Patent Application
20240122066
This application claims priority to and the benefit of Korean Patent Application No. 10-2022-0111658 filed in the Korean Intellectual Property Office on Sep. 2, 2022, 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 (e.g., 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 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 a light emitting device that generates light energy from electrical energy by supplying voltage or current to the electrodes.
Examples of the organic optoelectronic device may 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.
The embodiments may be realized by providing CLAIM LANGUAGE TO BE ADDED
The embodiments may be realized by providing a compound for an organic optoelectronic device, the compound being represented by Chemical Formula 1:
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 as claimed in claim 1, and the second compound is represented by Chemical Formula 2; or a combination of Chemical Formula 3 and Chemical Formula 4,
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 drawing in which:
the FIGURE is a cross-sectional view illustrating an organic light emitting diode according to an embodiment.
Example embodiments will now be described more fully hereinafter with reference to the accompanying drawing; 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 FIGURE, 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.
In the present specification, when a definition is not otherwise provided, “substituted” refers to replacement of at least one hydrogen of a substituent or a compound by deuterium, a halogen, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, a cyano group, or a combination thereof. As used herein, the term “or” is not necessarily an exclusive term, e.g., “A or B” would include A, B, or A and B.
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 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 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 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.
In this specification, “unsubstituted” means that a hydrogen atom remains as a hydrogen atom without being substituted with another substituent.
In this specification, hydrogen substitution (—H) may include deuterium substitution (-D) or tritium substitution (-T), e.g., some deuterium (or tritium) may naturally be included in addition to protium in any compound.
In the present specification, when a definition is not otherwise provided, “hetero” refers to one including one to three heteroatoms selected from N, O, S, P, and Si, and remaining carbons in one functional group.
In the present specification, “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.
In the present specification, “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” refers to an aryl group including at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryl groups are linked by a sigma bond directly, or when the heteroaryl group includes two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may include one to three heteroatoms.
More specifically, the substituted or unsubstituted C6 to C30 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted benzophenanthrenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof, but is not limited thereto.
More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted benzonaphthofuranyl group, a substituted or unsubstituted benzonaphthothiophenyl group, a substituted or unsubstituted benzofuranofluorenyl group, a substituted or unsubstituted benzothiophenefluorenyl group, or a combination thereof, but are not limited thereto.
In the present specification, hole characteristics refer to an ability to donate an electron to form a hole when an electric field is applied and that a hole formed in the anode may be easily injected into the light emitting layer and transported in the light emitting layer due to conductive characteristics according to a highest occupied molecular orbital (HOMO) level.
In addition, electron characteristics refer to an ability to accept an electron when an electric field is applied and that electron formed in the cathode may be easily injected into the light emitting layer and transported in the light emitting layer due to conductive characteristics according to a lowest unoccupied molecular orbital (LUMO) level.
Hereinafter, a compound for an organic optoelectronic device according to an embodiment is described.
The compound for an organic optoelectronic device according to an embodiment may be represented by, e.g., Chemical Formula 1.
In Chemical Formula 1, R1 to R5 may each independently be or include, e.g., hydrogen, deuterium, a cyano group, or a substituted or unsubstituted C1 to C10 alkyl group.
Ar1 and Ar2 may each independently be or include, e.g., a substituted or unsubstituted C6 to C30 aryl group.
m1 to m3 may each independently be, e.g., an integer of 1 to 4.
m4 may be, e.g., an integer of 1 to 3.
m5 may be, e.g., an integer of 1 to 5.
n1 may be, e.g., an integer of 0 to 2.
In an implementation, at least one of R3 and R4 may be deuterium or a C1 to C10 alkyl group substituted with one or more deuterium.
In the compound for an organic optoelectronic element represented by Chemical Formula 1, a 9-carbazole group may be directly or indirectly linked to triazine through p-phenylene, the 9-carbazole group may include a phenyl substituent at position 3, and the triazine group may have a structure including an aryl substituent.
The 9-carbazole group may be linked to the triazine through p-phenylene, and the LUMO electron cloud may expand, thereby lowering a LUMO energy level, further enhancing electron injection and electron transport capabilities, and lowering a driving voltage of a device including the compound.
