Patent Application
20240251672
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 devices 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 photoconductor 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 composition for an organic optoelectronic device that can implement a low-driving, high-efficiency, and long-life organic optoelectronic device.
Another embodiment provides an organic optoelectronic device including the composition for an organic optoelectronic device.
Another embodiment provides a display device including the organic optoelectronic device.
According to an embodiment, provided is a composition for an organic optoelectronic device including a first compound represented by Chemical Formula 1, and a second compound represented by a combination of Chemical Formula 2 and Chemical Formula 3.
In Chemical Formula 1,
According to another embodiment, provided is an organic optoelectronic device including an anode and a cathode facing each other, and at least one organic layer between the anode and the cathode, wherein the organic layer includes 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 with low driving, high efficiency, and long life-span can 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.
As used herein, 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, the “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 specific example of the present invention, the “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 specific example of the present invention, the “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 specific example of the present invention, the “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, “unsubstituted” refers to non-replacement of a hydrogen atom by another substituent and remaining of the hydrogen atom.
In the present specification, “deuterium substituted (-D)” may include “tritium substituted (-T)”.
As used herein, 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.
As used herein, “an aryl group” refers to a group including at least one hydrocarbon aromatic moiety, and all elements of the hydrocarbon aromatic moiety have p-orbitals which form conjugation, for example a phenyl group, a naphthyl group, and the like, two or more hydrocarbon aromatic moieties may be linked by a sigma bond and may be, for example a biphenyl group, a terphenyl group, a quaterphenyl group, and the like, and two or more hydrocarbon aromatic moieties are fused directly or indirectly to provide a non-aromatic fused ring, for example a fluorenyl group.
The aryl group may include a monocyclic, polycyclic, or fused ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional group.
As used herein, “a 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, “a heteroaryl group” may refer 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, a substituted or unsubstituted furanyl 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 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, a substituted or unsubstituted benzofuranpyrimidinyl group, a substituted or unsubstituted benzothiophenepyrimidinyl group, or a combination thereof, but is not limited thereto.
As used herein, 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 composition for an organic optoelectronic device according to an embodiment is described.
The composition for an organic optoelectronic device according to an embodiment includes a first compound represented by Chemical Formula 1 and a second compound represented by a combination of Chemical Formula 2 and Chemical Formula 3.
The first compound may be represented by Chemical Formula 1.
In Chemical Formula 1,
The first compound represented by Chemical Formula 1 has biscarbazole as the basic skeleton, and has a structure in which the benzene moiety of the carbazole is substituted with at least one deuterium, and at least one of the 9th (N-direction) substituents Ar1 and Ar2 of carbazole is substituted with at least one deuterium.
As the benzene moiety of carbazole and the 9th (N-direction) substituent of carbazole are simultaneously substituted with deuterium, a zero point energy and vibration energy of the compound may be further lowered. As a result, the energy of the ground state is further lowered, and the interaction between molecules is weakened, making it possible to make the thin film formed from this in an amorphous state, which improves heat resistance and life-span. In other words, if this is applied, it is possible to implement an organic light emitting diode with low driving, high efficiency, and especially long life-span.
Chemical Formula 1 may be expressed as, for example, any one of Chemical Formulas 1-1 to 1-10, depending on the linking position of carbazole.
When R1 is greater than or equal to 2, each R1 may be the same as or different from each other.
When R2 is greater than or equal to 2, each R2 may be the same as or different from each other.
When R3 is greater than or equal to 2, each R3 may be the same as or different from each other.
When R4 is greater than or equal to 2, each R4 may be the same as or different from each other.
When Ar6 is greater than or equal to 2, each Ar6 may be the same as or different from each other.
When Ar7 is greater than or equal to 2, each Ar7 may be the same as or different from each other.
When Ar8 is greater than or equal to 2, each Ar8 may be the same as or different from each other.
When Ar9 is greater than or equal to 2, each Ar9 may be the same as or different from each other.
For example, at least two of R1 to R4 may be deuterium.
For example, R1 to R4 may each be deuterium, m1 and m4 may each be an integer of 4, and m2 and m3 may each be an integer of 3.
For example, R1 and R2 may each be deuterium, m1 may be an integer from 1 to 4, m2 may be an integer from 1 to 3, and R3 and R4 may each be hydrogen.
