ORGANIC COMPOUND, ORGANIC LIGHT-EMITTING DIODE INCLUDING ORGANIC COMPOUND, AND DISPLAY DEVICE INCLUDING ORGANIC LIGHT-EMITTING DIODE

Abstract

The present invention relates to an organic compound, an organic light-emitting diode including the organic compound, and a display device including the organic light-emitting diode. More particularly, the present invention relates to an organic compound including a compound presented by Chemical Formula 1 and being capable of improving luminous efficacy, thermal stability, and lifespan properties, an organic light-emitting diode including the organic compound, and a display device including the organic light-emitting diode.

Claims

1. An organic compound represented by Chemical Formula 1 below: ##STR00049## wherein X.sub.1 to X.sub.3 are independently nitrogen (N) or carbon (C), and R.sub.1 to R.sub.7 are independently selected from the group consisting of hydrogen, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms.

2. The organic compound according to claim 1, wherein, in Chemical Formula 1, X.sub.1 to X.sub.3 are independently nitrogen (N) or carbon (C), and at least two of X.sub.1 to X.sub.3 are N.

3. The organic compound according to claim 1, wherein, in Chemical Formula 1, R.sub.1 to R.sub.7 are independently selected from the group consisting of hydrogen, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a phenanthrene group, a pyrenyl group, a perylenyl group, a chrysenyl group, a carbazole group, a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a pyradazine group, a quinolinyl group, an isoquinoline group, and an acridyl group.

4. The organic compound according to claim 1, wherein, in Chemical Formula 1, R.sub.3 is represented by one of Chemical Formulas 2-1 to 2-6 below: ##STR00050##

5. The organic compound according to claim 1, wherein Chemical Formula 1 is one of Chemical Formulas 1-1 to 1-13: ##STR00051## ##STR00052## ##STR00053## ##STR00054##

6. An electron transport material, comprising the organic compound according to claim 1.

7. An organic light-emitting diode, comprising the electron transport material according to claim 6.

8. The organic light-emitting diode according to claim 7, comprising a first electrode; a second electrode; and an organic material layer disposed between the first and second electrodes, wherein the organic material layer comprises the electron transport material.

9. The organic light-emitting diode according to claim 8, wherein the organic material layer comprises one or more selected from the group consisting of an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, and a hole injection layer.

10. A display device, comprising the organic light-emitting diode according to claim 6.

Description

EXAMPLES

Preparation Example 1

[0077] 1) Preparation of Compound 1-1

##STR00008##

[0078] 100 g (450.03 mmol, 1 eq) of phenanthren-9-ylboronic acid, 78 g (450.03 mmol, 1 eq) of 4-bromophenol, 26 g (22.54 mmol, 0.05 eq) of Pd(PPh.sub.3).sub.4, and 187 g (1,352 mmol, 3 eq) of K.sub.2CO.sub.3 were added to a 5 L round flask, and toluene, ethanol (Et-OH), and H.sub.2O were added thereto in an amount of 2.2 L, 450 mL, and 450 mL, respectively, followed by reflux stirring. After reaction, extraction was performed using CH.sub.2Cl.sub.2/H.sub.2O, and a CH.sub.2Cl.sub.2 layer was dried using MgSO.sub.4. Then, purification was performed using a silica-gel column to obtain 103 g of Compound 1-1 in a yield of 85%.

[0079] 2) Preparation of Compound 1-2

##STR00009##

[0080] 100 g (359.91 mmol, 1 eq) of 4-phenanthren-9-yl-phenol, 74.8 g (739.83 mmol, 2 eq) of triethyl amine, and 1.8 L of methylene chloride (MC) were added to a 5 L round flask and stirred at 0° C. Then, 125 g (443.90 mmol, 1.2 eq) of trifluoromethane sulfuric anhydride was added dropwise thereto, followed by stirring for 1 hour. After reaction, extraction was performed using CH.sub.2Cl.sub.2/H.sub.2O, and a CH.sub.2Cl.sub.2 layer was dried using MgSO.sub.4. Then, purification was performed using a silica-gel column to obtain 119 g of Compound 1-2 in a yield of 80%.

