Patent Application
20210273179
A compound for an organic optoelectronic device, a composition for an organic optoelectronic device, an organic optoelectronic device, and a display device are disclosed.
An organic optoelectronic device (organic optoelectronic diode) is a device capable of converting electrical energy and optical energy to each other.
Organic optoelectronic device may be largely divided into two types according to a principle of operation. One is a photoelectric device that generates electrical energy by separating excitons formed by light energy into electrons and holes, and transferring the electrons and holes to different electrodes, respectively and the other is light emitting device that generates light energy from electrical energy by supplying voltage or current to the electrodes.
Examples of the organic optoelectronic device include an organic photoelectric device, an organic light emitting diode, an organic solar cell, and an organic photo conductor drum.
Among them, organic light emitting diodes (OLEDs) are attracting much attention in recent years due to increasing demands for flat panel display devices. The organic light emitting diode is a device that converts electrical energy into light, and the performance of the organic light emitting diode is greatly influenced by an organic material between electrodes.
An embodiment provides a compound for an organic optoelectronic device capable of implementing a high efficiency and long life-span organic optoelectronic device.
Another embodiment provides a composition for an organic optoelectronic device including the compound for an organic optoelectronic device.
Another embodiment provides an organic optoelectronic device including the compound for an organic optoelectronic device or the composition for an organic optoelectronic device.
Another embodiment provides a display device including the organic optoelectronic device.
According to an embodiment, a compound for an organic optoelectronic device represented by Chemical Formula 1 is provided.
In Chemical Formula 1,
R1 to R3 are independently hydrogen, deuterium, a cyano group, or a substituted or unsubstituted C1 to C10 alkyl group,
n is one of integers of 0 to 2, and
Ar1 and Ar2 are independently a substituted or unsubstituted C6 to C30 aryl group,
when n is 0, the case where Ar1 and Ar2 are unsubstituted phenyl groups at the same time is excluded.
According to another embodiment, a composition for an organic optoelectronic device includes the aforementioned compound for an organic optoelectronic device (hereinafter, “a first compound for an organic optoelectronic device), and a second compound for an organic optoelectronic device represented by Chemical Formula 2.
In Chemical Formula 2,
Y1 and Y2 are independently a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,
L1 and L2 are independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,
Ra and R4 to R7 are independently hydrogen, deuterium, a cyano group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group, and
m is an integer of 0 to 2.
According to another embodiment, an organic optoelectronic device includes an anode and a cathode facing each other, and at least one organic layer between the anode and the cathode, and the organic layer includes the compound for an organic optoelectronic device or the composition for an organic optoelectronic device.
According to another embodiment, a display device including the organic optoelectronic device is provided.
High efficiency and long life-span organic optoelectronic devices may be implemented.
Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the present invention is not limited thereto and the present invention is defined by the scope of claims.
In the present specification, when a definition is not otherwise provided, “substituted” refers to replacement of at least one hydrogen of a substituent or a compound by deuterium, a halogen, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, a cyano group, or a combination thereof.
In one example of the present invention, “substituted” refers to replacement of at least one hydrogen of a substituent or a compound by deuterium, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a cyano group. In addition, in specific examples of the present invention, “substituted” refers to replacement of at least one hydrogen of a substituent or a compound by deuterium, a C1 to C20 alkyl group, a C6 to C30 aryl group, or a cyano group. In addition, in specific examples of the present invention, “substituted” refers to replacement of at least one hydrogen of a substituent or a compound by deuterium, a C1 to C5 alkyl group, a C6 to C18 aryl group, or a cyano group. In addition, in specific examples of the present invention, “substituted” refers to replacement of at least one hydrogen of a substituent or a compound by deuterium, a cyano group, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group.
In the present specification, when a definition is not otherwise provided, “hetero” refers to one including one to three heteroatoms selected from N, O, S, P, and Si, and remaining carbons in one functional group.
In the present specification, “aryl group” refers to a group including at least one hydrocarbon aromatic moiety, and may include a group in which all elements of the hydrocarbon aromatic moiety have p-orbitals which form conjugation, for example a phenyl group, a naphthyl group, and the like, a group in which two or more hydrocarbon aromatic moieties may be linked by a sigma bond, for example a biphenyl group, a terphenyl group, a quarterphenyl group, and the like, and a group in which two or more hydrocarbon aromatic moieties are fused directly or indirectly to provide a non-aromatic fused ring, for example, a fluorenyl group, and the like.
