Patent Application
20220069229
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 that converts electrical energy into photoenergy, and vice versa.
An organic optoelectronic device may be classified as follows in accordance with its driving principles. One is a photoelectric device where excitons are generated by photoenergy, separated into electrons and holes, and are transferred to different electrodes to generate electrical energy, and the other is a light emitting device where a voltage or a current is supplied to an electrode to generate photoenergy from electrical energy.
Examples of the organic optoelectronic device may be an organic photoelectric device, an organic light emitting diode, an organic solar cell, and an organic photo conductor drum.
Of these, an organic light emitting diode (OLED) has recently drawn attention due to an increase in demand for flat panel displays. The organic light emitting diode converts electrical energy into light, and the performance of organic light emitting diode is greatly influenced by the organic materials disposed between electrodes.
An embodiment provides a compound for an organic optoelectronic device capable of realizing 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 the organic optoelectronic device or the composition for the 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,
Ar1 is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group,
L1 is an unsubstituted biphenylene group, and
R1 to R8 are independently hydrogen, deuterium, a cyano group, a halogen group, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.
According to another embodiment, a composition for an organic optoelectronic device includes a first compound for an organic optoelectronic device and a second compound for an organic optoelectronic device, wherein the first compound for the organic optoelectronic device is represented by the Chemical Formula 1, the second compound for the organic optoelectronic device is represented by Chemical Formula 2; or a combination of Chemical Formula 3 and Chemical Formula 4.
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,
L2 and L3 are independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,
Ra and R9 to R12 are independently hydrogen, deuterium, a cyano group, a halogen group, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group, and
m is an integer of 0 to 2;
In Chemical Formula 3 and Chemical Formula 4,
Y3 and Y4 are independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,
adjacent two *'s of Chemical Formula 3 is linked with Chemical Formula 4,
* of Chemical Formula 3 that are not linked with Chemical Formula 4 are independently C-La-Rb,
La, L4, and L5 are independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group, and
Rb and R12 to R15 are independently hydrogen, deuterium, a cyano group, a halogen group, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.
According to another embodiment, an organic optoelectronic device includes an anode and a cathode facing each other, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer includes the aforementioned 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.
An organic optoelectronic device having high efficiency and a long life-span may be realized.
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 (D), 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, 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, a cyano group, or a C1 to C5 alkylsilyl 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 trimethylsilyl group, a phenyl group, a biphenyl group, 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.
In the present specification, “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, 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 a 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 a lowest unoccupied molecular orbital (LUMO) level.
Hereinafter, a compound according to an embodiment is described.
The compound according to an embodiment is represented by Chemical Formula 1.
In Chemical Formula 1,
Ar1 is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group,
L1 is an unsubstituted biphenylene group,
R1 to R8 are independently hydrogen, deuterium, a cyano group, a halogen group, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.
The compound represented by Chemical Formula 1 may have a structure of one carbazole group directly linking with triazine without a linking group in an N-direction and another carbazole group linking with the triazine through biphenylene in an N-direction with the triazine in the core.
Since one carbazole group is directly linked with the triazine without a linking group in the N-direction, that is, at a position No. 9, the compound may have a relatively deep LUMO energy level and thus an advantage for electron injection and transportation.
In addition, since another carbazole group is linked with the triazine in the N-direction, that is, at the position No. 9, a π-bond through a C—N bond is broken, and thus an electron cloud between HOMO-LUMO may be clearly localized into a hole transport moiety and an electron transport moiety, and this localization may more effectively occur, as the carbazole group is linked with the triazine through the biphenylene, and resultantly, a life-span improvement effect may be maximized.
In other words, in a device including the compound represented by Chemical Formula 1, hole/electron injection and transportation may be promoted, and the electron cloud may be effectively localized, and thus a stable structure for both electrons and holes is realized, and accordingly, more advantageous characteristics for a life-span may be obtained.