[0081] 3) Preparation of Compound 1-3

##STR00010##

[0082] 100 g (248 mmol, 1 eq) of 4-(phenanthren-9-yl)phenyl trifluoromethanesulfonate, 126 g (497.03 mmol, 2 eq) of 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane), 14.3 g (24.85 mmol, 0.1 eq) of Pd(dba).sub.2, 13.9 g (49.70 mmol, 0.2 eq) of Pcy3, 97.5 g (994.06 mmol, 4 eq) of potassium acetate, and 1.2 L of 1,4-dioxane were added to a 3 L round flask, followed by reflux stirring. After reaction, extraction was performed using CH.sub.2Cl.sub.2/H.sub.2O, and a CH.sub.2Cl.sub.2 layer was dried using MgSO.sub.4. Then, purification was performed using a silica-gel column to obtain 56 g of Compound 1-3 in a yield of 90%.

[0083] 4) Preparation of Compound 1-4

##STR00011##

[0084] 50 g (131.47 mmol, 1 eq) of 4,4,5,5-tetramethyl-2-(4-(phenanthren-9-yl)phenyl)-1,3,2-dioxaborolane, 59.4 g (262.95 mmol, 2 eq) of 2,4-dichloro-6-phenyl-1,3,5-triazine, 7.6 g (6.57 mmol, 0.05 eq) of Pd(PPh.sub.3).sub.4, and 54.5 g (394.43 mmol, 3 eq) of K.sub.2CO.sub.3 were added to a 3 L round flask, and then toluene, ethanol (Et-OH), and H.sub.2O were added thereto in an amount of 1.3 L, 260 mL, and 260 mL, respectively, followed by reflux stirring. After reaction, extraction was performed using CH.sub.2Cl.sub.2/H.sub.2O, and a CH.sub.2Cl.sub.2 layer was dried using MgSO.sub.4. Then, purification was performed using a silica-gel column to obtain 40.8 g of Compound 1-4 in a yield of 70%.

[0085] 5) Preparation of Desired Compounds

##STR00012##

[0086] Compound 1-4 (1 eq), Ar1-X (1 eq) shown in Table 1 below, Pd (PPh.sub.3).sub.4 (0.05 eq), and K.sub.2CO.sub.3 (3 eq) were added to a 500 mL round flask, and then toluene, Et-OH, and H.sub.2O were added thereto, followed by reflux stirring. After reaction, extraction was performed using CH.sub.2Cl.sub.2/H.sub.2O, and a CH.sub.2Cl.sub.2 layer was dried using MgSO.sub.4. Then, purification was performed using a silica-gel column to obtain desired compounds having structures shown in Table 1 below.

TABLE-US-00001 TABLE 1 Formula Ar1-X Yield (%) Desired compounds 1-1 [00013] 75 [00014] 1-2 [00015] 71 [00016] 1-3 [00017] 70 [00018] 1-7 [00019] 65 [00020] 1-10 [00021] 67 [00022] 1-11 [00023] 69 [00024] 1-12 [00025] 64 [00026]

Preparation Example 2

[0087] 1) Preparation of Compound 2-1

##STR00027##

[0088] 50 g (291.98 mmol, 1 eq) of 9H-carbazole, 109 g (437.98 mmol, 1.5 eq) of 5-bromo-[1,1′-biphenyl]-2-ol, 5.56 g (87.59 mmol, 0.2 q) of Cu, 120 g (875.96 mmol, 3 eq) of K.sub.2CO.sub.3, and 38.5 g (145.99 mmol, 0.5 eq) of 18-Crown-6 were added to a 2 L round flask, and then 970 mL of nitrobenzene was added thereto, followed by reflux stirring. After reaction, filtration was performed using a Celite hot filter, and distillation was performed. Then, purification was performed using a silica-gel column to obtain 49.5 g of Compound 2-2 in a yield of 50%.