The aryl group may include a monocyclic, polycyclic or fused ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional group.
“Heterocyclic group” is a generic concept of a heteroaryl group, and may include at least one heteroatom selected from N, O, S, P, and Si instead of carbon (C) in a cyclic compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof. When the heterocyclic group is a fused ring, the entire ring or each ring of the heterocyclic group may include one or more heteroatoms.
For example, “heteroaryl group” refers to an aryl group including at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryl groups are linked by a sigma bond directly, or when the heteroaryl group includes two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may include one to three heteroatoms.
More specifically, the substituted or unsubstituted C6 to C30 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof, but is not limited thereto.
More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzthiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, but is not limited thereto.
In the present specification, hole characteristics refer to an ability to donate an electron to form a hole when an electric field is applied and that a hole formed in the anode may be easily injected into the light emitting layer and transported in the light emitting layer due to conductive characteristics according to the highest occupied molecular orbital (HOMO) level.
In addition, electron characteristics refer to an ability to accept an electron when an electric field is applied and that electron formed in the cathode may be easily injected into the light emitting layer and transported in the light emitting layer due to conductive characteristics according to the lowest unoccupied molecular orbital (LUMO) level.
Hereinafter, a compound for an organic optoelectronic device according to an embodiment is described.
The compound for an organic optoelectronic device according to an embodiment is represented by Chemical Formula 1.
In Chemical Formula 1,
R1 to R3 are independently hydrogen, deuterium, a cyano group, or a substituted or unsubstituted C1 to C10 alkyl group,
n is one of integers of 0 to 2, and
Ar1 and Ar2 are independently a substituted or unsubstituted C6 to C30 aryl group, provided that, when n is 0, the case where Ar1 and Ar2 are unsubstituted phenyl groups at the same time is excluded.
In the compound for an organic optoelectronic device represented by Chemical Formula 1, a 9-carbazole group is directly or indirectly linked to triazine through p-phenylene, the 9-carbazole group includes a phenyl substituent at position 3, and the triazine group has a structure including an aryl substituent.
As the 9-carbazole group is linked to the triazine through p-phenylene, the LUMO electron cloud expands, thereby lowering a LUMO energy level, further enhancing electron injection and electron transport capabilities, thereby lowering a driving voltage of a device including the compound.
In addition, as the 9-carbazole group includes a phenyl substituent at the position 3 and the triazine group includes an aryl substituent, hole injection and hole transport capabilities are also enhanced to achieve an appropriate charge balance in the light emitting layer, resulting in improvement of efficiency and life-span of the device including the compound.
For example, n may be an integer of 0 or 1, and
for example Chemical Formula 1 may be represented by Chemical Formula 1A or Chemical Formula 1B.
In Chemical Formula 1A and Chemical Formula 1B, R1 to R3, Ar1, and Ar2 are the same as described above.
For example, one of Ar1 and Ar2 of Chemical Formula 1A may be an unsubstituted phenyl group, and the other may be a substituted phenyl group, a substituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted fluorenyl group.
For example, Ar1 and Ar2 of Chemical Formula 1B may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted fluorenyl group.
For example, Ar1 and Ar2 may independently be selected from the groups of Group I.
In Group I, * is a linking point
In an example embodiment, Ar1 and Ar2 may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group, but are not limited thereto.
In a specific embodiment, when n=0, one of Ar1 and Ar2 may be an unsubstituted phenyl group, and the other may be a substituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group.
In addition, when n=1, Ar1 and Ar2 may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group.
For example, the aforementioned compound for an organic optoelectronic device may be one selected from compounds of Group 1, but is not limited thereto.
The composition for an organic optoelectronic device according to another embodiment includes the compound for an organic optoelectronic device (hereinafter referred to as “a first compound for an organic optoelectronic device”) and a second compound for an organic optoelectronic device represented by Chemical Formula 2.
In Chemical Formula 2,
Y1 and Y2 are independently a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,
L1 and L2 are independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,
R1 and R4 to R7 are independently hydrogen, deuterium, a cyano group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group, and m is an integer of 0 to 2.