In addition, the 9-carbazole group may include a phenyl substituent at the 3rd position and the triazine group may include an aryl substituent, and hole injection and hole transport capabilities may also be enhanced to achieve an appropriate charge balance in the light emitting layer, resulting in improvement of efficiency and life-span of the device including the compound.
In an implementation, at least one of R3 and R4 in Chemical Formula 1 may be, e.g., deuterium or a C1 to C10 alkyl group substituted with at least one deuterium.
In an implementation, at least one deuterium substitution may be included, and when deuterium substitution is performed, a ground state energy may be lowered due to lower zero-point energy and lower vibrational energy compared to unsubstituted compounds, and intermolecular interactions may be reduced. It can be made into an amorphous state, and heat resistance may be further improved and life-span of an organic light emitting diode to which it is applied may be more effectively improved. Accordingly, the life-span may be dramatically improved through deuterium substitution.
In an implementation, at least one of R3 and R4 may be deuterium or a C1 to C10 alkyl group substituted with one or more deuterium. In an implementation, at least one R5 may be deuterium or a C1 to C10 alkyl group substituted with one or more deuterium.
In an implementation, at least one of R3 and R4 may be deuterium or a C1 to C10 alkyl group substituted with one or more deuterium, at least one R5 may be a deuterium or a C1 to C10 alkyl group substituted with one or more deuterium, and at least one R2 may be deuterium or a C1 to C10 alkyl group substituted with one or more deuterium.
In an implementation, n1 may be 1 or 2, at least one of R3 and R4 may be a deuterium or a C1 to C10 alkyl group substituted with one or more deuterium, at least one R5 may be a deuterium or a C1 to C10 alkyl group substituted with one or more deuterium, at least one R2 may be deuterium or a C1 to C10 alkyl group substituted with one or more deuterium, and at least one R1 may be a deuterium or a C1 to C10 alkyl group substituted with one or more deuterium.
In an implementation, each of R3 to R5 may be deuterium, m3 may be 4, m4 may be 3, and m5 may be 5.
In an implementation, at least one of R3 and R4 may be deuterium or a C1 to C10 alkyl group substituted with one or more deuterium, at least one R5 may be deuterium or a C1 to C10 alkyl group substituted with one or more deuterium, at least one R2 may be deuterium or a C1 to C10 alkyl group substituted with one or more deuterium, at least one R1 may be deuterium or a C1 to C10 alkyl group substituted with one or more deuterium, and at least one of Ar1 and Ar2 may be a C6 to C30 aryl group substituted with one or more deuterium.
In an implementation, n1 may be 0 or 1.
In an implementation, n1 may be 0, and the compound may be represented by Chemical Formula 1A.
In an implementation, n1 may be 1, and the compound may be represented by Chemical Formula 1B.
In Chemical Formula 1A and Chemical Formula 1B, R1 to R5 may each independently be, e.g., hydrogen, deuterium, a cyano group, or a substituted or unsubstituted C1 to C10 alkyl group.
Ar1 and Ar2 may each independently be, e.g., a substituted or unsubstituted C6 to C30 aryl group,
m1 to m3 may each independently be, e.g., an integer of 1 to 4.
m4 may be, e.g., an integer of 1 to 3.
m5 may be, e.g., an integer of 1 to 5.
In an implementation, at least one of R3 and R4 may be, e.g., deuterium or a C1 to C10 alkyl group substituted with one or more deuterium.
In an implementation, Ar1 and Ar2 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 phenanthrenyl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted fluorenyl group.
In an implementation, Ar1 may 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 phenanthrenyl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted fluorenyl group.
In an implementation, Ar2 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, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted fluorenyl group.
In an implementation, Ar1 and Ar2 may each independently be, e.g., a group Group I.
In Group I, R6 to R10 may each independently be, e.g., hydrogen, deuterium, a cyano group, a substituted or unsubstituted C1 to C10 alkyl group, or substituted or unsubstituted C6 to C12 aryl group.
m6 may be, e.g., an integer of 1 to 5,
m7 may be, e.g., an integer of 1 to 4.
m8 may be, e.g., an integer of 1 to 7.
m9 may be, e.g., an integer of 1 to 3.
m10 may be, e.g., 1 or 2.
* is a linking point.
In an implementation, Chemical Formula 1 may be represented by, e.g., one of Chemical Formula 1C to Chemical Formula 1F.