For example, R3 and R4 may each be deuterium, m3 may be an integer from 1 to 3, m4 may be an integer from 1 to 4, and R1 and R2 may each be hydrogen.
For example, R1 and R4 may each be deuterium, m1 and m4 may each be an integer from 1 to 4, and R2 and R3 may each be hydrogen.
For example, R1 to R3 may each be deuterium, m2 and m3 may each be an integer of 1 to 3, m1 may be an integer of 1 to 4, and R4 may be deuterium or a C6 to C30 aryl group substituted or unsubstituted with deuterium.
As an example, depending on the substitution position of the deuterium substituted for R1 to R4, Chemical Formula 1 may be represented by any of Chemical Formulas 1a to 1e.
In Chemical Formula 1a to Chemical Formula 1e, L1, L2, Ar1, Ar2, and Ar6 to Ar9 are the same as described above.
Ar6 to Ar9 are each independently a C6 to C30 aryl group substituted or unsubstituted with hydrogen or deuterium,
For example, at least one of Ar1 and Ar2 may be a phenyl group substituted with at least one deuterium, a biphenyl group substituted with at least one deuterium, a terphenyl group substituted with at least one deuterium, a naphthyl group substituted with at least one deuterium, an anthracenyl group substituted with at least one deuterium, a phenanthrenyl group substituted with at least one deuterium, a triphenylene group substituted with at least one deuterium, a fluorenyl group substituted with at least one deuterium, a dibenzofuranyl group substituted with at least one deuterium, or a dibenzothiophenyl group substituted with at least one deuterium.
As a specific example, at least one of Ar1 and Ar2 may be a phenyl group substituted with at least one deuterium, a biphenyl group substituted with at least one deuterium, a terphenyl group substituted with at least one deuterium, a triphenylene group substituted with at least one deuterium, a dibenzofuranyl group substituted with at least one deuterium, or a dibenzothiophenyl group substituted with at least one deuterium.
As a specific example, Ar6 to Ar9 may each independently be a C6 to C20 aryl group unsubstituted or substituted with hydrogen or deuterium.
For example, Ar6 to Ar9 may each independently be hydrogen, a phenyl group substituted or unsubstituted with deuterium, a biphenyl group substituted or unsubstituted with deuterium, a terphenyl group substituted or unsubstituted with deuterium, a naphthyl group substituted or unsubstituted with deuterium, a phenanthrenyl group substituted or unsubstituted with deuterium, an anthracenyl group substituted or unsubstituted with deuterium, a triphenylene group substituted or unsubstituted with deuterium, or a fluorenyl group substituted or unsubstituted with deuterium.
For example, L1-Ar1 and L2-Ar2 in Chemical Formula 1 may each independently be selected from the substituents listed in Group I-1 and Group I-2, and at least one of L1-Ar1 and L2-Ar2 may be selected from among the listed substituents in Group I-2.
In Group I-1 and Group I-2, * is a linking point.
For example, Chemical Formula 1 may be represented by Chemical Formula 1-8a or Chemical Formula 1-8e.
In Chemical Formula 1-8a and Chemical Formula 1-8e,
For example, Ar9 may be a phenyl group substituted or unsubstituted with deuterium, a biphenyl group substituted or unsubstituted with deuterium, a terphenyl group substituted or unsubstituted with deuterium, a naphthyl group substituted or unsubstituted with deuterium, a phenanthrenyl group substituted or unsubstituted with deuterium, an anthracenyl group substituted or unsubstituted with deuterium, a triphenylene group substituted or unsubstituted with deuterium, or a fluorenyl group substituted or unsubstituted with deuterium.
For example, the compound for an organic optoelectronic device represented by Chemical Formula 1 may be one selected from the compounds listed in Group 1, but is not limited thereto.
As a more specific example, the compound for an organic optoelectronic device according to the present invention may be represented by Chemical Formula 1-8a,
The second compound may be represented by a combination of Chemical Formula 2 and Chemical Formula 3.
In Chemical Formula 2 and Chemical Formula 3,
The second compound can be used in the light emitting layer together with the first compound to improve luminous efficiency and life-span characteristics by increasing charge mobility and stability.
For example, the second compound may be represented by any one of Chemical Formula 2A, Chemical Formula 2B, Chemical Formula 2C, Chemical Formula 2D, Chemical Formula 2E, and Chemical Formula 2F.