[0089] 2) Preparation of Compound 2-2

##STR00028##

[0090] 50 g (147.30 mmol, 1 eq) of 5-(4a,4b,8a,9a-tetrahydro-9H-carbazol-9-yl)-[1,1′-biphenyl]-2-ol, 29.8 g (294.60 mmol, 2 eq) of triethyl amine, and 730 mL of methylene chloride (MC) were added to a 2 L round flask and stirred at 0° C. Then, 49.87 g (176.76 mmol, 1.2 eq) of trifluoromethane sulfuric anhydride was added dropwise thereto, followed by stirring for 1 hour. After reaction, extraction was performed using CH.sub.2Cl.sub.2/H.sub.2O, and a CH.sub.2Cl.sub.2 layer was dried using MgSO.sub.4. Then, purification was performed using a silica-gel column to obtain 57 g of Compound 2-3 in a yield of 82%.

[0091] 3) Preparation of Compound 2-3

##STR00029##

[0092] 50 g (106.04 mmol, 1 eq) of 5-(4a,4b,8a,9a-tetrahydro-9H-carbazol-9-yl)-[1,1′-biphenyl]-2-yl trifluoromethanesulfonate, 53.87 g (212.09 mmol, 2 eq) of 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane), 6.1 g (10.60 mmol, 0.1 eq) of Pd(dba).sub.2, 5.9 g (21.21 mmol, 0.2 eq) of Pcy3, 97.5 g (994.06 mmol, 4 eq) of potassium acetate, and 1.1 L of 1,4-dioxane were added to a 3 L round flask, followed by reflux stirring. After reaction, extraction was performed using CH.sub.2Cl.sub.2/H.sub.2O, and a CH.sub.2Cl.sub.2 layer was dried using MgSO.sub.4. Then, purification was performed using a silica-gel column to obtain 41 g of Compound 2-4 in a yield of 87%.

[0093] 4) Preparation of Compound 2-4

##STR00030##

[0094] 40 g (89.00 mmol, 1 eq) of 9-(6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1′-biphenyl]-3-yl)-4a,4b,8a,9a-tetrahydro-9H-carbazole, 40.2 g (178.01 mmol, 2 eq) of 2,4-dichloro-6-phenyl-1,3,5-triazine, 51.4 g (4.45 mmol, 0.05 eq) of Pd(PPh.sub.3).sub.4, and 36.8 g (267.02 mmol, 3 eq) of K.sub.2CO.sub.3 were added to a 2 L round flask, and then toluene, ethanol (Et-OH), and H.sub.2O were added thereto in an amount of 445 mL, 90 mL, and 90 mL, respectively, followed by reflux stirring. After reaction, extraction was performed using CH.sub.2Cl.sub.2/H.sub.2O, and a CH.sub.2Cl.sub.2 layer was dried using MgSO.sub.4. Then, purification was performed using a silica-gel column to obtain 32.8 g of Compound 2-5 in a yield of 72%.

[0095] 5) Preparation of Desired Compound

##STR00031##

[0096] Compound 2-4 (1 eq), Ar2-X (1 eq) shown in Table 2 below, Pd (PPh.sub.3).sub.4 (0.05 eq), and K.sub.2CO.sub.3 (3 eq) were added to a 500 mL round flask, and toluene, Et-OH, and H.sub.2O were added thereto, followed by reflux stirring. After reaction, extraction was performed using CH.sub.2Cl.sub.2/H.sub.2O, and a CH.sub.2Cl.sub.2 layer was dried using MgSO.sub.4. Then, purification was performed using a silica-gel column to obtain a desired compound having structures shown in Table 2 below.