In Chemical Formula 1C to Chemical Formula 1F, R1 to R5 may each independently be, e.g., hydrogen, deuterium, a cyano group, or a substituted or unsubstituted C1 to C10 alkyl group.
Ar1 and Ar2 may each independently be, e.g., a substituted or unsubstituted C6 to C30 aryl group.
m1 to m3 may each independently be, e.g., an integer of 1 to 4.
m4 may be, e.g., an integer of 1 to 3.
m5 may be, e.g., an integer of 1 to 5.
n1 may be, e.g., an integer of 0 to 2.
In an implementation, any one of Ar1 and Ar2 in Chemical Formula 1C to Chemical Formula 1F may be, e.g., a C6 to C30 aryl group substituted with one or more deuterium.
In an implementation, Ar1 and Ar2 in Chemical Formula 1C to Chemical Formula 1F may each independently be, e.g., a C6 to C30 aryl group substituted with one or more deuterium.
In an implementation, the compound represented by Chemical Formula 1 may be, e.g., a compound of Group 1.
A composition for an organic optoelectronic device according to another embodiment may include, e.g., a first compound and a second compound. In an implementation, the first compound may be the aforementioned compound for an organic optoelectronic device (represented by Chemical Formula 1), and the second compound may be represented by, e.g., Chemical Formula 2; or a combination of Chemical Formula 3 and Chemical Formula 4.
In Chemical Formula 2, R11 to R15 and Ar5 to Ar8 may each independently be or include, e.g., hydrogen, deuterium, a cyano group, a halogen, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.
Ar3 and Ar4 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.
m11, m14, and m15 may each independently be, e.g., an integer of 1 to 4.
m12 and m13 may each independently be, e.g., an integer of 1 to 3.
n2 may be, e.g., an integer of 0 to 2;
In Chemical Formula 3 and Chemical Formula 4, two adjacent ones of a1* to a4* of Chemical Formula 3 may be linking carbons linked at * of Chemical Formula 4, and the remaining two of a1* to a4* of Chemical Formula 3, not linked at * of Chemical Formula 4, may be, e.g., C-La-Ra. As used herein, the term “linking carbon” refers to a shared carbon at which fused rings are linked.
L, L, and L4 may each independently be or include, e.g., a single bond or a substituted or unsubstituted C6 to C20 arylene group.
Ra, Ar11, Ar12, R16, and R17 may each independently be or include, e.g., hydrogen, deuterium, a cyano group, a halogen, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.
Ar9 and Ar10 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.
m16 and m17 may each independently be, e.g., an integer of 1 to 4.
The second compound may be used (e.g., mixed) together with the first compound in the light emitting layer to increase charge mobility and stability, thereby improving luminous efficiency and life-span characteristics.
In an implementation, Ar3 and Ar4 in Chemical Formula 2 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, or a substituted or unsubstituted fluorenyl group.
L1 and L2 in Chemical Formula 2 may each independently be, e.g., a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.
R11 to R15 and Ar5 to Ar8 in Chemical Formula 2 may each independently be, e.g., hydrogen, deuterium, or a substituted or unsubstituted C6 to C12 aryl group.
n2 may be, e.g., 0 or 1.
For example, “substituted” in Chemical Formula 2 may mean that at least one hydrogen is substituted with 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 2 may be represented by, e.g., one of Chemical Formula 2-1 to Chemical Formula 2-15.
In Chemical Formula 2-1 to Chemical Formula 2-15, R11 to R15 and Ar5 to Ar8 may each independently be, e.g., hydrogen, deuterium, or a substituted or unsubstituted C6 to C12 aryl group. Moieties*-L1-Ar3 and *-L2-Ar4 may each independently be, e.g., a moiety of Group II.
In Group II, D is deuterium.
m14 may be, e.g., an integer of 0 to 5.
m15 may be, e.g., an integer of 0 to 7.
m16 may be, e.g., an integer of 0 to 4.
m17 may be, e.g., an integer of 0 to 3.
m18 may be, e.g., an integer of 0 or 2.
* is a linking point.
In an implementation, Chemical Formula 2 may be represented by Chemical Formula 2-8.
In an implementation, moieties *-L1-Ar3 and *-L2-Ar4 in Chemical Formula 2-8 may each independently be a moiety of Group II.