The second compound for an organic optoelectronic device is used in the light emitting layer together with the compound for an organic optoelectronic device to increase charge mobility and stability, thereby improving luminous efficiency and life-span characteristics.
For example, Y1 and Y2 of Chemical Formula 2 may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted pyridinyl group.
In an embodiment, Y1 and Y2 of Chemical Formula 2 may independently be a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group, but are not limited thereto.
For example, L1 and L2 of Chemical Formula 2 may independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, R4 to R7 of Chemical Formula 2 may independently be hydrogen, deuterium, or a substituted or unsubstituted C6 to C12 aryl group, and m may be 0 or 1.
In an embodiment, L1 and L2 of Chemical Formula 2 may independently be a single bond, a substituted or unsubstituted phenylene group, R4 to R7 of Chemical Formula 2 may independently be hydrogen, and m may be 0, but is not limited thereto.
For example, “substituted” of Chemical Formula 2 refers to replacement of at least one hydrogen by deuterium, a C1 to C4 alkyl group, a C6 to C18 aryl group, or a C2 to C30 heteroaryl group.
In a specific embodiment, Chemical Formula 2 may be represented by Chemical Formula 2A.
In Chemical Formula 2A, Y1, Y2, L1, L2, Ra, and R4 to R7 are the same as described above.
For example, Chemical Formula 2 is one of the structures of Group II and *-L1-Y1 and *-L2-Y2 may be one of the substituents of Group III.
In Groups II and III, * is a linking point.
In an embodiment, Chemical Formula 2 is represented by Chemical Formula C-8 or Chemical Formula C-17 of Group II, and *-L1-Y1 and *-L2-Y2 may be selected from Group III.
Specifically, Y1 and Y2 in Chemical Formula 2 may independently be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group, and for example, *-L1-Y1 and *-L2-Y2 may be selected from B-1, B-2, and B-3 of Group III, but are not limited thereto.
In a specific embodiment of the present invention, the first compound for an organic optoelectronic device may be represented by Chemical Formula 1A or 1B, and the second compound for an organic optoelectronic device may be represented by Chemical Formula 2A.
Herein, R1 to R3 in Chemical Formula 1A and Chemical Formula 1B may be each hydrogen, and Ar1 and Ar2 in Chemical Formula 1A may be independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group, provided that Ar1 and Ar2 are not simultaneously unsubstituted phenyl groups, and
Ar1 and Ar2 in Chemical Formula 1B may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group.
In addition, Y1 and Y2 in Chemical Formula 2A may independently be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group, and L1 and L2 may independently be a single bond, or a substituted or unsubstituted C6 to C12 arylene group, and R4 to R7 may each be hydrogen.
For example, the second compound for an organic optoelectronic device may be one selected from compounds of Group 2, but is not limited thereto.
The first compound for the organic optoelectronic device and the second compound for the organic optoelectronic device may be included in a weight ratio of 1:99 to 99:1. Within the range, a desirable weight ratio may be adjusted using an electron transport capability of the first compound for the organic optoelectronic device and a hole transport capability of the second compound for the organic optoelectronic device to realize bipolar characteristics and thus to improve efficiency and life-span. Within the range, they may be for example included in a weight ratio of about 10:90 to about 90:10, about 20:80 to about 80:20, for example about 20:80 to about 70:30, about 20:80 to about 60:40, and about 20:80 to about 50:50. For example, they may be included in a weight ratio of 20:80 to 40:60, for example, a weight ratio of 30:70, 40:60, or 50:50, for example a weight ratio of 30:70.
In addition to the aforementioned first compound for an organic optoelectronic device and second compound for an organic optoelectronic device, at least one compound may be further included.
The aforementioned compound for an organic optoelectronic device or composition for an organic optoelectronic device may be a composition further including a dopant.
The dopant may be, for example, a phosphorescent dopant, such as a red, green, or blue phosphorescent dopant, and may be, for example, a green or red phosphorescent dopant.
The dopant is a material mixed with the compound for an organic optoelectronic device or composition for an organic optoelectronic device in a small amount to cause light emission and may be generally a material such as a metal complex that emits light by multiple excitation into a triplet or more. The dopant may be, for example an inorganic, organic, or organic-inorganic compound, and one or more types thereof may be used.
