Patent Application
20220140257
This application claims priority to and the benefit of Korean Patent Application No. 10-2020-0146197 filed in the Korean Intellectual Property Office on Nov. 4, 2020 and Korean Patent Application No. 10-2021-0148039 filed in the Korean Intellectual Property Office on Nov. 1, 2021, the entire contents of which are incorporated herein by reference.
Embodiments relate to a compound for an organic optoelectronic device, a composition for an organic optoelectronic device, an organic optoelectronic device, and a display device.
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 divided into two types according to a principle of operation. One type 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 another type 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 may be influenced by an organic material between electrodes.
The embodiments may be realized by providing a compound for an organic optoelectronic device, the compound being represented by a combination of Chemical Formula 1 and Chemical Formula 2,
wherein, in Chemical Formulas 1 and 2, Ar is a substituted or unsubstituted C12 to C30 aryl group, two adjacent ones of a1* to a4* of Chemical Formula 1 are linking carbons linked at * of Chemical Formula 2, the remaining two of a1* to a4* of Chemical Formula 1, not linked at * of Chemical Formula 2, are C—Ra, Ra and R1 to R13 are each independently hydrogen, deuterium, a cyano group, a halogen, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, and R14 is a substituted or unsubstituted C6 to C20 aryl group.
The embodiments may be realized by providing a composition for an organic optoelectronic device, the composition comprising a first compound and a second compound, wherein the first compound is the compound according to an embodiment, and the second compound is represented by Chemical Formula 3; or a combination of Chemical Formula 4 and Chemical Formula 5,
in Chemical Formula 3, Y1 and Y2 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, L1 and L2 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group, Rb and R15 to R24 are each independently hydrogen, deuterium, a cyano group, a halogen, a substituted or unsubstituted amino 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 4 and Chemical Formula 5, Y3 and Y4 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, two adjacent ones of b1* to b4* of Chemical Formula 4 are linking carbons linked at * of Chemical Formula 5, the remaining two of b1* to b4* of Chemical Formula 4, not linked at * of Chemical Formula 5, are C-La-Rc, La, L3, and L4 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group, and Rc and R25 to R32 are each independently hydrogen, deuterium, a cyano group, a halogen, a substituted or unsubstituted amino 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 embodiments may be realized by providing 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 at least one organic layer includes the compound according to an embodiment.
The embodiments may be realized by providing 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 at least one organic layer includes the composition according to an embodiment.
The embodiments may be realized by providing a display device comprising the organic optoelectronic device according to an embodiment.
Features will be apparent to those of skill in the art by describing in detail exemplary embodiments with reference to the attached drawings in which:
Example embodiments will now be described more fully hereinafter with reference to the accompanying drawings; however, they may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey exemplary implementations to those skilled in the art.
In the drawing figures, the dimensions of layers and regions may be exaggerated for clarity of illustration. It will also be understood that when a layer or element is referred to as being “on” another layer or element, it can be directly on the other layer or element, or intervening layers may also be present. In addition, it will also be understood that when a layer is referred to as being “between” two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present. Like reference numerals refer to like elements throughout. As used herein, the term “or” is not an exclusive term, e.g., “A or B” would include A, B, or A and B.
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, 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 a specific example, 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 a specific example, 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 a specific example, 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.
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 quarterphenyl 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, 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 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, e.g., a combination of Chemical Formula 1 and Chemical Formula 2.
In Chemical Formulas 1 and 2, Ar may be or may include, e.g., a substituted or unsubstituted C12 to C30 aryl group.
Two adjacent ones of a1* to a4* of Chemical Formula 1 may be linking carbons linked at * of Chemical Formula 2, the remaining two of a1* to a4* of Chemical Formula 1, not linked at * of Chemical Formula 2, may be C—Ra. As used herein, the term “linking carbon” refers to a shared carbon at which fused rings are linked.
Ra and R1 to R13 may each independently be or include, e.g., hydrogen, deuterium, a cyano group, a halogen, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
R14 may be or may include, e.g., a substituted or unsubstituted C6 to C20 aryl group.
The compound represented by the combination of Chemical Formula 1 and Chemical Formula 2 may include an indolocarbazole skeleton, and may have a structure in which it is directly substituted with a triazine moiety on one of the two N atoms of the indolocarbazole, and substituted with a substituted or unsubstituted C12 or higher aryl group on the other of the two N atoms of the indolocarbazole.
In addition, the triazine moiety may include a dibenzofuran group as a substituent thereon, and the dibenzofuran group may further include a substituted or unsubstituted phenyl group thereon.
As such, by designing a structure wrapped with or including indolocarbazole, triazine, and dibenzofuranyl groups, the interference of negative ions in the electron transport region may be minimized, and thus degradation of the device may be reduced or prevented.
In an implementation, the compound may be substituted with a triazine moiety on the N atom of indolocarbazole, and the it-bond may be broken by forming a C—N bond, thereby preventing the HOMO electron cloud from expanding. This may facilitate effective localization, which may help achieve a long life-span effect.
According to the substitution position of the substituted or unsubstituted phenyl group that further substitutes the dibenzofuran group, Chemical Formula 2 may be, e.g., represented by one of Chemical Formula 2-1 to Chemical Formula 2-4.
In Chemical Formula 2-1 to Chemical Formula 2-4, the definitions of R5 to R14, and * may be the same as described above.
In an implementation, Chemical Formula 2-1 may be, e.g., represented by one of Chemical Formula 2-1-i to Chemical Formula 2-1-iv.
In Chemical Formula 2-1-i to Chemical Formula 2-1-iv, the definitions of R5 to R14, and * may be the same as described above.
In an implementation, Chemical Formula 2-2 may be, e.g., represented by one of Chemical Formula 2-2-i to Chemical Formula 2-2-iv.
In Chemical Formula 2-2-i to Chemical Formula 2-2-iv, the definitions of R5 to R14, and * may be the same as described above.
In an implementation, Chemical Formula 2-3 may be, e.g., represented by one of Chemical Formula 2-3-i to Chemical Formula 2-3-iv.
In Chemical Formula 2-3-i to Chemical Formula 2-3-iv, the definitions of R5 to R14, and * may be the same as described above.
In an implementation, Chemical Formula 2-4 may be, e.g., represented by one of Chemical Formula 2-4-i to Chemical Formula 2-4-iv.
In Chemical Formula 2-4-i to Chemical Formula 2-4-iv, the definitions of R5 to R14, and * may be the same as described above.
In an implementation, the compound for an organic optoelectronic device according to an embodiment may be represented by a combination of Chemical Formula 1 and one of Chemical Formula 2-1-i to Chemical Formula 2-1-iv.
In an implementation, the compound for an organic optoelectronic device according to another embodiment may be represented by a combination of Chemical Formula 1 and Chemical Formula 2-2-ii.
In an implementation, the compound for an organic optoelectronic device according to another embodiment may be represented by a combination of Chemical Formula 1 and Chemical Formula 2-3-i.