Particularly, the compound includes the triazine as a central core and thus may secure rapid electron injection and mobility and have a charge balance with the carbazole moiety having a strong hole mobility, which may greatly contribute to the long life-span characteristics.
For example, L1 may be one selected from the linking groups of Group I.
In Group I, *a1 is a linking portion with triazine of Chemical Formula 1, and *a2 is a linking portion with carbazole of Chemical Formula 1.
Particularly, the biphenylene may be a combination of para and meta linkages, for example the L1 may be represented as L-2 or L-4.
For example, Ar1 may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group.
For example, Ar1 may be a phenyl group unsubstituted or substituted with deuterium (D), a phenyl group unsubstituted or substituted with a cyano group, a phenyl group unsubstituted or substituted with a C1 to C5 alkylsilyl group, a biphenyl group unsubstituted or substituted with deuterium (D), a biphenyl group unsubstituted or substituted with a cyano group, or a biphenyl group unsubstituted or substituted with a C1 to C5 alkylsilyl group, and
according to an embodiment, Ar1 may be a phenyl group unsubstituted or substituted with deuterium, a phenyl group unsubstituted or substituted with a cyano group, a phenyl group unsubstituted or substituted with a C1 to C5 alkylsilyl group, or an unsubstituted biphenyl group.
In the most specific embodiment, Ar1 may be an unsubstituted phenyl group, but is not limited thereto.
For example, R1 to R4 may independently be hydrogen, deuterium, a cyano group, a halogen group, a C1 to C10 alkyl group, or a C6 to C12 aryl group, and
for example, R1 to R4 may independently be hydrogen, a cyano group, a C1 to C5 alkyl group, or a phenyl group, and
in the most specific embodiment, R1 to R4 may be all hydrogen, but are not limited thereto.
For example, R5 to R8 may independently be hydrogen, deuterium, a cyano group, a halogen group, a C1 to C10 alkyl group, or a C6 to C12 aryl group, and
for example, R5 to R8 may independently be hydrogen, a cyano group, a C1 to C5 alkyl group, or a phenyl group,
In the most specific embodiment, R5 to R8 may be all hydrogen, but are not limited thereto.
For a specific example, Ar1 may be an unsubstituted phenyl group and R5 to R8 may be all hydrogen.
For example, the compound for the organic optoelectronic device represented by Chemical Formula 1 may be one of compounds of Group 1, but is not limited thereto.
A composition for an organic optoelectronic device according to another embodiment includes a first compound for an organic optoelectronic device and a second compound for an organic optoelectronic device, wherein the first compound for the organic optoelectronic device is represented by Chemical Formula 1 and the second compound for the organic optoelectronic device is represented by Chemical Formula 2; or a combination of Chemical Formula 3 and Chemical Formula 4.
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,
L2 and L3 are independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,
Ra and R9 to R12 are independently hydrogen, deuterium, a cyano group, a halogen group, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, and
m is an integer of 0 to 2;
In Chemical Formula 3 and Chemical Formula 4,
Y3 and Y4 are independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,
adjacent two *'s of Chemical Formula 3 is linked with Chemical Formula 4,
* of Chemical Formula 3 that are not linked with Chemical Formula 4 are independently C-La-Rb,
La, L4, and L5 are independently a single bond, or a substituted or unsubstituted C6 to
C20 arylene group, and
Rb and R12 to R15 are independently hydrogen, deuterium, a cyano group, a halogen group, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.
The second compound for the organic optoelectronic device may be used in a light emitting layer with the first compound for the organic optoelectronic device to improve luminous efficiency and life-span characteristics by increasing charge mobility and stability.
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,
L2 and L3 of Chemical Formula 2 may independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group,
R9 to R12 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.
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 of the present invention, Chemical Formula 2 may be represented by one of Chemical Formula 2-1 to Chemical Formula 2-15.
In Chemical Formula 2-1 to Chemical Formula 2-15, R9 to R12 may independently be hydrogen, or a substituted or unsubstituted C6 to C12 aryl group and *-L2-Y1 and *-L3-Y2 may independently be one of substituents of Group II.