In an implementation, the second compound may be represented by, e.g., a combination of Chemical Formula 3 and Chemical Formula 4.
In Chemical Formula 3 and Chemical Formula 4, two adjacent ones of a1* to a4* of Chemical Formula 3 may be linking carbons linked at * of Chemical Formula 4, and the remaining two of a1* to a4* of Chemical Formula 3, not linked at * of Chemical Formula 4, may be, e.g., C-La-Ra.
La, L3, and L4 may each independently be, e.g., a single bond or a substituted or unsubstituted C6 to C20 arylene group.
Ra, Ar11, Ar12, R16, and R17 may each independently be, e.g., hydrogen, deuterium, a cyano group, a halogen, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.
Ar9 and Ar10 may each independently be, e.g., a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group.
m16 and m17 may each independently be, e.g., an integer of 1 to 4.
In an implementation, the second compound represented by the combination of Chemical Formula 3 and Chemical Formula 4 may be represented by Chemical Formula 3A, Chemical Formula 3B, Chemical Formula 3C, Chemical Formula 3D, or Chemical Formula 3E.
In Chemical Formula 3A to Chemical Formula 3E, Ar9, Ar10, L3, L4, Ar11, Ar12, R16, and R17 may be defined the same as those described above.
La1 to La4 may be defined the same as L3 and L4 described above.
Ra1 to Ra4 may be defined the same as Ar11, Ar12, R16, and R17.
In an implementation, Ar9 and Ar10 in 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.
Ra1 to Ra4, Ar11, Ar12, R16, and R17 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, moieties *-L3-Ar9 and *-L4-Ar10 In Chemical Formula 3 and 4 may each independently be, e.g., a moiety of Group II.
In an implementation, Ra1 to Ra4, Ar11, Ar12, R16, and R17 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, Ra1 to Ra4, Ar11, Ar12, R16, and R17 may each independently be, e.g., hydrogen, deuterium, a cyano group, or a substituted or unsubstituted phenyl group.
In an implementation, Ra1 to Ra4, Ar11, Ar12, R16, and R17 may each independently be, e.g., hydrogen, deuterium, or a substituted or unsubstituted phenyl group.
In an implementation, the second compound may be, e.g., represented by Chemical Formula 2-8, and in Chemical Formula 2-8, Ar3 and Ar4 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, L1 and L2 may each independently be, e.g., a single bond, or a substituted or unsubstituted C6 to C20 arylene group, and Ar5 to Ar8 and R11 to R14 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 may be represented by, e.g., Chemical Formula 3C, and in Chemical Formula 3C, La3 and LM may each 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, Ar11, Ar2, R16, R17, Ra3 and Ra4 may each independently be, e.g., hydrogen, deuterium, or a phenyl group, and Ar9 and Ar10 may each independently be 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 may be, e.g., a compound of Group 2.
In an implementation, examples of Compound B-1 to Compound B-150 listed in Group 2 in which at least one hydrogen is substituted with deuterium may be as follows.
(Dn means the number of deuterium substituted, and represents a structure substituted with one or more deuterium)
For Compound B-151 to Compound B-195 of Group 2, specific structures according to the deuterium substitution position and substitution ratio are exemplarily shown below.
When deuterium is substituted, it is not limited to the compounds exemplified herein, and the deuterium substitution position and deuterium substitution ratio may include all changeable ranges within the ranges of Compound B-1 to Compound B-195 or the other chemical formulae above.
In addition, further examples of Compound C-1 to Compound C-57 listed in Group 2 in which at least one hydrogen is substituted with deuterium are shown below.
(Dn means the number of deuterium substituted, and represents a structure substituted with one or more deuterium)
For Compound C-58 to Compound C-72 of Group 2, specific structures according to the deuterium substitution position and substitution ratio are exemplarily shown herein.
When deuterium is substituted, it is not limited to the compounds exemplified below, and the deuterium substitution position and deuterium substitution ratio may include all changeable ranges within the ranges of Compound C-1 to Compound C-72 or the other chemical formulae.