In Chemical Formula 2A to Chemical Formula 2F, Ar3 to Ar5, L3 to L6, and R5 to R12 are the same as described above,
For example, Ar3 to Ar5 of Chemical Formulas 2 and 3 may each independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl 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, Ar3 to Ar5 in Chemical Formula 2 and Chemical Formula 3 may each be independently selected from the substituents listed in Group II.
In Group II, * is a linking point.
In an example embodiment, Ra1 to Ra4 and R5 to R12 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, Ra1 to Ra4 and R5 to R12 may each independently be hydrogen, deuterium, a cyano group, or a substituted or unsubstituted phenyl group.
In a more specific embodiment, R5 to R12 may each independently be hydrogen, deuterium, or a cyano group,
In a specific embodiment of the present invention, the second compound may be represented by Chemical Formula 2B, wherein in Chemical Formula 2B, La1 and L2 may be a single bond, L3 to L6 may each independently be a single bond or a substituted or unsubstituted C6 to C12 arylene group, R5 to R12, Ra1, and Ra2 may each independently be hydrogen, deuterium or a substituted or unsubstituted phenyl group, and Ar3 to Ar5 may each independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group.
For example, the second compound may be one selected from the compounds of Group 2, but is not limited thereto.
In a more specific embodiment of the present invention, the first compound may be represented by Chemical Formula 1-8a, and the second compound may be represented by Chemical Formula 2B.
The first compound and the second compound may be included in a weight ratio of, for example, 1:99 to 99:1. Within the range, a desirable weight ratio may be adjusted using an electron transport capability of the first compound and a hole transport capability of the second compound 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 10:90 to 90:10, 20:80 to 80:20, for example, 20:80 to 70:30, 20:80 to 60:40, or 30:70 to 60:40. As a specific example, it may be included in a weight ratio of 40:60, 50:50, or 60:40.
In addition to the first and second compounds described above, one or more compounds may be further included.
For example, the composition for an organic optoelectronic device described above may further include a dopant.
The dopant may be, for example, a phosphorescent dopant, for example a phosphorescent dopant of red, green or blue, and may be, for example, a red phosphorescent dopant.
The dopant is a material mixed with the 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 may include one or two or more types.
An example of the dopant may be a phosphorescent dopant, and examples of the phosphorescent dopant may include 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.
L7MX [Chemical Formula Z]
In Chemical Formula Z, M is a metal, and L7 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 L7 and X may be, for example a bidentate ligand.
Examples of the ligands represented by L7 and X may be selected from the formulas listed in Group A, but are not limited thereto.
In Group A,
For example, a dopant represented by Chemical Formula V may be included.
In Chemical Formula V,
For example, the dopant represented by Chemical Formula Z-1 may be included.
In Chemical Formula Z-1, rings A, B, C, and D are each independently 5- or 6-membered carbocyclic or heterocyclic ring;
The dopant according to an embodiment may be a platinum complex, and may be represented by Chemical Formula VI.
In Chemical Formula VI,
Hereinafter, an organic optoelectronic device to which the aforementioned compound for an organic optoelectronic device is applied will be 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 photoconductor 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, and BaF2/Ca, but is not limited thereto.
The organic layer 105 may include the aforementioned composition for an organic optoelectronic device.
The organic layer 105 may include the light emitting layer 130, and the light emitting layer 130 may include the aforementioned composition for an organic optoelectronic device.
The composition for an organic optoelectronic device further including a dopant may be, for example, a red light emitting composition.
The light emitting layer 130 may include, for example, the aforementioned composition for an organic optoelectronic device as a phosphorescent host.
The organic layer may further include a charge transport region in addition to the light emitting layer.
The charge transport region may be, for example, the hole transport region 140.
The hole transport region 140 may further increase hole injection and/or hole mobility between the anode 120 and the light emitting layer 130 and block electrons.
Specifically, the hole transport region 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 B may be included in at least one of the hole transport layer and the hole transport auxiliary layer.
In the hole transport region, in addition to the compounds described above, known compounds disclosed in U.S. Pat. No. 5,061,569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A, etc. and compounds having a similar structure may also be used.
Also, the charge transport region may be, for example, the electron transport region 150.