In Group II, * is a linking portion.
In an embodiment, Chemical Formula 2 may be represented by Chemical Formula 2-8.
In addition, *-L1-Y1 and *-L2-Y2 of Chemical Formula 2-8 may independently be Group II, and may be one of for example B-1, B-2, and B-3.
In the most specific embodiment, *-L1-Y1 and *-L2-Y2 may be all represented by B-2 of Group II, but is not limited thereto.
For example, the second compound for the organic optoelectronic device represented by the combination of Chemical Formula 3 and Chemical Formula 4 may be represented by one of Chemical Formula 3A, Chemical Formula 3B, Chemical Formula 3C, Chemical Formula 3D, and Chemical Formula 3E.
In Chemical Formula 3A to Chemical Formula 3E, Y3 and Y4, L4 and L5, and R13 to R16 are the same as described above,
La1 to La4 are the same as L4 and L5 described above, and
Rb1 to Rb4 are the same as R13 to R16 described above.
For example, Y3 and Y4 of Chemical Formulae 3 and 4 may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, and
Rb1 to Rb4 and R13 to R16 may independently be hydrogen, deuterium, a cyano group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.
In a specific embodiment of the present invention, Y3 and Y4 of Chemical Formulae 3 and 4 may independently be selected from substituents of Group III.
In Group III, * is a linking portion with L4 and L5, respectively.
In an embodiment, Rb1 to Rb4 and R13 to R16 may independently be hydrogen, deuterium, a cyano group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.
For example, Rb1 to Rb4 and R13 to R16 may independently be hydrogen, deuterium, a cyano group, or a substituted or unsubstituted phenyl group, and
in a specific embodiment, Rb1 to Rb4 may independently be hydrogen, and R13 to R16 may independently be hydrogen or a phenyl group.
In a specific embodiment of the present invention, the second compound for the organic optoelectronic device may be represented by Chemical Formula 2-8 or Chemical Formula 3C.
Herein, Y1 to Y4 of Chemical Formula 2-8 and Chemical Formula 3C may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, L2 to L5, La1 and La2 may independently be a single bond, or a substituted or unsubstituted C6 to C20 arylene group, and Rb1, and R9 to R16 may independently be hydrogen, deuterium, a cyano group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.
In the most specific embodiment, *-L2-Y1, *-L3-Y2, *-L4-Y3, and *-L5-Y4 of Chemical Formula 2-8 and Chemical Formula 3C may be all represented by B-2 of Group III, but are not limited thereto.
For example, the second compound for the organic optoelectronic device may be one selected from the 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 for example 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, it may be, for example, a weight ratio of about 10:90 to 90:10, about 20:80 to 80:20, for example a weight ratio of about 20:80 to about 70:30, about 20:80 to about 60:40, and about 20:80 to about 50:50. For example, the weight ratio may be a weight ratio of 20:80 to 40:60 and for a specific example, the weight ratio may be a weight ratio of 30:70, 40:60, or 50:50. More specifically, it may be a weight ratio of 30:70 or 50:50.
At least one compound may be included in addition to the first compound for the organic optoelectronic device and second compound for the organic optoelectronic device.
The compound for the organic optoelectronic device or the composition for the organic optoelectronic device may be a composition that further includes a dopant.
The dopant may be for example a phosphorescent dopant, may be for example red, green, or blue phosphorescent dopant, may be for example red or green phosphorescent dopant.
The dopant is mixed in a small amount in the compound or composition for the organic optoelectronic device 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 kinds thereof may be used.
The dopant may be for example a phosphorescent dopant and examples of the phosphorescent dopant may be an organometallic 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.
L5MXa [Chemical Formula Z]
In Chemical Formula Z, M is a metal, and L5 and Xa 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 L and X may be for example a bidendate ligand.
The compound for the organic optoelectronic device or the composition for the organic optoelectronic device may be formed by a dry film deposition such as chemical vapor deposition (CVD).