In an implementation, the compound for an organic optoelectronic device according to another embodiment may be represented by a combination of Chemical Formula 1 and Chemical Formula 2-4-iv.
In the combination of Chemical Formula 1 and Chemical Formula 2-1-i, steric hindrance may occur as the dibenzofuranyl group is substituted on the triazine at the 1-position thereon and the dibenzofuranyl group is further substituted with the aryl group at the 8-position thereof, and thus a three-dimensional structure may be formed while having a non-planar angle with the triazine.
In an implementation, when the substituent is located at the 8-position of the dibenzofuran, it may have a larger angle. The larger the angle, the closer the shape of the molecule to a spherical shape, and the closer the molecule is to a spherical shape, the more densely it is arranged in the deposition process.
This structural feature may help reduce a gap between molecules to facilitate the flow of electrons/holes and may also facilitate formation of excitons, and thus low-driving, high-efficiency, and long life-span devices may be realized as a whole.
Therefore, it is possible to realize high-efficiency and long life-span characteristics of the organic light emitting diode to which it is applied.
In an implementation, the combination of Chemical Formula 1 and Chemical Formula 2 may be represented by, e.g., one of Chemical Formula 1A to Chemical Formula 1F, depending on the fusion form of indolocarbazole.
In Chemical Formula 1A to Chemical Formula 1F, Ar, and R1 to R14 may be defined the same as those described above.
Ra1 to Ra4 may each independently be defined the same as Ra.
In an implementation, the compound for an organic optoelectronic device according to an embodiment may be represented by, e.g., Chemical Formula 1B, Chemical Formula 1C, Chemical Formula 1E, or Chemical Formula 1F.
In an implementation, the compound for an organic optoelectronic device may be represented by, e.g., Chemical Formula 1B, Chemical Formula 1C, or Chemical Formula 1F.
In an implementation, the compound for an organic optoelectronic device may be represented by a combination of Chemical Formula 1 and Chemical Formula 2-1-i.
In an implementation, the combination of Chemical Formula 1 and Chemical Formula 2-1-i may be represented by, e.g., one of Chemical Formula 1A-1 to Chemical Formula 1F-1, depending on the fusion form of indolocarbazole.
In Chemical Formula 1A-1 to Chemical Formula 1F-1, Ar, and R1 to R14 may be defined the same as those described above.
Ra1 to Ra4 may each independently be defined the same as Ra.
In an implementation, the compound for an organic optoelectronic device according to an embodiment may be represented by, e.g., Chemical Formula 1B-1, Chemical Formula 1C-1, Chemical Formula 1E-1, or Chemical Formula 1F-1.
In an implementation, the compound for an organic optoelectronic device may be represented by, e.g., Chemical Formula 1B-1, Chemical Formula 1C-1, or Chemical Formula 1F-1.
In an implementation, the compound for an organic optoelectronic device may be represented by, e.g., a combination of Chemical Formula 1 and Chemical Formula 2-2-ii.
In an implementation, the compound for an organic optoelectronic device may be represented by, e.g., Chemical Formula 1B-2.
In Chemical Formula 1B-2, Ar, R1 to R14, Ra1 and Ra4 may be defined the same as those described above.
In an implementation, the compound for an organic optoelectronic device may be represented by, e.g., a combination of Chemical Formula 1 and Chemical Formula 2-3-i.
In an implementation, the compound for an organic optoelectronic device may be represented by, e.g., Chemical Formula 1B-3.
In Chemical Formula 1B-3, Ar, R1 to R14, Ra3 and Ra4 may be defined the same as those described above.
In an implementation, the compound for an organic optoelectronic device may be represented by, e.g., a combination of Chemical Formula 1 and Chemical Formula 2-4-iv.
In an implementation, the compound for an organic optoelectronic device may be represented by, e.g., Chemical Formula 1B-4.
In Chemical Formula 1B-4, Ar, R1 to R14, Ra3 and Ra4 may be defined the same as those described above.
In an implementation, Ar may be, e.g., 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, or a substituted or unsubstituted triphenylene group.
In an implementation, Ar may be, e.g., a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group.
In an implementation, Ar may be, e.g., a group of Group I.
In Group I, * is a linking point (e.g., with N of Chemical Formula 1).
In an implementation, R14 may be, e.g., a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted naphthyl group.
In an implementation, R14 may be, e.g., a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group.
In an implementation, when R14 is substituted, it may be substituted with, e.g., a cyano group or a phenyl group.
In an implementation, R9 to R13 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group.
In an implementation, R9 to R13 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group.
In an implementation, R1 to R8 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group.
In an implementation, R1 to R8 may each independently be, e.g., hydrogen, deuterium, or a substituted or unsubstituted phenyl group.
In an implementation, the compound for an organic optoelectronic device represented by the combination of Chemical Formula 1 and Chemical Formula 2 may be, e.g., a compound of Group 1.
A composition for an organic optoelectronic device according to an embodiment may include, e.g., a first compound for an organic optoelectronic device, and a second compound for an organic optoelectronic device (e.g., as a mixture). The first compound for an organic optoelectronic device may be the aforementioned compound for an organic optoelectronic device (e.g., represented by the combination of Chemical Formulas 1 and 2) and the second compound for an organic optoelectronic device may be represented by, e.g., Chemical Formula 3; or a combination of Chemical Formula 4 and Chemical Formula 5.
In Chemical Formula 3, Y1 and Y2 may each independently be or include, e.g., a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.
L1 and L2 may each independently be or include, e.g., a single bond or a substituted or unsubstituted C6 to C20 arylene group.
Rb and R15 to R24 may each independently be or include, e.g., hydrogen, deuterium, a cyano group, a halogen, a substituted or unsubstituted amino 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.
m may be, e.g., an integer of 0 to 2.
In Chemical Formula 4 and Chemical Formula 5, Y3 and Y4 may each independently be or include, e.g., a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.
Two adjacent ones of b1* to b4* of Chemical Formula 4 may be linking carbons linked at * of Chemical Formula 5, the remaining two of b1* to b4* of Chemical Formula 4, not linked at * of Chemical Formula 5, may be C-La-Rc.
La, L3, and L4 may each independently be or include, e.g., a single bond or a substituted or unsubstituted C6 to C20 arylene group.
Rc and R25 to R32 may each independently be or include, e.g., hydrogen, deuterium, a cyano group, a halogen, a substituted or unsubstituted amino 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 an organic optoelectronic device may be used in the light emitting layer together with the first compound for an organic optoelectronic device to help improve the mobility of charges and improve stability, thereby improving luminous efficiency and life-span characteristics.
In an implementation, Y1 and Y2 of Chemical Formula 3 may each independently be, e.g., 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 implementation, L1 and L2 of Chemical Formula 3 may each independently be, e.g., a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.
In an implementation, R15 to R24 of Chemical Formula 3 may each independently be, e.g., hydrogen, deuterium, or a substituted or unsubstituted C6 to C12 aryl group.
m may be, e.g., 0 or 1.
In an implementation, “substituted” of Chemical Formula 3 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 an implementation, Chemical Formula 3 may be represented by, e.g., one Chemical Formula 3-1 to Chemical Formula 3-15.