The first compound and the second compound may be included in a weight ratio of, e.g., about 1:99 to about 99:1. Within the above range, bipolar properties may be implemented by matching an appropriate weight ratio using electron transport capability of the first compound and the hole transport capability of the second compound, to improve efficiency and life-span. Within this range, e.g., they may be included in a weight ratio of about 10:90 to about 90:10, about 20:80 to about 80:20, about 20:80 to about 70:30, about 20:80 to about 60:40, or about 30:70 to about 60:40. As a specific example, they may be included in a weight ratio of about 40:60, about 50:50, or about 60:40.
In addition to the aforementioned first compound and second compound, one or more compounds may be further included.
The aforementioned compound for an organic optoelectronic device or composition for an organic optoelectronic device may be a composition that further includes a dopant.
The dopant may be, e.g., a phosphorescent dopant, for example, a red, green, or blue phosphorescent dopant, and may be, e.g., a red or green phosphorescent dopant.
The dopant may be a material mixed with the compound or composition for an organic optoelectronic device in a small amount to cause light emission, and may be generally a material such as a metal complex that emits light by multiple excitation into a triplet or more. The dopant may be, e.g., an inorganic, organic, or organic/inorganic compound, and one or more types thereof may be used.
Examples of the dopant may include a phosphorescent dopant and examples of the phosphorescent dopant may be an organometal 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, e.g., a compound represented by Chemical Formula Z.
L5MX [Chemical Formula Z]
In Chemical Formula Z, M may be, e.g., a metal, L5 and X may each independently be, e.g., a ligand to form a complex compound with M.
The 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 each independently be, e.g., a bidentate ligand.
Examples of ligands represented by L5 and X may include ligands of Group A.
In Group A, R300 to R302 may each independently be, e.g., hydrogen, deuterium, a C1 to C30 alkyl group that is substituted or unsubstituted with a halogen, a C6 to C30 aryl group that is substituted or unsubstituted with a C1 to C30 alkyl, or a halogen.
R303 to R324 may each independently be, e.g., hydrogen, deuterium, halogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 amino group, a substituted or unsubstituted C6 to C30 arylamino group, SF5, a trialkylsilyl group having a substituted or unsubstituted C1 to C30 alkyl group, a dialkylarylsilyl group having a substituted or unsubstituted C1 to C30 alkyl group and a C6 to C30 aryl group, or a triarylsilyl group having a substituted or unsubstituted C6 to C30 aryl group.
In an implementation, the dopant may be, e.g., represented by Chemical Formula V.
In Chemical Formula V, R101 to R116 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or —SiR132R133R134.
R132 to R134 may each independently be, e.g., a substituted or unsubstituted C1 to C6 alkyl group.
In an implementation, at least one of R101 to R116 may be, e.g., a functional group represented by Chemical Formula V-1.
L100 may be, e.g., a bidentate ligand of a monovalent anion, and is a ligand that coordinates to iridium through a lone pair of carbons or heteroatoms.
m19 and m20 may each independently be, e.g., an integer of 0 to 3, and m19+m20 may be, e.g., an integer of 1 to 3.
In Chemical Formula V-1, R135 to R139 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or —SiR132R133R134.
* is a portion linked to a carbon atom.
In an implementation, a dopant represented by Chemical Formula Z-1 may be included.
In Chemical Formula Z-1, rings A, B, C, and D may each independently represent a 5-membered or 6-membered carbocyclic or heterocyclic ring.
RA, RB, RC, and RD may each independently represent mono-, di-, tri-, or tetra-substitution, or unsubstitution.
LB, LC, and LD may each independently be, e.g., a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO2, CRR′, SiRR′, GeRR′, or a combination thereof.
In an implementation, when nA is 1, LE is selected from a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO2, CRR′, SiRR′, GeRR′, and a combination thereof; when nA is 0, LE does not exist.
RA, RB, RC, RD, R, and R′ may each independently be, e.g., hydrogen, deuterium, a halogen, an alkyl group, a cycloalkyl group, a heteroalkyl group, an arylalkyl group, an alkoxy group, an aryloxy group, an amino group, a silyl group, an alkenyl group, a cycloalkenyl group, a heteroalkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and a combination thereof, any adjacent RA, RB, RC, RD, R, and R′ are optionally linked to each other to provide a ring; XB, XC, XD, and XE are each independently selected from carbon and nitrogen; and Q1, Q2, Q3, and Q4 each represent oxygen or a direct bond.