Hereinafter, an organic optoelectronic device including the compound for the organic optoelectronic device or the composition for the organic optoelectronic device is described.
The organic optoelectronic device may be any element 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 made of 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 made of a metal, a metal oxide and/or a conductive polymer. The cathode 110 may be for example a metal or an alloy thereof such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum silver, tin, lead, cesium, barium, and the like; 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 compound for the organic optoelectronic device or the composition for the organic optoelectronic device.
The organic layer 105 may include a light emitting layer 130 and the light emitting layer 130 may include the compound for the organic optoelectronic device or the composition for the organic optoelectronic device.
The composition for the organic optoelectronic device further including a dopant may be for example a green light emitting composition.
The light emitting layer 130 may include the first compound for the organic optoelectronic device and the second compound for the organic optoelectronic device described above as an example of 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 the compounds of Group A.
In more detail, 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 the compounds of Group D may be included in the hole transport auxiliary layer.
In addition to the compounds described above, the hole transport auxiliary layer may also include known compounds of U.S. Pat. No. 5,061,569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A, and the like, and compounds having similar structures.
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 as one specific examples of the present invention was synthesized through the following steps.
(Preparation of First Compound for Organic Optoelectronic Device)
58.81 g (260.15 mmol) of 2-phenyl-4,6-dichlorotriazine and 30 g (179.42 mmol) of carbazole were suspended in 500 ml of THF, and 18.11 g of NaO(t-Bu) was slowly added thereto and then, stirred at room temperature for 12 hours. When a reaction was complete, a solid generated therein was filtered, washed with distilled water and acetone, and dried to obtain 40 g (a yield of 62.5%) of Intermediate A as a target compound.
(LC/MS: Theoretical value: 356.81, Measured value: 357.30)
30.29 g (105 mmol) of 3-(9H-carbazole-9-yl)phenyl boronic acid, 20 g (105 mmol) of 1-bromo-4-chlorobenzene, 0.03 eq of Pd(PPh3)4, and 2 eq of K2CO3 were suspended in THF and distilled water and then, stirred for 12 hours. When a reaction was complete, an organic layer was extracted therefrom and then, concentrated and silica-gel columned to obtain 35 g (a yield: 94%) of Intermediate B as a target compound.
35 g (100 mmol) of Intermediate B synthesized according to Synthesis Example 2, 4.85 g (10 mmol) of Pd(dppf)Cl2, 29.12 g (300 mmol) of KOAc, 30.14 g (120 mmol) of bis(pinacolato)diboron, and 6.66 g (20 mmol) of P(Cy)3 were suspended in 500 ml of DMF and then, refluxed and stirred for 12 hours. When a reaction was completed, distilled water was added to the reaction solution and then, extracted/concentrated with methylene chloride and silica gel-columned to obtain 30.8 g (a yield of 70%) of intermediate C as a target compound.
5 g (14.01 mmol) of Intermediate A, 6.86 g (15.41 mmol) of Intermediate C, 0.49 g (0.42 mmol) of Pd(PPh3)4, and 3.87 g (28.03 mmol) of K2CO3 were suspended in 100 ml of THF and 50 ml of distilled water and then, refluxed and stirred for 12 hours. When a reaction was complete, the reaction solution was cooled down to room temperature, and a solid generated therein was filtered and washed with distilled water and acetone. Subsequently, the solid was heated with 200 ml of toluene and dissolved therein and then, silica gel-filtered, a filtrate therefrom was cooled down to room temperature, and a solid generated therein was filtered, washed with acetone, and dried to obtain 6.7 g of Compound A-1 (a yield of 74%).
(LC/MS: Theoretical value: 639.75, Measured value: 640.45)
20 g (69.66 mmol) of 4-(9H-carbazole-9-yl)phenyl boronic acid, 13.34 g (69.66 mmol) of 1-bromo-3-chlorobenzene, 2.42 g (2.09 mmol) of Pd(PPh3)4, and 19.25 g (139.31 mmol) of K2CO3 were suspended in 300 ml of THF and 150 ml of distilled water and then, synthesized according to the same method as Synthesis Example 2 to obtain 19.82 g (a yield of 81%) of Intermediate D.