In Chemical Formula 3-1 to Chemical Formula 3-15, R15 to R24 may each independently be, e.g., hydrogen or a substituted or unsubstituted C6 to C12 aryl group. In an implementation, moieties *-L1-Y1 and *-L2-Y2 may each independently be, e.g., a moiety of Group II.
In Group II, * is a linking point (e.g., with N of the chemical formulae).
In an implementation, Chemical Formula 3 may be represented by, e.g., Chemical Formula 3-8.
In an implementation, moieties *-L1-Y1 and *-L2-Y2 of Chemical Formula 3-8 may each independently be a moiety of Group II, e.g., C-1, C-2, C-3, C-16, or C-23.
In an implementation, moieties *-L1-Y1 and *-L2-Y2 may be, e.g., C-1, C-2, or C-3 of Group II.
In an implementation, the second compound for an organic optoelectronic device represented by the combination of Chemical Formula 4 and Chemical Formula 5 may be represented by, e.g., Chemical Formula Chemical Formula 4A, Chemical Formula 4B, Chemical Formula 4C, Chemical Formula 4D, or Chemical Formula 4E.
In Chemical Formula 4A to Chemical Formula 4E, Y3, Y4, L3, L4, and R25 to R32 may be defined the same as those described above.
La1 to La4 may be defined the same as L3 and L4.
Rc1 to Rc4 may be defined the same as R19 to R26.
In an implementation, Y3 and Y4 of Chemical Formulas 3 and 4 may each independently be, e.g., 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 an implementation, Rc1 to Rc4 and R25 to R32 may each independently be, e.g., 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 an implementation, Y3 and Y4 in Chemical Formulas 4 and 5 may each independently be, e.g., a group of Group III.
In Group III, * is a linking point with L3 and L4, respectively.
In an implementation, Rc1 to Rc4 and R25 to R32 may each independently be, e.g., 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 an implementation, Rc1 to Rc4 and R25 to R32 may each independently be, e.g., hydrogen, deuterium, a cyano group, or a substituted or unsubstituted phenyl group.
In an implementation, each of Rc1 to Rc4 may be, e.g., hydrogen, and R25 to R32 may each independently be, e.g., hydrogen or a phenyl group.
In an implementation, the second compound for an organic optoelectronic device may be represented by, e.g., Chemical Formula 3-8, wherein in Chemical Formula 3-8, Y1 and Y2 may each independently be, e.g., 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, L3 and L4 may each independently be, e.g., a single bond or a substituted or unsubstituted C6 to C20 arylene group, and R15 to R24 may each independently be, e.g., 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 an implementation, the second compound for an organic optoelectronic device may be represented by, e.g., Chemical Formula 4C or Chemical Formula 4D, wherein in Chemical Formula 4C and Chemical Formula 4D, La1 to La4 may be, e.g., a single bond, L3 and L4 may each independently be, e.g., a single bond or a substituted or unsubstituted C6 to C12 arylene group, R25 to R32, and Rc1 to Rc4 may each be, e.g., hydrogen, and Y3 and Y4 may each independently be, e.g., a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group.
In an implementation, the second compound for an organic optoelectronic device may be, e.g., a compound of Group 2.
The first compound for an organic optoelectronic device and the second compound for an organic optoelectronic device may be included, e.g., in a weight ratio of about 1:99 to about 99:1. Within the above range, an appropriate weight ratio may be adjusted using the electron transport capability of the first compound for the organic optoelectronic device and the hole transport capability of the second compound for an organic optoelectronic device to implement bipolar characteristics and to improve the efficiency and life-span. Within the above range, e.g., they may be included in a weight ratio of about 10:90 to about 90:10, about 10:90 to about 80:20, e.g., about 10:90 to about 70:30, or about 20:80 to about 70:30. In an implementation, they may be included in a weight ratio of about 20:80, about 30:70, or about 40:60.
In addition to the aforementioned first compound for an organic optoelectronic device and second compound for an organic optoelectronic device, one or more additional compounds 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, e.g., a phosphorescent dopant and may be, for example a red, green or blue phosphorescent dopant, for example a red or green phosphorescent dopant.
The dopant is a material mixed with the compound or composition for an organic optoelectronic device in a trace 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, e.g., 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. In an implementation, the phosphorescent dopant may be, e.g., a compound represented by Chemical Formula Z.
L5MX [Chemical Formula Z]
In Chemical Formula Z, M may be, e.g., a metal, and L5 and X may each independently be, e.g., ligands forming a complex with M.
M may be, e.g., Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof, and L5 and X may be, e.g., a bidentate ligand.
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 a suitable device to convert electrical energy into photoenergy and vice versa, and may be, e.g., an organic photoelectric device, an organic light emitting diode, an organic solar cell, or 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, e.g., a metal, a metal oxide or a conductive polymer. The anode 120 may be, e.g., a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or the like or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or 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, or polyaniline.
The cathode 110 may be made of a conductor having a small work function to help electron injection, and may be, e.g., a metal, a metal oxide, or a conductive polymer. The cathode 110 may be, e.g., a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum silver, tin, lead, cesium, barium, or the like, or an alloy thereof; or a multi-layer structure material such as LiF/Al, LiO2/Al, LiF/Ca, or BaF2/Ca.
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 the light emitting layer 130, and the light emitting layer 130 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 the dopant may be, e.g., a red light emitting composition.
The light emitting layer 130 may include, e.g., the aforementioned first compound for an organic optoelectronic device and second compound for an organic optoelectronic device, respectively, as a phosphorescent host.
The organic layer may further include a charge transport region in addition to the light emitting layer.
The auxiliary layer may be, e.g., the hole auxiliary layer 140.
Referring to
In the hole transport region, in addition to the compounds described above, other suitable compounds may also be used.
In an implementation, the charge transport region may be, e.g., the electron transport region 150.
Referring to
In an implementation, 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. In an implementation, at least one of the compounds of Group F may be included in at least one of the electron transport layer and the electron transport auxiliary layer.
An embodiment may provide an organic light emitting diode including the light emitting layer 130 as the organic layer 105 as shown in
Another embodiment may provide an organic light emitting diode including a hole transport region 140 in addition to the light emitting layer 130 as the organic layer 105, as shown in
Another embodiment may provide an organic light emitting diode including an electron transport region 150 in addition to the light emitting layer 130 as the organic layer 105 as shown in
Another embodiment 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, an organic light emitting diode may further include an electron injection layer, a hole injection layer, or the like, in addition to the light emitting layer 130 as the organic layer 105 in each of
The organic light emitting diodes 100, 200, 300, and 400 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.
The following Examples and Comparative Examples are provided in order to highlight characteristics of one or more embodiments, but it will be understood that the Examples and Comparative Examples are not to be construed as limiting the scope of the embodiments, nor are the Comparative Examples to be construed as being outside the scope of the embodiments. Further, it will be understood that the embodiments are not limited to the particular details described in the Examples and Comparative Examples.