Examples of the dopant may be a phosphorescent dopant and examples of the phosphorescent dopant may be an organic metal compound including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. The phosphorescent dopant may be, for example a compound represented by Chemical Formula Z, but is not limited thereto.
L3MX [Chemical Formula Z]
In Chemical Formula Z, M is a metal, and L3 and X are the same or different, and are a ligand to form a complex compound with M.
The M may be for example Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof, and the L3 and X may be, for example a bidendate ligand.
The aforementioned compound for an organic optoelectronic device or composition for an organic optoelectronic device may be formed by a dry film formation method such as chemical vapor deposition (CVD).
Hereinafter, an organic optoelectronic device including the aforementioned compound for an organic optoelectronic device or composition for an organic optoelectronic device is described.
The organic optoelectronic device may be any device to convert electrical energy into photoenergy and vice versa without particular limitation, and may be, for example an organic photoelectric device, an organic light emitting diode, an organic solar cell, and an organic photo-conductor drum.
Herein, an organic light emitting diode as one example of an organic optoelectronic device is described referring to drawings.
Referring to
The anode 120 may be made of a conductor having a large work function to help hole injection, and may be for example a metal, a metal oxide and/or a conductive polymer. The anode 120 may be, for example a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, and the like or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and the like; a combination of a metal and an oxide such as ZnO and Al or SnO2 and Sb; a conductive polymer such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (PEDOT), polypyrrole, and polyaniline, but is not limited thereto.
The cathode 110 may be made of a conductor having a small work function to help electron injection, and may be for example a metal, a metal oxide and/or a conductive polymer. The cathode 110 may be for example a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum silver, tin, lead, cesium, barium, and the like, or an alloy thereof; a multi-layer structure material such as LiF/Al, LiO2/Al, LiF/Ca, LiF/Al, and BaF2/Ca, but is not limited thereto.
The organic layer 105 may include the aforementioned compound for an organic optoelectronic device or composition for an organic optoelectronic device.
The organic layer 105 may include a light emitting layer 130 that may include the aforementioned compound for an organic optoelectronic device or composition for an organic optoelectronic device.
The composition for an organic optoelectronic device further including a dopant may be, for example, a green or red light emitting composition.
The light emitting layer 130 may include, for example, the aforementioned first compound for an organic optoelectronic device and second compound for an organic optoelectronic device as a phosphorescent host.
The organic layer may further include an auxiliary layer in addition to the light emitting layer.
The auxiliary layer may be, for example, a hole auxiliary layer 140.
Referring to
The hole auxiliary layer 140 may include for example at least one of compounds of Group D.
Specifically, the hole auxiliary layer 140 may include a hole transport layer between the anode 120 and the light emitting layer 130 and a hole transport auxiliary layer between the light emitting layer 130 and the hole transport layer, and at least one of compounds of Group D may be included in the hole transport auxiliary layer.
In the hole transport auxiliary layer, known compounds disclosed in U.S. Pat. No. 5,061,569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A, and the like and compounds similar thereto may be used in addition to the compound.
In an embodiment, in
The organic light emitting diodes 100 and 200 may be manufactured by forming an anode or a cathode on a substrate, forming an organic layer using a dry film formation method such as a vacuum deposition method (evaporation), sputtering, plasma plating, and ion plating, and forming a cathode or an anode thereon.
The organic light emitting diode may be applied to an organic light emitting display device.
Hereinafter, the embodiments are illustrated in more detail with reference to examples. However, these examples are exemplary, and the present scope is not limited thereto.
Hereinafter, starting materials and reactants used in examples and synthesis examples were purchased from Sigma-Aldrich Co. Ltd., TCI Inc., Tokyo chemical industry or P&H tech as far as there in no particular comment or were synthesized by known methods.
(Preparation of Compound for Organic Optoelectronic device)
The compound for an organic optoelectronic device as one specific examples of the present invention was synthesized through the following steps.