The electron transport region 150 may further increase electron injection and/or electron mobility and block holes between the cathode 110 and the light emitting layer 130.
Specifically, the electron transport region 150 may include an electron transport layer between the cathode 110 and the light emitting layer 130, and an electron transport auxiliary layer between the light emitting layer 130 and the electron transport layer, and at least one of the compounds of Group C may be included in at least one of the electron transport layer and the electron transport auxiliary layer.
An embodiment of the present invention may provide an organic light emitting diode including the light emitting layer as the organic layer.
Another embodiment of the present invention may provide an organic light emitting diode including a hole transport region and the light emitting layer as the organic layer.
Another embodiment of the present invention may provide an organic light emitting diode including an electron transport region and the light emitting layer as the organic layer.
An embodiment of the present invention may provide an organic light emitting diode including a hole transport region 140 and an electron transport region 150 in addition to the light emitting layer 130 as the organic layer 105, as shown in
In another embodiment of the present invention, an organic light emitting diode may further include an electron injection layer (not shown), a hole injection layer (not shown), etc. in addition to the light emitting layer as the organic layer.
The organic light emitting diodes may be manufactured by forming an anode or a cathode on a substrate, and then forming an organic layer by a dry film method such as vacuum deposition, 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 scope of claims 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 is no particular comment or were synthesized by known methods.
The compounds presented as a more specific example of the compound of the present invention were synthesized through the following steps.
The compounds presented as a more specific example of the compound of the present invention were synthesized through the following steps.
Compound Int 1 was synthesized by referring to the method disclosed in Korean Publication No. 10-2016-0049842.
30 g (0.0535 mol) of Compound Int 1, 40 g (0.267 mol) of trifluoromethanesulfonic acid, and 282 g (3.35 mol) of D6-benzene were put and then, stirred at 10° C. for 24 hours. Subsequently, purified water was thereto and then, neutralized with a saturated K3PO4 solution. An organic layer therefrom was concentrated and column-purified to obtain 18 g of Compound 1-38 (a white solid, LC-Mass Mz 578.79, C42H10D18N2).
35 g (0.095 mol) of (phenyl-4-boronic acid)-9H-carbazole, 17 g (0.105 mol) of bromobenzene-Ds, 3.3 g (0.0028 mol) of Pd(PPh3)4, 32.7 g (0.237 mol) of K2CO3, 120 ml of purified water, and 320 ml of THF were put and then, stirred under reflux. When a reaction was completed, purified water was added thereto after cooling to separate an organic layer, and the organic layer was concentrated. The concentrated product was column-purified to obtain 25 g of Int 2 (a molecular weight: 324.43).
20 g (0.062 mol) of Int 2 was dissolved in 200 ml of DMF, and 11.5 g (0.065 mol) of NBS was slowly added thereto at 0° C. The obtained mixture was stirred at room temperature to complete a reaction, and purified water was added thereto to produce a solid. The solid was column-purify to obtain 23 g of Int 3 (a molecular weight: 403.33).
20 g (0.0496 mol) of Int 3, 22 g (0.06 mol) of phenyl-9H-carbazole-3-boronic ester, 1.72 g (0.0015 mol) of Pd(PPh3)4, 13.7 g (0.099 mol) of K2CO3, 50 ml of purified water, and 165 ml of THF were put and stirred under reflux. When a reaction was completed, purified water thereto after cooling was added thereto to separate an organic layer, and then, the organic layer was concentrated. The concentrated product was column-purified to obtain 11.5 g of Compound Y1 (a molecular weight: 565.72).
47 g (0.281 mol) of carbazole, 50 g (0.310 mol) of bromobenzene-D, 53 g (0.028 mol) of CuI, 58 g (0.42 mol) of K2CO3, 5 g (0.028 mol) of 1,10-phenanthroline, and 560 ml of DMF were put and stirred under reflux. When a reaction was completed, a solid was produced by adding purified water thereto after cooling to room temperature. The solid was column-purified to obtain 62 g of Int 4 (a molecular weight: 248.33).
62 g (0.25 mol) of Int 4 was added to DMF and dissolved therein. Subsequently, 45 g (0.25 mol) of NBS was slowly added thereto at 0° C. and then, stirred at room temperature to complete a reaction. Subsequently, purified water was added to the reaction solution to produce crystals, and the solids were column-purified to obtain 80 g of Int 5 (a molecular weight: 327.23).