Hereinafter, starting materials and reactants used in examples and synthesis examples were purchased from Sigma-Aldrich Co. Ltd., TCI Inc., Tokyo Chemical Industry Co., Ltd., or P&H Tech Co., Ltd., as far as there is no particular comment or were synthesized by suitable methods.
(Preparation of Compound for Organic Optoelectronic Device)
Under a nitrogen atmosphere, cyanamide (50 g, 1,189 mmol) was dissolved in 0.2 L of deionized water, and sodium hydroxide (90.6 g, 2,264 mmol) and benzamidine hydrochloride (117 g, 1,132 mmol) were sequentially slowly added thereto and then, stirred at room temperature for 12 hours. When a reaction was completed, a solid produced therein was filtered and dried at room temperature to obtain Intermediate I-1 (148 g, 90%).
HRMS (70 eV, EI+): m/z calcd for C8H7N3: 145.0640, found: 145.
Elemental Analysis: C, 66%; H, 5%
Under a nitrogen atmosphere, 2-chloro-3-fluorobenzoic acid (50 g, 286 mmol) purchased from Tokyo Chemical Industry Co., Ltd. (http://www.tcichemicals.com/) was dissolved in 0.5 L of thionyl chloride and then, heated under reflux at 80° C. for 1 hour. When a reaction was completed, 0.1 L of toluene was added thereto, and the solvent was all removed by using a rotary decompression concentrator. The residue was vacuum-dried at room temperature to obtain Intermediate I-2 (54.3 g, 99%).
HRMS (70 eV, EI+): m/z calcd for C7H3Cl2FO: 191.9545, found: 191.
Elemental Analysis: C, 44%; H, 2%
Under a nitrogen atmosphere, 2,3-dichloroanisole (200 g, 1,130 mmol) purchased from Tokyo Chemical Industry Co., Ltd. was dissolved in 1 L of tetrahydrofuran, and then, 0.31 L of a phenyl magnesium bromide solution (3.0 M in diethyl ether) purchased from Sigma Aldrich Co., Ltd. (http://www.sigmaaldrich.com/) was slowly added thereto in a dropwise fashion at 0° C. When a reaction was completed, ammonium chloride (75.6 g, 1,413 mmol) saturated in water was added to the reaction solution and then, extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and then, concentrated under a reduced pressure. The obtained residue was purified through flash column chromatography, obtaining Intermediate I-3 (471 g, 50%).
HRMS (70 eV, EI+): m/z calcd for C13H11ClO: 218.0498, found: 218.
Elemental Analysis: C, 71%; H, 5%
Under a nitrogen atmosphere, 0.15 L of a dimethylamine solution (2.0 M in THF) and triethylamine (60.5 g, 598 mmol) were dissolved in 0.5 L of tetrahydofuran (THF), and Intermediate I-2 (57.8 g, 299 mmol) dissolved in 0.5 L of THF was slowly added thereto in a dropwise fashion at 0° C. After stirring the mixture for 1 hour, water was added to the reaction solution and then, extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining Intermediate I-4 (57.7 g, 96%).
HRMS (70 eV, EI+): m/z calcd for C9H9ClFNO: 201.0357, found: 201.
Elemental Analysis: C, 54%; H, 5%
Under a nitrogen atmosphere, Intermediate I-4 (57.7 g, 286 mmol) was dissolved in 1 L of acetonitrile (ACN), and Intermediate I-1 (41.5 g, 286 mmol) and phosphorus oxychloride (48.2 g, 315 mmol) were added thereto and then, heated under reflux at 90° C. for 2 days. When a reaction was completed, a solid produced therein was filtered, washed with distilled water and ethanol, and dried, obtaining Intermediate I-5 (46.7 g, 51%).
HRMS (70 eV, EI+): m/z calcd for C15H8Cl2FN3: 319.0079, found: 319.
Elemental Analysis: C, 56%; H, 3%
Under a nitrogen atmosphere, 11-(biphenyl-4-yl)-11,12-dihydroindolo[2,3-a]carbazole (100 g, 245 mmol) purchased from Ukseung Chemical Co., Ltd. (http://www.ukseung.co.kr/) was dissolved in 1 L of dimethylformamide (DMF), and sodium hydride (7.05 g, 294 mmol) was added thereto at 0° C. and then, stirred. After 1 hour, Intermediate I-5 (94.1 g, 294 mmol) was added thereto and then, stirred for 1 hour. When a reaction was completed, water was added to the reaction solution at 0° C. and then, extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining Intermediate I-6 (142 g, 84%).
HRMS (70 eV, EI+): m/z calcd for C45H27ClFN5: 691.1939, found: 691.
Elemental Analysis: C, 84%; H, 4%
Under a nitrogen atmosphere, Intermediate I-6 (140 g, 202 mmol) was dissolved in 1 L of xylene, and then, bis(pinacolato)diboron (61.6 g, 243 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.85 g, 2.02 mmol), tricyclohexylphosphine (2.27 g, 8.08 mmol), and potassium acetate (59.5 g, 606 mmol) were added thereto and then, heated under reflux for 13 hours. When a reaction was completed, water was added to the reaction solution and then, extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining Intermediate I-7 (39.6 g, 25%).
HRMS (70 eV, EI+): m/z calcd for C51H39BFN5O2: 783.3181, found: 783.
Elemental Analysis: C, 78%; H, 5%
Under a nitrogen atmosphere, Intermediate I-7 (38 g, 48.5 mmol) was dissolved in 0.3 L of dioxane, and then, Intermediate I-3 (15.9 g, 72.7 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.33 g, 1.46 mmol), tricyclohexylphosphine (2.04 g, 7.28 mmol), and potassium phosphate tribasic (30.9 g, 146 mmol) were added thereto and then, heated under reflux for 15 hours. When a reaction was completed, water was added to the reaction solution and then, extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining Intermediate I-8 (22.4 g, 55%).
HRMS (70 eV, EI+): m/z calcd for C58H38FN5O: 839.3060, found: 839.
Elemental Analysis: C, 83%; H, 5%
Under a nitrogen atmosphere, Intermediate I-8 (22 g, 26.2 mmol) and pyridine hydrochloride (15.1 g, 131 mmol) were heated under reflux at 180° C. for 12 hours. When a reaction was completed, water was added to the reaction solution and then, extracted with ethyl acetate (EA), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining Intermediate I-9 (17.3 g, 80%).
HRMS (70 eV, EI+): m/z calcd for C57H36FN5O: 825.2904, found: 825.
Elemental Analysis: C, 83%; H, 4%
Under a nitrogen atmosphere, Intermediate I-9 (10 g, 12.1 mmol) was dissolved in 0.1 L of N-methyl-2-pyrrolidone (NMP) and then, potassium carbonate (3.35 g, 24.2 mmol) was added thereto and then, heated under reflux for 3 hours. When a reaction was completed, water was added to the reaction solution and then, extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining Compound 1 (7.51 g, 77%).