(Preparation of First Compound for Organic Optoelectronic device)
1) Synthesis of Intermediate A-2-1
30 g (87.2 mmol) of 2-chloro-4-phenyl-6-(4-biphenyl)-1,3,5-triazine was put along with 100 mL of tetrahydrofuran, 100 mL of toluene, and 100 mL of distilled water in a 500 mL round-bottomed flask, and 0.9 equivalent of (4-chlorophenyl)boronic acid, 0.03 equivalent of tetrakistriphenylphosphine palladium, and 2 equivalents of potassium carbonate were added thereto and then, heated and refluxed under a nitrogen atmosphere. After 6 hours, the reaction solution was cooled down, an aqueous layer was removed therefrom, and then, an organic layer therefrom was dried under a reduced pressure. The obtained solid was washed with water and hexane and recrystallized with 200 mL of toluene to 24 g (yield: 65%) of Intermediate A-2-1.
2) Synthesis of Intermediate A-2-2
3-bromocarbazole (35 g, 142 mmol) was dissolved in tetrahydrofuran 0.5 L in a 1 L round-bottomed flask, and phenylboronic acid (17.3 g, 142 mmol) and tetrakistriphenylphosphine palladium (8.2 g, 7.1 mmol) were added thereto and then, stirred. Subsequently, potassium carbonate (49.1 g, 356 mmol) saturated in water was added thereto and then, heated and refluxed at 80° C. for 12 hours. When a reaction was complete, water was added to the reaction solution and then, extracted with dichloromethane, treated with anhydrous magnesium sulfite to remove moisture, and then, filtered and concentrated under a reduced pressure. This obtained residue was separated and purified through column chromatography to obtain 22.0 g (yield: 64%) of Intermediate A-2-2.
3) Synthesis of Compound A-2
Intermediate A-2-1 (24 g, 57.2 mmol), 1 equivalent of Intermediate A-2-2, 1.5 equivalent of sodium t-butoxide (NaOtBu), 0.04 equivalent of Pd2(dba)3, and 1.5 equivalent of tri t-butylphosphine (P(tBu)3) (50% in toluene) were added to xylene (300 mL) and then, heated and refluxed under a nitrogen flow for 12 hours. After removing the xylene, a solid crystallized by adding 200 mL of methanol to the obtained mixture was filtered, dissolved in monochlorobenzene (MCB), and filtered through silica gel/Celite, and the organic solvent in an appropriate amount was concentrated to obtain 22.2 g (yield: 62%) of Compound A-2.
1) Synthesis of Intermediate A-25-1
21.4 g (yield: 66%) of Intermediate A-25-1 was obtained in the same manner as in the step 1) of Synthesis Example 1 by using 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (30 g, 77.3 mmol).
2) Synthesis of Compound A-25
19.8 g (yield: 62%) of Compound A-25 was obtained in the same manner as in the step 3) of Synthesis Example 1 by using Intermediate A-25-1 (21.4 g, 51 mmol).
Compound A-3 was synthesized in the same manner as in step 3) of Synthesis Example 1 by using intermediate A-3-1 (CAS no. 1910061-39-0).
Compound A-15 was synthesized in the same manner as in the step 3) of Synthesis Example 1 by using Intermediate A-15-1 (CAS no. 2305965-85-7).
Compound R-1 was synthesized in the same manner as in Synthesis Example 1 using 2-chloro-4,6-diphenyl-1,3,5-triazine.
Compound R-2 was synthesized in the same manner as in Synthesis Example 1 by using (3-chlorophenyl) boronic acid instead of the (4-chlorophenyl) boronic acid.
Compound R-3 was synthesized in the same manner as in Synthesis Example 1 by using (4-biphenyl) boronic acid instead of the phenylboronic acid in the step 2) of Synthesis Example 1.
1) Synthesis of Intermediate R-4-1
1 equivalent of intermediate A-2-2, 1.2 equivalents of 4-chloro-1-bromobenzene, 2 equivalents of sodium t-butoxide, and 0.05 equivalent of Pd2(dba)3 were suspended at 0.2 M in xylene, and 2 equivalents of tri-tertiarybutylphosphine was added thereto and then, refluxed and stirred for 18 hours. Subsequently, methanol was added with 1.5 times of the solvent thereto and then, stirred, and a solid obtained therefrom was filtered and washed with 300 mL of water. The solid was recrystallized with monochlorobenzene to obtain Intermediate R-4-1 (yield: 85%).