TABLE-US-00002 TABLE 2 Formula Ar2-X Yield (%) Desired compound 1-6 [00032] 73 [00033]

Preparation Example 3

[0097] 1) Preparation of Compound 3-1

##STR00034##

[0098] 100 g (343.45 mmol, 1 eq) of (4-(4a,4b,8a,9a-tetrahydro-9H-carbazol-9-yl)phenyl)boronic acid, 155 g (686.90 mmol, 2 eq) of 2,4-dichloro-6-phenyl-1,3,5-triazine, 19.83 g (17.17 mmol, 0.05 eq) of Pd(PPh.sub.3).sub.4, and 142 g (1,030.36 mmol, 3 eq) of K.sub.2CO.sub.3 were added to a 5 L round flask, and toluene, ethanol (Et-OH), and H.sub.2O were added thereto in an amount of 1.7 L, 350 mL, and 350 mL, respectively, followed by reflux stirring. After reaction, extraction was performed using CH.sub.2Cl.sub.2/H.sub.2O, and a CH.sub.2Cl.sub.2 layer was dried using MgSO.sub.4. Then, purification was performed using a silica-gel column to obtain 105 g of Compound 3-1 in a yield of 70%.

[0099] 2) Preparation of Desired Compounds

##STR00035##

[0100] Compound 3-1 (1 eq), Ar3-X (1 eq) shown in Table 3 below, Pd (PPh.sub.3).sub.4 (0.05 eq), and K.sub.2CO.sub.3 (3 eq) were added to a 500 mL round flask, and toluene, Et-OH, and H.sub.2O were added thereto, followed by reflux stirring. After reaction, extraction was performed using CH.sub.2Cl.sub.2/H.sub.2O, and a CH.sub.2Cl.sub.2 layer was dried using MgSO.sub.4. Then, purification was performed using a silica-gel column to obtain desired compounds having structures shown in Table 3 below. The obtained desired compounds were confirmed by the results of NMR and FD-MS analysis shown in Tables 4 and 5.

TABLE-US-00003 TABLE 3 Formula Ar1-X Yield (%) Desired compounds 1-4 [00036] 74 [00037] 1-5 [00038] 72 [00039] 1-13 [00040] 68 [00041]