HRMS (70 eV, EI+): m/z calcd for C57H35N5O: 805.2842, found: 805.
Elemental Analysis: C, 85%; H, 4%
Intermediate I-10 (111 g, 98%) was obtained according to the same method as in Synthesis Example 1 except that biphenyl-4-carboximidamide hydrochloride (100 g, 512 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C14H11N3: 221.0953, found: 221.
Elemental Analysis: C, 76%; H, 5%
Intermediate I-11 (93.4 g, 95%) was obtained according to the same method as in Synthesis Example 5 except that Intermediate I-4 (50 g, 248 mmol) and Intermediate I-10 (54.9 g, 248 mmol) were used.
HRMS (70 eV, EI+): m/z calcd for C21H12C12FN3: 395.0392, found: 395.
Elemental Analysis: C, 64%; H, 3%
Intermediate I-12 (173 g, 91%) was obtained according to the same method as in Synthesis Example 6 except that 11-(biphenyl-4-yl)-11,12-dihydroindolo[2,3-a]carbazole (100 g, 248 mmol) purchased from Ukseung Chemical Co., Ltd. and Intermediate I-11 (118 g, 298 mmol) were used.
HRMS (70 eV, EI+): m/z calcd for C51H31ClFN5: 767.2252, found: 767.
Elemental Analysis: C, 80%; H, 4%
Intermediate I-13 (36.9 g, 30%) was obtained according to the same method as Synthesis Example 7 except that Intermediate I-12 (110 g, 143 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C57H43BFN5O2: 859.3494, found: 859.
Elemental Analysis: C, 80%; H, 5%
Intermediate I-14 (17.9 g, 48%) was obtained according to the same method as Synthesis Example 8 except that Intermediate I-13 (35 g, 40.7 mmol) and Intermediate I-3 (13.4 g, 61.1 mmol) were used.
HRMS (70 eV, EI+): m/z calcd for C64H42FN5O: 915.3373, found: 915.
Elemental Analysis: C, 84%; H, 5%
Intermediate I-15 (13.3 g, 90%) was obtained according to the same method as Synthesis Example 9 except that Intermediate I-14 (15 g, 16.4 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C63H40FN5O: 901.3217, found: 901.
Elemental Analysis: C, 84%; H, 4%
Compound 5 (7.34 g, 75%) was obtained according to the same method as Synthesis Example 10 except that Intermediate I-15 (10 g, 11.1 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C63H39N5O: 881.3155, found: 881.
Elemental Analysis: C, 86%; H, 4%
Intermediate I-16 (171 g, 90%) was obtained according to the same method as Synthesis Example 6 except that 11-(biphenyl-3-yl)-11,12-dihydroindolo[2,3-a]carbazole (100 g, 248 mmol) purchased from Ukseung Chemical Co., Ltd. and Intermediate I-11 (118 g, 298 mmol) were used.
HRMS (70 eV, EI+): m/z calcd for C51H31ClFN5: 767.2252, found: 767.
Elemental Analysis: C, 80%; H, 4%
Intermediate I-17 (26.5 g, 23%) was obtained according to the same method as Synthesis Example 7 except that Intermediate I-16 (150 g, 195 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C57H43BFN5O2: 859.3494, found: 859.
Elemental Analysis: C, 80%; H, 5%
Intermediate I-18 (10.4 g, 39%) was obtained according to the same method as Synthesis Example 8 except that Intermediate I-17 (25 g, 29.1 mmol) and Intermediate I-3 (9.54 g, 43.6 mmol) were used.
HRMS (70 eV, EI+): m/z calcd for C64H42FN5O: 915.3373, found: 915.
Elemental Analysis: C, 84%; H, 5%
Intermediate I-19 (9.35 g, 95%) was obtained according to the same method as Synthesis Example 9 except that Intermediate I-18 (10 g, 10.9 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C63H40FN5O: 901.3217, found: 901.
Elemental Analysis: C, 84%; H, 4%
Compound 29 (6.86 g, 78%) was obtained according to the same method as Synthesis Example 10 except that Intermediate I-19 (9 g, 9.98 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C63H39N5O: 881.3155, found: 881.
Elemental Analysis: C, 86%; H, 4%
Intermediate I-20 was synthesized according to a method described in WO2018-095391.
HRMS (70 eV, EI+): m/z calcd for C30H20N2: 408.1626, found: 408.
Elemental Analysis: C, 88%; H, 5%
Under a nitrogen atmosphere, Intermediate I-20 (100 g, 245 mmol) was dissolved in 1 L of xylene, and Intermediate I-11 (116 g, 294 mmol), tris(dibenzylideneacetone)dipalladium (0) (6.73 g, 7.35 mmol), tris(tert butyl)phosphine (5.95 g, 29.4 mmol), and cesium carbonate (95.8 g, 294 mmol) were sequentially added thereto and then, heated under reflux at 130° C. for 14 hours. When a reaction was completed, water was added to the reaction solution and then, extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining Intermediate I-21 (122 g, 65%).
HRMS (70 eV, EI+): m/z calcd for C51H31ClFN5: 767.2252, found: 767.
Elemental Analysis: C, 80%; H, 4%
Intermediate I-22 (34.9 g, 26%) was obtained according to the same method as Synthesis Example 7 except that Intermediate I-21 (120 g, 156 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C57H43BFN5O2: 859.3494, found: 859.
Elemental Analysis: C, 80%; H, 5%
Intermediate I-23 (9.91 g, 31%) was obtained according to the same method as Synthesis Example 8 except that Intermediate I-22 (30 g, 34.9 mmol) and Intermediate I-3 (11.4 g, 52.3 mmol) were used.
HRMS (70 eV, EI+): m/z calcd for C64H42FN5O: 915.3373, found: 915.
Elemental Analysis: C, 84%; H, 5%
Intermediate I-24 (8.70 g, 93%) was obtained according to the same method as Synthesis Example 9 except that Intermediate I-23 (9.5 g, 10.4 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C63H40FN5O: 901.3217, found: 901.
Elemental Analysis: C, 84%; H, 4%
Compound 31 (5.95 g, 76%) was obtained according to the same method as Synthesis Example 10 except that Intermediate I-24 (8 g, 8.87 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C63H39N5O: 881.3155, found: 881.
Elemental Analysis: C, 86%; H, 4%
Intermediate I-25 was synthesized according to a method described in KR10-2031300.
HRMS (70 eV, EI+): m/z calcd for C30H20N2: 408.1626, found: 408.
Elemental Analysis: C, 88%; H, 5%
Intermediate I-26 (175 g, 93%) was obtained according to the same method as Synthesis Example 6 except that Intermediate I-25 (100 g, 245 mmol) and Intermediate I-11 (146 g, 367 mmol) were used.
HRMS (70 eV, EI+): m/z calcd for C51H31ClFN5: 767.2252, found: 767.
Elemental Analysis: C, 80%; H, 4%
Intermediate I-27 (38.0 g, 20%) was obtained according to the same method as Synthesis Example 7 except that Intermediate I-26 (170 g, 221 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C57H43BFN5O2: 859.3494, found: 859.