17 g (a yield of 68%) of Intermediate E was synthesized according to the same method d as Synthesis Example 3 except that 19.82 g (56.01 mmol) of Intermediate D synthesized according to Synthesis Example 5 was used.
6 g (a yield of 74%) of Compound A-3 was synthesized according to the same method d as Synthesis Example 4 except that 4.55 g (12.7 mmol) of Intermediate A synthesized according to Synthesis Example 1 and 5.79 g (13.01 mmol) of Intermediate E synthesized according to Synthesis Example 6 were used.
(LC/MS: Theoretical value: 639.75, Measured value: 640.44)
5.0 g (11.23 mmol) of Intermediate C synthesized according to Synthesis Example 3, 3 g (11.23 mmol) of 2-chloro-4,6-diphenyltriazine, 0.03 eq of Pd(PPh3)4, and 2 eq of K2CO3 were suspended in THF and distilled water and then, refluxed and stirred for 12 hours. When a reaction was complete, a solid generated therein was filtered and washed with distilled water and acetone. The solid was recrystallized in monochlorobenzene to obtain 4 g (a yield of 65%) of Comparative Compound R1.
(LC/MS: Theoretical value: 550.65, Measured value: 551.4)
10 g (54.23 mmol) of cyanuric chloride and 18.13 g (108.45 mmol) of carbazole were suspended in 250 ml of THF, and 7.81 g (81.35 mmol) of NaO(t-Bu) was slowly added thereto and then, stirred for 12 hours. When a reaction was complete, a solid generated therein was filtered and then, washed with distilled water and acetone/hexane to obtain 12 g (a yield of 49.6%) of Intermediate F.
6 g (13.46 mmol) of Intermediate F synthesized according to Synthesis Example 9, 5.13 g (14.13 mmol) of 4-(9H-carbazole-9-yl)biphenyl boronic acid, 0.47 g (0.40 mmol) of Pd(PPh3)4, and 3.72 g (26.91 mmol) of K2CO3 were suspended in 100 ml of THF and 50 ml of distilled water and then, stirred for 12 hours. When a reaction was complete, a solid generated therein was filtered and washed with distilled water/acetone. The solid was heated with 300 ml of dichlorobenzene and dissolved therein and then, silica-gel filtered, a filtrate therefrom was cooled down to room temperature, and a solid generated therein was filtered and dried to obtain 3.9 g (a yield of 40%) of Comparative Compound R2.
(LC/MS: Theoretical value: 728.84, Measured value: 729.6)
36.9 g (200 mmol) of cyanuric chloride and 33.4 g (200 mmol) of carbazole were suspended in 300 ml of THF, and 19.22 g (200 mmol) of NaO(t-Bu) was slowly added thereto at 0° C. When a reaction was complete, a solid generated therein was filtered and then, washed with distilled water/acetone/hexane to obtain 10 g (a yield of 16%) of Intermediate Gas a target compound.
4.9 g (15.55 mmol) of Intermediate G synthesized according to Synthesis Example 11, 6.69 g (15.55 mmol) of Intermediate I (refer to Synthesis Example 3 of Korea Patent Laid-Open Publication No. 10-2014-0135524), 0.89 g (0.78 mmol) of Pd(PPh3)4, and 5.37 g (38.87 mmol) of K2CO3 were suspended in 50 ml of THF/50 ml of toluene/50 ml of distilled water and then, stirred for 12 hours. When a reaction was complete, a solid generated therein was filtered, washed with distilled water/acetone, and dried to obtain 5 g (a yield of 56%) of Intermediate H as a target compound.