TABLE-US-00004 TABLE 4 Formula .sup.1H NMR (CDCl.sub.3), 300 MHz 1-1 9.08(1H,d),8.84(1H,d),8.55(1H,d),8.36(2H,d),8.27(1H,d),8.19(1H,d), 8.05(1H,s), 7.96~7.90(8H,m), 7.70~7.50(9H,m), 7.35(1H,t), 7.25~7.16(4H,m) 1-2 9.08(1H,d),8.84(1H,d),8.55(1H,d),8.40~8.27(4H,m),8.19(1H,d), 8.10~7.90(7H,m), 7.79~7.41(15H,m),7.25~7.16(4H,m) 1-3 9.08(1H,d),8.84(1H,d),8.55(1H,d),8.36(2H,d),8.27(1H,d),8.19(1H,d), 8.08~7.90(8H,m),7.70~7.35(l1H,m),7.25~7.16(8H,m) 1-4 9.08(1H,d),8.84(1H,d),8.55(1H,d),8.36(2H,d),8.27(1H,d),8.19~8.13 (3H,m),8.05(1H,d),7.94~7.90(6H,m),7.79~7.35(16H,m),7.20~7.16 (2H,m) 1-5 9.08(1H,d),8.84~8.79(2H,d),8.55(1H,d),8.36(2H,d),8.19~8.13(3H,m), 8.06~8.05(2H,d), 7.96~7.91(6H,m),7.79~7.35(15H,m), 7.20~7.16(2H,m) 1-6 9.08(1H,d),8.84(1H,d),8.55(1H,d),8.40~8.36(3H,m),8.27(1H,d), 8.19~8.02(6H,m) 7.94~7.90(2H,d),7.70~7.35(21H,m),7.20~7.16(2H,m) 1-7 9.08(1H,d),8.84(1H,d),8.55(1H,d),8.36~8.27(4H,m),8.06~8.05(2H,m), 7.96~7.90(8H,m),7.70~7.63(4H,m),7.50~7.35(6H,m),7.25~7.19(7H,m) 1-8 9.08(1H,d),8.84(1H,d),8.55(1H,d),8.35~8.13(7H,m),8.05(1H,d), 7.94~7.90(6H,m) 7.79~7.35(16H,m),7.20~7.16(2H,m) 1-9 9.09(2H,d),8.84(1H,d),8.55(1H,d),8.49(1H,d),8.30~8.16(6H,m), 8.08~7.90(9H,m), 7.70~7.50(8H,m),7.35(1H,t),7.25~7.16(4H,m) 1-10 9.08(1H,d),8.84(1H,d),8.59(1H,s),8.55(1H,s),8.36(2H,d),8.27 (2H,s),8.19(1H,d) 8.05(1H,s),7.96~7.90(4H,m),7.70~7.41(16H,m),7.25~7.16(8H,m) 1-11 9.08(1H,d),8.84(1H,d),8.55(1H,d),8.40~8.27(5H,m),8.06~7.90(8H,m), 7.79~7.63(6H,m),7.50~7.35(9H,m),7.25~7.16(7H,m) 1-12 9.08(1H,d),8.84(1H,d),8.55(1H,d),8.36~8.27(4H,m),8.06~7.90(9H,m), 7.70~7.63 (4H,m), 7.50~7.41 (7H,m), 7.25~7.16 (11H,m) 1-13 9.08(1H,d),8.84(1H,d),8.79(1H,d),8.55(1H,d),8.36~8.32(4H,m),8.19 (1H,d),8.05(1H.s),7.94~7.90(6H,m),7.70~7.35 (20H,m),7.20~7.16(2H,t)

TABLE-US-00005 TABLE 5 Compounds FD-MS Compounds FD-MS 1-1 m/z = 650.25 1-2 m/z = 726.28 C47H30N4 = 650.79 C53H34N4 = 726.88 1-3 m/z = 726.28 1-4 m/z = 726.28 C53H34N4 = 726.88 C53H34N4 = 726.88 1-5 m/z = 726.28 1-6 m/z = 802.31 C53H34N4 = 726.88 C59H38N = 802.98 1-7 m/z = 726.28 1-8 m/z = 725.28 C53H34N4 = 726.88 C54H35N3 = 725.90 1-9 m/z = 699.27 1-10 m/z = 802.31 C52H33N = 699.86 C59H38N = 802.98 1-11 m/z = 802.31 1-12 m/z = 802.31 C59H38N = 802.98 C59H38N = 802.98 1-13 m/z = 802.31 C59H38N = 802.98

Example 1

[0101] A substrate used to fabricate a device was ultrasonically cleaned with distilled water for 10 minutes, dried in an oven set at 100° C. for 30 minutes, and then transferred to a vacuum deposition chamber.

[0102] In Example 1, a top emission substrate was used, and an anode was formed of a metal/ITO layer. Silver (Ag) was used as the metal, and the thickness of indium tin oxide (ITO) was 10 nm. On the ITO electrode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic light-emitting layer, an electron transport layer, and an electron injection layer were sequentially deposited.

[0103] Specifically, the hole injection layer (HIL) was deposited to have a thickness of 5 nm. In addition, on the hole injection layer, the hole transport layer (HTL) was deposited to have a thickness of 120 nm. On the deposited hole transport layer, an electron blocking layer (EBL) was deposited to have a thickness of 15 nm. Then, to form the organic light-emitting layer, a BH compound was deposited to have a thickness of 20 nm, and 5% by weight of a BD compound was added as an impurity. In addition, Chemical Formula 1-1 prepared in Preparation Example 1 and lithium quinolate (LiQ) were mixed in a weight ratio of 2:1. Then, to form the electron transport layer (ETL), the mixture was deposited on the organic light-emitting layer to have a thickness of 30 nm. In addition, to form the electron injection layer (EIL), LiF was deposited to have a thickness of 1 nm.