Elemental Analysis: C, 80%; H, 5%
Intermediate I-28 (13.8 g, 37%) was obtained according to the same method as Synthesis Example 8 except that Intermediate I-27 (35 g, 40.7 mmol) and Intermediate I-3 (13.4 g, 61.1 mmol) were used.
HRMS (70 eV, EI+): m/z calcd for C64H42FN5O: 915.3373, found: 915.
Elemental Analysis: C, 84%; H, 5%
Intermediate I-29 (11.6 g, 91%) was obtained according to the same method as Synthesis Example 9 except that Intermediate I-28 (13 g, 14.2 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C63H40FN5O: 901.3217, found: 901.
Elemental Analysis: C, 84%; H, 4%
Compound 32 (7.14 g, 73%) was obtained according to the same method as Synthesis Example 10 except that Intermediate I-29 (10 g, 11.1 mmol) was used.
HRMS (70 eV, EI+): m/z calcd for C63H39N5O: 881.3155, found: 881.
Elemental Analysis: C, 86%; H, 4%
Compound Host 1 was synthesized according to a method described in KR10-2069310.
HRMS (70 eV, EI+): m/z calcd for C51H31N5O: 729.2529, found: 729.
Elemental Analysis: C, 84%; H, 4%
Compound Host 2 was synthesized according to a method described in WO2016-194604.
HRMS (70 eV, EI+): m/z calcd for C45H29N5: 639.2423, found: 639.
Elemental Analysis: C, 84%; H, 5%
Compound Host 3 was synthesized according to a method described in KR2018-0137772.
HRMS (70 eV, EI+): m/z calcd for C57H35N5O: 805.2842, found: 805.
Elemental Analysis: C, 85%; H, 4%
Compound A-136 was synthesized according to a method described in EP3034581.
HRMS (70 eV, EI+): m/z calcd for C42H28N2: 560.2252, found: 560.
Elemental Analysis: C, 90%; H, 5%
Compound A-99 was synthesized according to a method described in KR10-2019-0000597.
HRMS (70 eV, EI+): m/z calcd for C48H32N2: 636.2565, found: 636.
Elemental Analysis: C, 91%; H, 5%
Compound HT5 was synthesized according to a method described in EP2947071.
HRMS (70 eV, EI+): m/z calcd for C48H32N2: 636.2565, found: 636.
Elemental Analysis: C, 91%; H, 5%
Compound B-4 was synthesized according to a method described in KR10-2031300.
HRMS (70 eV, EI+): m/z calcd for C42H28N2: 560.2252, found: 560.
Elemental Analysis: C, 90%; H, 5%
Compound B-57 was synthesized according to a method described in WO2018-095391.
HRMS (70 eV, EI+): m/z calcd for C48H32N2: 636.2565, found: 636.
Elemental Analysis: C, 91%; H, 5%
Under a nitrogen atmosphere, 2,6-dimethoxyphenylboronic acid (100 g, 550 mmol) purchased from Tokyo Chemical Industry Co., Ltd. (http://www.tcichemicals.com/) was dissolved in 1.1 L of tetrahydrofuran (THF) and then, 2-bromo-4-chloro-1-fluorobenzene (115 g, 550 mmol) and tetrakis(triphenylphosphine)palladium (12.7 g, 11.0 mmol) were added thereto, and then, stirred. Potassium carbonate (190 g, 1,375 mmol) saturated in water was added thereto and then, heated under reflux at 80° C. for 12 hours. When a reaction was completed, water was added to the reaction solution and then, extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and then, concentrated under a reduced pressure. The obtained residue was purified through flash column chromatography, obtaining Intermediate I-30 (95.3 g, 65%).
HRMS (70 eV, EI+): m/z calcd for C14H12ClFO2: 266.0510, found: 266.
Elemental Analysis: C, 63%; H, 5%
Intermediate I-30 (95 g, 356 mmol) was used to obtain Intermediate I-31 (77.3 g, 91%) according to the same method as Synthesis Example 9.
HRMS (70 eV, EI+): m/z calcd for C12H8ClFO2: 238.0197, found: 238.
Elemental Analysis: C, 60%; H, 3%
Intermediate I-31 (77 g, 323 mmol) was used to obtain Intermediate I-32 (37.4 g, 53%) according to the same method as Synthesis Example 10.
HRMS (70 eV, EI+): m/z calcd for C12H7ClO2: 218.0135, found: 218.
Elemental Analysis: C, 66%; H, 3%
Under a nitrogen atmosphere, intermediate I-32 (37 g, 169 mmol) was dissolved in 1 L of dichloromethane (DCM), and then, the temperature was lowered to 0° C. Pyridine (57.3 g, 203 mmol) was added thereto, stirred for 30 minutes, trifluoromethanesulfonic anhydride (16.1 g, 203 mmol) was slowly added thereto, and then stirred. After 3 hours, reaction solution was cooled down at 0° C., water was slowly added thereto for 3 hours and then, extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and then, concentrated under a reduced pressure. The obtained residue was purified through flash column chromatography, obtaining Intermediate I-33 (46.2 g, 78%).
HRMS (70 eV, EI+): m/z calcd for C13H6C1F3O4S: 349.9627, found: 350.
Elemental Analysis: C, 45%; H, 2%
Intermediate I-33 (46 g, 131 mmol) and phenyl boronic acid (16.0 g, 131 mmol) were used to obtain Intermediate I-34 (34.7 g, 95%) according to the same method as Synthesis Example 43.
HRMS (70 eV, EI+): m/z calcd for C18H11ClO: 278.0498, found: 278.
Elemental Analysis: C, 78%; H, 4%
Intermediate I-34 (34.0 g, 122 mmol) was used to obtain Intermediate I-35 (33.0 g, 73%) according to the same method as Synthesis Example 7.
HRMS (70 eV, EI+): m/z calcd for C24H23BO3: 370.1740, found: 370.
Elemental Analysis: C, 78%; H, 6%
Intermediate I-35 (33.0 g, 89.1 mmol) and 2,4-dichloro-6-phenyl-1,3,5-triazine (30.2 g, 134 mmol) were used to obtain Intermediate I-36 (19.7 g, 51%) according to the same method as Synthesis Example 43.
HRMS (70 eV, EI+): m/z calcd for C27H16ClN3O: 433.0982, found: 433.
Elemental Analysis: C, 75%; H, 4%
11-(biphenyl-4-yl)-11,12-dihydroindolo[2,3,a]carbazole (10 g, 24.5 mmol) purchased from Ukseung Chemical Co., Ltd. (http://www.ukseung.co.kr/) and Intermediate I-36 (12.8 g, 29.4 mmol) were used to obtain Compound 33 (15.8 g, 80%) according to the same method as Synthesis Example 6.
HRMS (70 eV, EI+): m/z calcd for C57H35N5O: 805.2842, found: 805.