The dopant according to an embodiment may be a platinum complex, and may be, e.g., represented by Chemical Formula VI.
In Chemical Formula VI, X100 may be, e.g., O, S, or NR31.
R117 to R131 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or —SiR132R133R134.
R132 to R134 may each independently be, a substituted or unsubstituted C1 to C6 alkyl group.
In an implementation, at least one of R117 to R131 may be, e.g., —SiR132R133R134 or a tert-butyl group.
In an implementation, R132 to R134 may each independently be, a substituted or unsubstituted C1 to C6 alkyl group.
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, 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.
The FIGURE is a cross-sectional view illustrating an organic light emitting diode according to an embodiment.
Referring to the FIGURE, an organic light emitting diode 100 according to an embodiment may include an anode 120 and a cathode 110 facing each other and an organic layer 105 between the anode 120 and cathode 110.
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; or 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, and the like, or an alloy thereof, or a multi-layer structure material such as LiF/Al, LiO2/Al, LiF/Ca, LiF/Al, 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 a dopant may be, e.g., a green light emitting composition.
The light emitting layer 130 may include, e.g., the aforementioned compound for an organic optoelectronic device or 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, e.g., a hole transport region 140.
The hole transport region 140 may help further increase hole injection and/or hole mobility and block electrons between the anode 120 and the light emitting layer 130.
In an implementation, 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. In an implementation, 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.
(Dn means the number of deuterium substituted, and represents a structure substituted with one or more deuterium)
In the hole transport region 140, other suitable may be used in addition to the aforementioned compounds.
In an implementation, the charge transport region may be, e.g., an electron transport region 150.
The electron transport region 150 may help further increase electron injection and/or electron mobility and block holes between the cathode 110 and the light emitting layer 130.
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 C 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 a light emitting layer as an organic layer.
Another embodiment may provide an organic light emitting diode including a light emitting layer and a hole transport region as an organic layer.
Another embodiment may provide an organic light emitting diode including a light emitting layer and an electron transport region as an organic layer.
As shown in the FIGURE, the organic light emitting diode according to an embodiment may include a hole transport region 140 and an electron transport region 150 in addition to the light emitting layer 130 as the organic layer 105.
In an implementation, the 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 as the aforementioned organic layer.
The organic light emitting diode 100 may be produced by forming an anode or a cathode on a substrate, forming an organic layer using a dry film formation method such as a vacuum deposition method (evaporation), sputtering, plasma plating, and ion plating, and forming a cathode or an anode thereon.
The organic light emitting diode may be applied to an organic light emitting display device.
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, or P&H tech as far as there is no particular comment or were synthesized by known methods.
(Preparation of Compound for Organic Optoelectronic Device)
1st Step: Synthesis of Intermediate 1-6-1
30 g (123.3 mmol) of 3-phenyl-9H-carbazole, 355.3 mL of benzene-d6, and 92.5 mL (616.5 mmol) of trifluoromethanesulfonic acid (triflic acid) were put in a 1 L round-bottomed flask and heated under reflux under a nitrogen atmosphere. After 48 hours, the reaction solution was cooled, and 460 mL of D2O was added thereto and then, stirred for 30 minutes. 100 g of K3PO4 was added thereto for neutralization, obtaining a white solid. The obtained solid was dissolved in 1 L of toluene and then, silica gel-filtered, and a filtrate therefrom was recrystallized and dried, obtaining 29.5 g (yield: 94%) of Intermediate 1-6-1.
2nd Step: Synthesis of Intermediate 1-6-2
In a 500 mL round-bottomed flask, Intermediate 1-6-1 (29.5 g, 115.5 mmol), 1-bromo-4-chloro-2,3,5,6-tetradeuteriumbenzene (22.6 g, 115.5 mmol), 2.2 g (11.6 mmol) of CuI, 2.1 g (11.6 mmol) of 1,10-phenanthroline, and 24 g (173.3 mmol) of K2CO3 were dissolved in 230 mL of DMF and then, heated under reflux for 12 hours. When a reaction was completed, the resultant was cooled, water was added thereto, and a solid crystallized therein was filtered. The solid was dissolved in toluene, silica gel-filtered, concentrated, and dried, obtaining 36 g (yield: 84%) of Intermediate 1-6-2.