2) Synthesis of Intermediate R-4-2
16.42 g (46.4 mmol) of Intermediate R-4-1 was added to 200 mL of toluene in a 500 mL round-bottomed flask, and 0.05 equivalent of dichlorodiphenylphosphinoferrocene palladium, 1.2 equivalents of bispinacolto diboron, and 2 equivalents of potassium acetate were added thereto under a nitrogen and then, heated and refluxed for 18 hours. The reaction solution was cooled down and then, dripped into 1 L of water to capture a solid. The solid was dissolved in boiling toluene to treat activated carbon and filtered through silica gel, and a filtrate therefrom was concentrated. The concentrated solid was stirred with a small amount of hexane and filtered to obtain Intermediate R-4-2 (yield: 85%).
3) Synthesis of Intermediate R-4-3
22.6 g (100 mmol) of 2,4-dichloro-6-phenyltriazine was added to 100 mL of tetrahydrofuran, 100 mL of toluene, and 100 mL of distilled water in a 500 mL round-bottomed flask, and 0.9 equivalent of dibenzofuran-3-boronic acid, 0.03 equivalent of tetrakistriphenylphosphine palladium, and 2 equivalents of potassium carbonate were added thereto and then, heated and refluxed under a nitrogen. After 6 hours, the reaction solution was cooled down, an aqueous layer was removed therefrom, and then, an organic layer therein was dried under a reduced pressure. The obtained solid was washed with water and hexane and recrystallized in 200 mL of toluene to obtain 26.0 g (yield: 60%) of Intermediate R-4-3.
4) Synthesis of Compound R-4
1 equivalent of Intermediate R-4-2 was added to 80 mL of tetrahydrofuran and 40 mL of distilled water in a 500 mL round-bottomed flask, 1 equivalent of Intermediate R-4-3, 0.03 equivalent of tetrakistriphenylphosphine palladium, and 2 equivalents of potassium carbonate were added thereto and then, heated and refluxed under a nitrogen atmosphere. After 18 hours, the reaction solution was cooled down, and a solid precipitated therein was filtered and washed with 500 mL of water. The solid was recrystallized with 500 mL of monochlorobenzene to obtain (yield: 70%) of Compound R-4.
Compound R-5 (yield: 70%) was obtained by the same synthesis method as in step 4) of Comparative Synthesis Example 4, using 9-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl)-carbazole (cas: 785051-54-9) and Intermediate R-1-1.
1) Synthesis of Compound R-6-1
Intermediate R-6-1 (yield: 75%) was obtained by the same synthesis method as in the step 2) of Synthesis Example 1 by using 3,6-dibromo-9H-carbazole.
2) Synthesis of Comparative Compound R-6
Compound R-6 (yield: 70%) was obtained by the same synthesis method as in the step 3) of Synthesis Example 1 by using Intermediate R-6-1.
Compound B-99 was synthesized in the same manner as known in US2017-0317293A1.
The glass substrate coated with ITO (Indium tin oxide) at a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After washing with the distilled water, the glass substrate was washed with a solvent such as isopropyl alcohol, acetone, methanol, and the like ultrasonically and dried and then, moved to a plasma cleaner, cleaned by using oxygen plasma for 10 minutes, and moved to a vacuum depositor. This obtained ITO transparent electrode was used as an anode, Compound A was vacuum-deposited on the ITO substrate to form a 700 Å-thick hole injection layer, and Compound B was deposited to be 50 Å-thick on the injection layer, and then Compound C was deposited to be 1020 Å-thick to form a hole transport layer. On the hole transport layer, 400 Å-thick light emitting layer was formed by using Compound A-2 obtained in Synthesis Example 1 as a host and doping 15 wt % of PhGD as a dopant by a vacuum-deposition. Subsequently, on the light emitting layer, a 300 Å-thick electron transport layer was formed by simultaneously vacuum-depositing Compound D and Liq in a ratio of 1:1, and on the electron transport layer, Liq and Al were sequentially vacuum-deposited to be 15 Å-thick and 1200 Å-thick, manufacturing an organic light emitting diode.
The organic light emitting diode had a five-layered organic thin layer, and specifically the following structure.