2.4 g (4.11 mmol) of Intermediate H synthesized according to Synthesis Example 12, 1.67 g (4.53 mmol) of 9-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-9H-carbazole, 0.14 g (0.12 mmol) of Pd(PPh3)4, and 1.14 g (8.23 mmol) of K2CO3 were suspended in 50 ml of THF and 50 ml of DIW and then, refluxed and stirred for 12 hours. When a reaction was complete, a solid generated therein was filtered and then, washed with distilled water and acetone. The solid was heated with 100 ml of dichlorobenzene and dissolved therein and then, silica-gel filtered, and a filtrate therefrom was cooled down to room temperature. A solid generated in the filtrate was filtered and washed with acetone to obtain 2.94 g (a yield of 89.5%) of Comparative Compound R3 as a target compound.
(LC/MS: Theoretical value: 789.92, Measured value: 790.40)
(Preparation of Second Compound for Organic Optoelectronic Device)
Compound B-99 was synthesized in the same manner as known in US2017-0317293A1.
8 g (31.2 mmol) of 5,8-Dihydroindolo[2,3-c]carbazole (CAS No.: 200339-30-6), 20.5 g (73.32 mmol) of 4-iodobiphenyl, 1.19 g (6.24 mmol) of CuI, 1.12 g (6.24 mmol) of 1,10-phenanthoroline, and 12.9 g (93.6 mmol) of K2CO3 were put in a round-bottomed flask, and 50 ml of DMF was added thereto and then, refluxed and stirred under a nitrogen atmosphere for 24 hours. When a reaction was complete, distilled water was added thereto to extract crystals, which were filtered. The solid was dissolved in 250 ml of xylene and then, silica gel filtered and extracted as a white solid to obtain 16.2 g (a yield of 93%) of Compound C-4.
LC/MS calculated for: C42H28N2 Exact Mass: 560.2252 found for: 561.23
(Manufacture of Organic Light Emitting Diode)
A glass substrate coated with ITO (indium tin oxide) as a 1500 Å-thick thin film was washed with distilled water. After washing with the distilled water, the glass substrate was ultrasonic wave-washed with a solvent such as isopropyl alcohol, acetone, methanol, and the like 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 A-1 of Synthesis Example 4 as a host and 7 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[A-1:PhGD (7 wt %)] (400 Å)/Compound D:Liq (300 Å)/Liq (15 Å)/Al (1200 Å).
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
Each diode of Example 2 to Example 9 and Comparative Example 1 to Comparative Example 5 was manufactured according to the same method as Example 1 except that the hosts and ratios thereof were changed as shown in Tables 1 to 5.
Evaluation: Life-span Increasing Synergy Effect
Life-span characteristics of the organic light emitting diodes according to Example 1 to Example 9 and Comparative Example 1 to Comparative Example 5 were evaluated. Specific measurement methods are as follows, and the results are shown in Tables 1 to 5.
(1) Measurement of Life-span
T90 life-spans of the organic light emitting diodes according to Examples 1 to 9 and Comparative Examples 1 to 5 were measured as a time when their luminance decreased to 90% relative to the initial luminance (cd/m2) after emitting light with 24000 cd/m2 as the initial luminance (cd/m2) and measuring their luminance decrease depending on a time with a Polanonix life-span measurement system.
(2) Calculation of T90 life-span ratio (%)
Relative comparison values of T90 (h) between a single host or a mixed host examples (first compound as the first host) with the same second host and a mixed host comparative example (comparative compound as the first host).
T90 life-span ratio (%)={[T90 (h) of Example (first compound used alone or as a mixed host)/[T90 (h) of Comparative Example (comparative compound used alone or as a mixed host)]}×100
Referring to Tables 1 to 5, the compounds according to the present invention exhibited significantly improved life-spans compared with the comparative compounds.
Although preferred examples of the present invention have been described in detail hereinabove, the right scope of the present invention is not limited thereto, and it should be clearly understood that many variations and modifications of those skilled in the art using the basic concept of the present invention, which is defined in the following claims, will also belong to the right scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2018-0167505 | Dec 2018 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2019/016164 | 11/22/2019 | WO | 00 |