Elemental Analysis: C, 85%; H, 4%
4,4,5,5-tetramethyl-2-(9-phenyldibenzofuran-3-yl)-1,3,2-dioxaborolane (30 g, 81 mmol) purchased from Gemchem (http://www.ytgemchem.com) and 2,4-dichloro-6-phenyl-1,3,5-triazine (27.5 g, 122 mmol) were used to obtain Intermediate I-37 (24.6 g, 70%) according to the same method as Synthesis Example 43.
HRMS (70 eV, EI+): m/z calcd for C27H16ClN3O: 433.0982, found: 433.
Elemental Analysis: C, 75%; H, 4%
11-(biphenyl-4-yl)-11,12-dihydroindolo[2,3,a]carbazole (10 g, 24.5 mmol) purchased from Ukseung Chemical Co., Ltd. (http://www.ukseung.co.kr/) and Intermediate I-37 (12.8 g, 29.4 mmol) were used to obtain Compound 34 (16.8 g, 85%) according to the same method as Synthesis Example 6.
HRMS (70 eV, EI+): m/z calcd for C57H35N5O: 805.2842, found: 805.
Elemental Analysis: C, 85%; H, 4%
4,4,5,5-tetramethyl-2-(9-phenyldibenzofuran-4-yl)-1,3,2-dioxaborolane (30 g, 81 mmol) purchased from Gemchem (http://www.ytgemchem.com) and 2,4-dichloro-6-phenyl-1,3,5-triazine (27.5 g, 122 mmol) were used to obtain Intermediate I-38 (21.8 g, 62%) according to the same method as Synthesis Example 43.
HRMS (70 eV, EI+): m/z calcd for C27H16ClN3O: 433.0982, found: 433.
Elemental Analysis: C, 75%; H, 4%
11-(biphenyl-4-yl)-11,12-dihydroindolo[2,3,a]carbazole (10 g, 24.5 mmol) purchased from Ukseung Chemical Co., Ltd. (http://www.ukseung.co.kr/) and Intermediate I-38 (12.8 g, 29.4 mmol) were used to obtain Compound 35 (15.1 g, 78%) according to the same method as Synthesis Example 6.
HRMS (70 eV, EI+): m/z calcd for C57H35N5O: 805.2842, found: 805.
Elemental Analysis: C, 85%; H, 4%
Phenyl boronic acid (50 g, 410 mmol) purchased from Tokyo chemical industry and 4,6-dibromobenzofuran (160 g, 492 mmol) were used to obtain Intermediate I-39 (45.1 g, 34%) according to the same method as Synthesis Example 43.
HRMS (70 eV, EI+): m/z calcd for C18H11BrO: 321.9993, found: 321.
Elemental Analysis: C, 67%; H, 3%
Intermediate I-39 (44 g, 136 mmol) was used to obtain Intermediate I-40 (35.3 g, 70%) according to the same method as Synthesis Example 7.
HRMS (70 eV, EI+): m/z calcd for C24H23BO3: 370.1740, found: 370.
Elemental Analysis: C, 78%; H, 6%
Intermediate I-40 (35 g, 94.5 mmol) and 2,4-dichloro-6-phenyl-1,3,5-triazine (25.6 g, 113 mmol) were used to obtain Intermediate I-41 (30.8 g, 75%) according to the same method as Synthesis Example 43.
HRMS (70 eV, EI+): m/z calcd for C27H16ClN3O: 433.0982, found: 433.
Elemental Analysis: C, 75%; H, 4%
11-(biphenyl-4-yl)-11,12-dihydroindolo[2,3,a]carbazole (10 g, 24.5 mmol) purchased from Ukseung Chemical Co., Ltd. (http://www.ukseung.co.kr/) and Intermediate I-41 (12.8 g, 29.4 mmol) were used to obtain Compound 73 (12.8 g, 65%) according to the same method as Synthesis Example 6.
HRMS (70 eV, EI+): m/z calcd for C57H35N5O: 805.2842, found: 805.
Elemental Analysis: C, 85%; H, 4%
Phenyl boronic acid (50 g, 410 mmol) purchased from Tokyo chemical industry and 2,8-dibromobenzofuran (160 g, 492 mmol) were used to obtain Intermediate I-42 (39.8 g, 30%) according to the same method as Synthesis Example 43.
HRMS (70 eV, EI+): m/z calcd for C18H11BrO: 321.9993, found: 321.
Elemental Analysis: C, 67%; H, 3%
Intermediate I-42 (39 g, 121 mmol) was used to obtain Intermediate I-43 (37.1 g, 83%) according to the same method as Synthesis Example 7.
HRMS (70 eV, EI+): m/z calcd for C24H23BO3: 370.1740, found: 370.
Elemental Analysis: C, 78%; H, 6%
Intermediate I-43 (37 g, 100 mmol) and 2,4-dichloro-6-phenyl-1,3,5-triazine (27.2 g, 120 mmol) were used to obtain Intermediate I-44 (26.9 g, 62%) according to the same method as Synthesis Example 43.
HRMS (70 eV, EI+): m/z calcd for C27H16ClN3O: 433.0982, found: 433.
Elemental Analysis: C, 75%; H, 4%
11-(biphenyl-4-yl)-11,12-dihydroindolo[2,3,a]carbazole (10 g, 24.5 mmol) purchased from Ukseung Chemical Co., Ltd. (http://www.ukseung.co.kr/) and Intermediate I-44 (12.8 g, 29.4 mmol) were used to obtain Compound 74 (14.0 g, 71%) according to the same method as Synthesis Example 6.
HRMS (70 eV, EI+): m/z calcd for C57H35N5O: 805.2842, found: 805.
Elemental Analysis: C, 85%; H, 4%
Under a nitrogen atmosphere, 1-boromo-4-chloro-2-methoxybenzene (50 g, 226 mmol) purchased from Tokyo Chemical Industry Co., Ltd. was dissolved in 500 mL of tetrahydrofuran, and then, the temperature was lowered to −78° C. 2.5 M of n-BuLi dissolved in hexane (108 mL, 271 mmol) was slowly added thereto in a dropwise fashion for 10 minutes, and after 30 minutes, triisopropyl borate (51.0 g, 271 mmol) was added. When a reaction was completed, the reaction solution was neutralized by adding 1N HCl (271 mL, 271 mmol). And then, extracted with ethylacetate (EA), treated with anhydrous magnesium sulfate to remove moisture. The obtained residue was washed with hexane and dichloromethane (DCM), obtaining Intermediate I-46 (35.8 g, 85%).
HRMS (70 eV, EI+): m/z calcd for C7H8BClO3: 186.0255, found: 186.
Elemental Analysis: C, 45%; H, 4%
Intermediate I-46 (35 g, 188 mmol) and 2-bromo-3-chloro-1-fluorobenzene (39.3 g, 188 mmol) were used to obtain Intermediate I-47 (46.2 g, 91%) according to the same method as Synthesis Example 43.
HRMS (70 eV, EI+): m/z calcd for C13H9Cl2FO: 270.0014, found: 270.
Elemental Analysis: C, 58%; H, 3%
Intermediate I-47 (46 g, 170 mmol) was used to obtain Intermediate I-48 (38.4 g, 88%) according to the same method as Synthesis Example 9.