ITO/Compound A (700 Å)/Compound B (50 Å)/Compound C (1020 Å)/EML
Compound A: N4,N4′-diphenyl-N4,N4′-bis(9-phenyl-9H-carbazol-3-yl)biphenyl-4,4′-diamine
Compound B: 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT-CN),
Compound C: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine
Compound D: 8-(4-(4,6-di(naphthalen-2-yl)-1,3,5-triazin-2-yl)phenyl)quinoline
As described in Tables 1 to 4, each diode of Examples 2 to 5, Comparative Examples 1 to 5, and reference example was manufactured according to the same method as Example 1 except that a host, a ratio of the host, and a dopant ratio were changed.
Driving voltage, luminous efficiency, and life-span characteristics of the organic light emitting diodes of Examples 1 to 5, Comparative Examples 1 to 5, and reference example were evaluated. Specific measurement methods are as follows, and the results are shown in Tables 1 to 4.
(1) Measurement of Current Density Change Depending on Voltage Change
The obtained organic light emitting diodes were measured regarding a current value flowing in the unit device, while increasing the voltage from 0 V to 10 V using a current-voltage meter (Keithley 2400), and the measured current value was divided by area to provide the results.
(2) Measurement of Luminance Change Depending on Voltage Change
Luminance was measured by using a luminance meter (Minolta Cs-1000A), while the voltage of the organic light emitting diodes was increased from 0 V to 10 V.
(3) Measurement of Luminous Efficiency
Current efficiency (cd/A) at the same current density (10 mA/cm2) were calculated by using the luminance and current density from the items (1) and (2).
(4) Measurement of Life-Span
The organic light emitting diodes of Examples 1 to 5, Comparative Examples 1 to 5, and reference example were measured with respect to T90 life-spans by emitting light at initial luminance (cd/m2) of 24000 cd/m2 and measuring luminance decreases over time to obtain when the luminance decreased down to 90% of the initial luminance as T90 life-span.
(5) Measurement of Driving Voltage
A driving voltage of each diode was measured by using a current-voltage meter (Keithley 2400) at 15 mA/cm2.
(6) Calculation of T90 Life-Span Ratio (%)
Relative T90(h) comparison values of single hosts or mixed hosts of the examples applying the same second host (the first compound for an organic optoelectronic device as a first host) with a mixed host of the comparative example (the compound of comparative example or reference example as a first host) were calculated.
T90 life-span ratio (%)={[T90(h) of Example (applying the first compound for an organic optoelectronic device as a single host or a mixed host)/[T90(h) of Comparative Example (applying the compound of Comparative Example or Reference Example as a single host or a mixed host)]}×100
(7) Calculation of Driving Voltage Ratio (%)
Relative comparison values of the single hosts or of the mixed hosts obtained by applying the same second host of the examples (the first compound for an organic optoelectronic device as a first host) with the mixed host of the comparative example (the compound of comparative example or reference example as a first host) were calculated.
Driving voltage ratio (%)={[driving voltage (V) of Example (applying the first compound for an organic optoelectronic device as a single host or a mixed host)]/[driving voltage (V) of Comparative Example (the compound of Comparative Example or Reference Example as a single host or a mixed host]}×100
(8) Calculation of Luminous Efficiency Ratio (%)
Relative comparison values of the single hosts or the mixed hosts obtained by applying the same second host of the examples (applying the first compound for an organic optoelectronic device as a first host) with the mixed host of the comparative example (the compound of comparative example or reference example as a first host) were calculated.
Luminous efficiency ratio (%)={[luminous efficiency (cd/A) of Example (applying the first compound for an organic optoelectronic device as a single host or a mixed host))]/[luminous efficiency (cd/A) of Comparative Example (the compound of Comparative Example or Reference Example as a single host or a mixed host)]}×100
Referring to Tables 1 to 4, the compounds for an organic optoelectronic device according to the present invention exhibited a reduced driving voltage and improved life-span and luminous efficiency, compared with the compounds for an organic optoelectronic device according to the comparative examples.
While this invention has been described in connection with what is presently considered to be practical embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2018-0066252 | Jun 2018 | KR | national |
| 10-2019-0066084 | Jun 2019 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2019/006821 | 6/5/2019 | WO | 00 |