[0104] In the process, the deposition rate of the organic material layer was maintained at 0.5 to 1.0 Å/sec. During deposition, degree of vacuum was maintained at 1 to 4×10.sup.−7 torr.

[0105] In addition, to maximize a resonance effect, a translucent electrode (cathode) was disposed on the electron injection layer. In this case, a magnesium (Mg)-silver (Ag) alloy was used to form the translucent electrode, and the translucent electrode was formed to have a thickness of 14 nm.

[0106] Finally, to improve light efficiency, a capping layer (CPL) was deposited to have a thickness of 63 nm. In addition, after vacuum deposition, the substrate was transferred to a glove box, and an encapsulation process was performed. A glass cap having a moisture absorbent (getter) therein was used as a sealing member. In addition, compounds used in deposition of each layer are as follows.

##STR00042## ##STR00043##

Examples 2 to 13

[0107] Experiments were conducted in the same manner as in Example 1, except that the compounds of Table 6 were used instead of Chemical Formula 1-1.

Comparative Example 1

[0108] An experiment was conducted in the same manner as in Example 1, except that ET1 represented by the following chemical formula was used instead of Chemical Formula 1-1.

##STR00044##

Comparative Example 2

[0109] An experiment was conducted in the same manner as in Example 1, except that ET2 represented by the following chemical formula was used instead of Chemical Formula 1-1.

##STR00045##

Comparative Example 3

[0110] An experiment was conducted in the same manner as in Example 1, except that ET3 represented by the following chemical formula was used instead of Chemical Formula 1-1.

##STR00046##

Comparative Example 4

[0111] An experiment was conducted in the same manner as in Example 1, except that ET4 represented by the following chemical formula was used instead of Chemical Formula 1-1.

##STR00047##

Comparative Example 5

[0112] An experiment was conducted in the same manner as in Example 1, except that ET5 represented by the following chemical formula was used instead of Chemical Formula 1-1.

##STR00048##

Experimental Example

[0113] The driving voltage and luminous efficacy of the organic light-emitting devices manufactured in examples and comparative examples were measured at a current density of 10 mA/cm.sup.2. At this time, based on an initial luminance of 1,000 cd/m.sup.2, time (LT95) for luminance to reach 95% was measured, and the results are shown in Table 6 below.

TABLE-US-00006 TABLE 6 Chemical Voltage Current LT95 at 1,000 Classification Formula (V) efficiency (cd/A) cd/m.sup.2 (time) Example 1 1-1 3.81 7.81 231 Example 2 1-2 4.01 7.76 203 Example 3 1-3 3.98 7.61 207 Example 4 1-4 4.13 7.31 199 Example 5 1-5 4.11 7.33 183 Example 6 1-6 4.17 7.09 189 Example 7 1-7 3.89 7.80 229 Example 8 1-8 4.11 8.03 181 Example 9 1-9 4.23 7.98 173 Example 10 1-10 4.31 7.56 193 Example 11 1-11 3.99 7.43 191 Example 12 1-12 3.93 7.31 189 Example 13 1-13 4.03 7.18 183 Comparative ET1 4.59 6.81 101 Example 1 Comparative ET2 4.09 7.75 183 Example 2 Comparative ET3 4.21 7.63 161 Example 3 Comparative ET4 4.07 7.59 185 Example 4 Comparative ET5 4.18 7.71 153 Example 5

[0114] As shown in Table 6, it can be confirmed that, compared to Comparative Examples 1 to 5, the organic light-emitting diodes (Examples 1 to 13) including the organic compound of the present invention exhibit excellent driving voltage, luminous efficacy, and lifespan properties.