HRMS (70 eV, EI+): m/z calcd for C12H7Cl2FO: 255.9858, found: 256.
Elemental Analysis: C, 56%; H, 3%
Intermediate I-48 (38 g, 148 mmol) was used to obtain Intermediate I-49 (26.3 g, 75%) according to the same method as Synthesis Example 10.
HRMS (70 eV, EI+): m/z calcd for C12H6Cl2O: 235.9796, found: 236.
Elemental Analysis: C, 61%; H, 3%
Under a nitrogen atmosphere, intermediate I-49 (26 g, 110 mmol) was dissolved in 0.3 L of dioxane, and then, phenyl boronic acid (13.4 g, 110 mmol), tris(diphenylideneacetone)dipalladium(0) (1.01 g, 1.1 mmol), tris-tert butylphosphine (1.11 g, 5.5 mmol) and cesium carbonate (89.6 g, 275 mmol) were added thereto sequentially, heated under reflux at 110° C. for 8 hour. When a reaction was completed, water was added to the reaction solution, extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, filtered, and then, concentrated under a reduced pressure. The obtained residue was purified through flash column chromatography, obtaining Intermediate I-50 (16.9 g, 55%).
HRMS (70 eV, EI+): m/z calcd for C18H11ClO: 278.0498, found: 278.
Elemental Analysis: C, 78%; H, 4%
Intermediate I-50 (16.5 g, 59.2 mmol) was used to obtain Intermediate I-51 (17.5 g, 80%) according to the same method as Synthesis Example 7.
HRMS (70 eV, EI+): m/z calcd for C24H23BO3: 370.1740, found: 370.
Elemental Analysis: C, 78%; H, 6%
Intermediate I-51 (17.0 g, 45.9 mmol) and 2,4-dichloro-6-phenyl-1,3,5-triazine (12.5 g, 55.1 mmol) were used to obtain Intermediate I-52 (14.9 g, 75%) according to the same method as Synthesis Example 43.
HRMS (70 eV, EI+): m/z calcd for C27H16ClN3O: 433.0982, found: 433.
Elemental Analysis: C, 75%; H, 4%
11-(biphenyl-4-yl)-11,12-dihydroindolo[2,3,a]carbazole (10 g, 24.5 mmol) purchased from Ukseung Chemical Co., Ltd. (http://www.ukseung.co.kr/) and Intermediate I-52 (12.8 g, 29.4 mmol) were used to obtain Compound 75 (17.0 g, 86%) according to the same method as Synthesis Example 6.
HRMS (70 eV, EI+): m/z calcd for C57H35N5O: 805.2842, found: 805.
Elemental Analysis: C, 85%; H, 4%
(Manufacture of Organic Light Emitting Diode)
A glass substrate coated with a thin film of indium tin oxide (ITO) was washed with distilled water and ultrasonic waves. After washing with the distilled water, the glass substrate was ultrasonically washed with isopropyl alcohol, acetone, or methanol, 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 doped with 1% NDP-9 (commercially available from Novaled) was vacuum-deposited on an ITO substrate to form a 1,400 Å-thick hole transport layer, and Compound B was deposited on the hole transport layer to form a 350 Å-thick hole transport auxiliary layer. On the hole transport auxiliary layer, Compound 1 and Compound A-136 of the Synthesis Examples were used as a host, and the host was doped with 10 wt % of PhGD as a dopant to form a 400 Å-thick light emitting layer by vacuum deposition. Herein, Compound 1 and Compound A-136 were used in a weight ratio of 3:7. Then, 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 at 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 to finish manufacturing an organic light emitting diode.
ITO/Compound A (1% NDP-9 doping, 1,400 Å)/Compound B (350 Å)/[Compound 1:Compound A-136:PhGD=3:7:10 wt %)] (400 Å)/Compound C (50 Å)/Compound D:LiQ (300 Å)/LiQ (15 Å)/Al (1,200 Å).
Compound A: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine
Compound B: N,N-bis(9,9-dimethyl-9H-fluoren-4-yl)-9,9-spirobi(fluorene)-2-amine
Compound C: 2-(3-(3-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)phenyl)-4,6-diphenyl-1,3,5-triazine
Compound D: 8-(4-(4,6-di(naphthalen-2-yl)-1,3,5-triazin-2-yl)phenyl)quinolone
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 5 was used instead of Compound 1.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 29 was used instead of Compound 1.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 31 was used instead of Compound 1.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 32 was used instead of Compound 1.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound A-99 was used instead of Compound A-136.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound A-31 was used instead of Compound A-136.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound B-4 was used instead of Compound A-136.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound B-57 was used instead of Compound A-136.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 1 and Compound A-136 were used in a weight ratio of 4:6 instead of 3:7.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 1 and Compound A-136 were used in a weight ratio of 2:8 instead of 3:7.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound Host 1 was used instead of Compound 1.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound Host 2 was used instead of Compound 1.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound Host 3 was used instead of Compound 1.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 33 was used instead of Compound 1.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 34 was used instead of Compound 1.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 35 was used instead of Compound 1.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 73 was used instead of Compound 1.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 74 was used instead of Compound 1.
An organic light emitting diode was manufactured according to the same method as Example 1 except that Compound 75 was used instead of Compound 1.
Evaluation
The driving voltages, luminous efficiency, and lifespan characteristics of the organic light emitting diodes according to Examples 1 to 17 and Comparative Examples 1 to 3 were evaluated.
Specific measurement methods are as follows, and the results are shown in Table 1.
(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 of the device 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
Luminous efficiency (cd/A) at the same current density (10 mA/cm2) were calculated by using the luminance, current density, and a voltage from the items (1) and (2).
(4) Measurement of Life-Span
The luminance (cd/m2) at 24,000 cd/m2 was maintained and the time for the current efficiency (cd/A) to decrease to 97% was measured to obtain the results.
(5) Measurement of Driving Voltage
A driving voltage of each diode was measured using a current-voltage meter (Keithley 2400) at 15 mA/cm2.
Referring to Table 1, the organic light emitting diodes according to Examples 1 to 17 exhibited significantly improved driving voltage, luminous efficiency, and life-span characteristics, compared with the organic light emitting diodes according to Comparative Examples 1 to 3.
One or more embodiments may provide a compound for an organic optoelectronic device capable of implement an organic optoelectronic device having high efficiency and a long life-span.
Example embodiments have been disclosed herein, and although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purpose of limitation. In some instances, as would be apparent to one of ordinary skill in the art as of the filing of the present application, features, characteristics, and/or elements described in connection with a particular embodiment may be used singly or in combination with features, characteristics, and/or elements described in connection with other embodiments unless otherwise specifically indicated. Accordingly, it will be understood by those of skill in the art that various changes in form and details may be made without departing from the spirit and scope of the present invention as set forth in the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0146197 | Nov 2020 | KR | national |
| 10-2021-0148039 | Nov 2021 | KR | national |