80 g (0.245 mol) of Int 5, 120 g (0.27 mol) of 4-biphenyl-carbazole-3-boronic ester, 68 g (0.49 mol) of K2CO3, 14 g (0.0122 mol) of Pd(PPh3)4, 320 ml of purified water, and 490 ml of THF were put and stirred under reflux. When a reaction was completed, an organic layer was extracted by adding purified water thereto and then, concentrated. The mixture was column-purified to obtain 90 g of Compound Y2 (a molecular weight: 565.72).
11,12-dihydroindolo[2,3-a]carbazole (78.35 g, 305.69 mmol, CAS No. 60511-85-5), 3-bromobiphenyl (59.38 g, 254.74 mmol), NaOt-Bu (26.93 g, 280.22 mmol), and Pd2(dba)3 (7 g, 7.64 mmol) were suspended in 1,400 ml of toluene, and P(t-Bu)3 (3.64 m1, 15.28 mmol) was added thereto and then, stirred under reflux for 12 hours. Subsequently, distilled water was added to the reaction solution to separate the mixture. The obtained product was purified through silica gel column to obtain Intermediate M-2 (68.7 g, 57%).
2,4-dichloro-6-phenyl-1,3,5-triazine (74.50 g, 329.56 mmol) and 4-biphenylboronic acid (55.47 g, 280.12 mmol) were dissolved in 0.7 L of a mixed solution of tetrahydrofuran (THF) and distilled water (3:1), and sodium tert-butoxide (68.32 g, 494.34 mmol) was added thereto and then, stirred under reflux for 12 hours. After cooling the reaction solution and separating layers, an organic layer therefrom was collected therefrom and concentrated. The concentrated residue was purified through silica gel column to obtain Intermediate M-3 (75.9 g, 67%).
Compound B-12 was obtained in the same manner as in the method of synthesizing Intermediate M-2 by using Intermediate M-2 and Intermediate M-3.
A glass substrate coated with ITO (indium tin oxide) was washed with distilled water ultrasonic wave. 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 prepared ITO transparent electrode was used as an anode, Compound A doped with 3% NDP-9 (Novaled GmbH) was vacuum-deposited on the ITO substrate to form a 100 Å-thick hole injection layer, and Compound A was deposited on the hole injection layer to a thickness of 1350 Å to form a hole transport layer. Compound B was deposited on the hole transport layer to a thickness of 350 Å to form a hole transport auxiliary layer. On the hole transport auxiliary layer, Compound 1-38 and Compound B-12 obtained in the above synthesis examples were simultaneously used as hosts at a weight ratio of 4:6, and 10 wt % of PhGD was doped as a dopant to form a 330 Å-thick light emitting layer by vacuum deposition. Subsequently, Compound C was deposited on the light emitting layer to form a 50 Å-thick electron transport auxiliary layer, and Compound D and Liq were simultaneously vacuum deposited in a weight ratio of 1:1 to form a 300 Å-thick electron transport layer. 15 Å of LiQ and 1,200 Å of Al were sequentially vacuum-deposited on the electron transport layer to form a cathode, manufacturing an organic light emitting diode.
The structure was ITO/Compound A (3% NDP-9 doping, 100 Å)/Compound A (1350 Å)/Compound B (350 Å)/EML[90 wt % of host (Compound 1-38: Compound B-12=4:6 w/w): 10 wt % of PhGD] (330 Å)/Compound C (50 Å)/Compound D:LiQ (300 Å)/LiQ (15 Å)/Al (1200 Å).
Organic light emitting diodes according to Comparative Examples 1 to 3 were manufactured in the same manner as in Example 1, except that the host was changed as shown in Table 1.
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.
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.
Luminous 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).
The results were obtained by maintaining the luminance (cd/m2) at 24000 cd/m2 and measuring the time for the luminous efficiency (cd/A) to decrease to 95%.
The values shown in Table 1 are relative values based on the values of Comparative Example 2, respectively.
Referring to Table 1, life-span characteristics of the organic light emitting diode according to the example of the present invention are significantly improved compared to the organic light emitting diodes according to the comparative examples.
While this disclosure has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0088618 | Jul 2021 | KR | national |
| 10-2022-0082644 | Jul 2022 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2022/009716 | 7/6/2022 | WO |
