of the materials of the present invention are in particular comparable to the cost of the material of the invention compared to conventional EL materials, in contrast to conventional materials having better electrical conductivity. By the 1st position of 9-arylanthryl (1〇p〇siti(8) to the 2nd position of the antihrraCene (2-positicm), the effect of intermolecular orbital symmetry can be enhanced, 1 The energy level relationship with the dopant is more favorable, and the disadvantages of the conventional conventional 9,10-diarylfluorene structure are compensated for. The electroluminescent compound of the invention has high luminous efficiency and extremely long material life, so that it can be prepared The qLed device has a very long operating life. [Simple description of the drawing] Fig. 1 shows the luminous efficiency_current density property of Comparative Example 1; FIG. 2 shows the current density_voltage property of the blue 〇LED of Example 9; The graph shows the luminous efficiency and current density properties of the blue 〇LED of Example 9. 46 200829680 FIG. 4 shows the luminous efficiency-luminance property of the green OLED with the conventional electroluminescent material of Comparative Example 2; FIG. 5 shows Example 22 Luminous efficiency-current density property of green OLED; FIG. 6 shows luminous efficiency-current density properties of green OLEDs of Example 22, Comparative Example 3, and Comparative Example 4; and Green OLED of Example 22 and Comparative Example 2 of FIG. Comparison of color purity curves Fig. 0 [Description of main component symbols] (none) 47

Claims (1)

200829680 X. Patent application scope: 1. An organic electroluminescent material, which is represented by the following chemical formula 1: [Chemical Formula 1] Wherein, the core to R3 is independently a phenyl group or a c10 to c20 fused polycyclic aromatic ring, and the phenyl group of the core to R3 or the fused polycyclic aromatic ring of C1(C) to C2G can pass Ci to C20 An alkyl group, a Ci to C20 alkoxy group, a halogen, a C5 to (37 cycloalkyl group, a phenyl group or a fused polycyclic aromatic group. 2. The organic electroluminescent material according to claim 1, wherein the chemical formula 1 Ri to R3 are independently selected from the group consisting of phenyl, naphthyl, anthryl, fluorenyl, phenanthryl, fluorancenyl, fluorenyl, fluorenyl (perylenyl) or tetraphenyl (naphthacenyl); and phenyl, naphthyl, anthracenyl, fluorenyl, phenanthryl, fluorenyl, fluorenyl, fluorenyl and tetracene can be C! to C2G alkane An alkoxy group of C! to C2G, a halogen atom, a cycloalkyl group of c5 to c7, a phenyl group or a fused polycyclic aromatic group. 3. The organic electroluminescent material according to claim 2 , which is selected from compounds represented by the following chemical formula: 48 200829680 49 200829680 50 200829680 An organic electroluminescence device comprising: a first electrode; a second electrode; and one or more organic layers sandwiched between the first electrode and the second electrode, wherein the organic layer comprises a Or a plurality of compounds represented by Chemical Formula 1: [Chemical Formula 1] 51 200829680 The center to R3 is independently a phenyl or c10 to c20 fused polycyclic aromatic ring, and the phenyl or C1G to C2 R fused polycyclic aromatic ring of Ri to R3 can be passed through The organic electroluminescent device of claim 4, wherein the organic layer comprises an electroluminescent region, the electricity The electroluminescent device comprises one or more compounds represented by Chemical Formula 1 and one or more electroluminescent dopants. 6. The organic electroluminescent device of claim 5, wherein the electroluminescent dopant is selected a compound represented by one of Chemical Formulas 2 to 4: [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] Among them, Ar! and Αγ2 are selected from the group consisting of indenofluorene, fluorene and spiro-fluorene, and are represented by the following chemical formula 52 200829680 Six Τ Μ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ In the ring; Ar2 is the same, Ar3 is the same as private, and is the same as ^; 7 18 series, independently an aromatic ring, or a polycyclic aromatic ring in which two or more aromatic ring systems are fused; R19 to n22 are independently a direct bond or a branch having or without a functional substituent.链1 to 〇: 2()alkyl; &23 to R26 are independently a gas or aromatic group, and ^7 to Al*l are independently aromatic rings, or two or more of them The aromatic ring system is a fused polycyclic aromatic ring. An organic electroluminescent device according to the above item 6, wherein the electroluminescent dopant is selected from the group consisting of the following chemical formula: 53 200829680 54 200829680 55 200829680 56 200829680 57 200829680 58 200829680 59 200829680 60 200829680 P Η b Wherein r19 to r22 are a methyl group or an ethyl group. 8. The organic electroluminescent device according to claim 5, wherein the electroluminescent dopant is selected from the group consisting of compounds represented by one of Chemical Formulas (5) to (7): [Chemical Formula 5] 61 200829680 [Chemical Formula 7] Wherein R27 and R28 are independently a polycyclic aromatic ring in which two or more aromatic rings are fused; R29 to R32 are independently an aromatic ring; and each aromatic ring of R27 to R32 can pass through C! To C2G alkyl substitution. 9. The organic electroluminescent device of claim 8, wherein the electroluminescent dopant is selected from the group consisting of compounds represented by one of the following chemical formulas: 62 200829680 63 200829680 64 200829680 65