3rd Step: Synthesis of Intermediate 1-6-3
36 g (97.3 mmol) of Intermediate 1-6-2, 29.7 g (116.8 mmol) of bis(pinacolato) diboron, 2.67 g (2.9 mmol) of Pd2(dba)3, 4.1 g (14.6 mmol) of tricyclophosphine, 20.1 g (204.4 mmol) of potassium acetate, and 200 ml of xylene were put in a flask and stirred under reflux for 12 hours. When a reaction was completed, after removing the solvent, the resultant was column-purified, obtaining 36.5 g (yield: 81%) of Intermediate 1-6-3.
4th Step: Synthesis of Compound 1-6
25 g (51.6 mmol) of Intermediate 1-6-3, 16.9 g (55.7 mmol) of 2-[1,1′-biphenyl]-4-yl-4-chloro-6-phenyl-1,3,5-triazine (CAS No. 1472062-94-4), 1.8 g (1.6 mmol) of Pd(PPh3)4, 16.4 g (118.7 mmol) of K2CO3, 170 ml of THF, and 60 ml of distilled water were put in a flask and stirred under reflux for 12 hours. When a reaction was completed, the resultant was cooled to ambient temperature, and a solid produced by adding water thereto was filtered. The solid was dissolved in MCB (monochlorobenzene) and then, silica gel-filtered, recrystallized, and dried, obtaining 25 g (yield: 75%) of Compound 1-6.
In a 250 mL round flask, 1 equivalent of N-phenyl-3,3-bicarbazole, 1 equivalent of 2-bromo-9-phenylcarbazole, 1.5 equivalent of sodium t-butoxide, 0.03 equivalent of tris(dibenzylideneacetone) dipalladium, and 0.06 equivalent of tri t-butylphosphine were mixed with xylene (0.3 M) and then, heated under reflux for 15 hours under a nitrogen flow. The obtained mixture was added to 300 mL of methanol, and a solid crystallized therein was filtered and then, dissolved in dichlorobenzene, filtered with silica gel/Celite, and after removing an appropriate amount of the organic solvent, recrystallized with methanol, obtaining Compound B-139 at a yield of 67%.
Compound C-1 was synthesized in the same manner as in the 4th step of Synthesis Example 1 except that Intermediate C-1-1 (CAS No. 1793049-50-9), and Intermediate C-1-2 (CAS No. 1472729-59-1) were used.
Intermediate C-2-1 was synthesized in the same manner as in the 2nd step of Synthesis Example 1 except that 3-phenyl-9H-carbazole was used instead of Intermediate 1-6-1, and
Compound C-2 was synthesized in the same manner as in the 4th step of Synthesis Example 1 except that Intermediate C-2-1 was used instead of Intermediate 1-6-3.
Compound C-3 was synthesized by referring to Korean Registered Patent No. KR 2430047.
(Manufacture of Organic Light Emitting Diode)
A glass substrate coated with ITO (indium tin oxide) 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 3% NDP-9 (available from Novaled) was vacuum-deposited on the ITO substrate to form a 100 Å-thick hole injection layer, and Compound A was deposited to on the hole injection layer to form a 1,350 Å-thick hole transport layer. On the hole transport layer, a 350 Å-thick hole transport auxiliary layer was formed by depositing Compound B. On the hole transport auxiliary layer, a 400 Å-thick light emitting layer was formed by vacuum-depositing Compound 1-6 obtained in Synthesis Example 1 as a host, which was doped with 7 wt % of PhGD as a dopant. 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 at a ratio of 1:1 to form a 300 Å-thick electron transport layer. LiQ (15 Å) and Al (1,200 Å) were sequentially vacuum-deposited on the electron transport layer to form a cathode, thereby manufacturing an organic light emitting diode.
ITO/Compound A (3% NDP-9 doping, 100 Å)/Compound A (1,350 Å)/Compound B (350 Å)/EML [93 wt % of host (Compound 1-6): 7 wt % of PhGD] (400 Å)/Compound C (50 Å)/Compound D:LiQ (300 Å)/LiQ (15 Å)/Al (1,200 Å).
A glass substrate coated with ITO (indium tin oxide) 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 3% NDP-9 (available from Novaled) was vacuum-deposited on the ITO substrate to form a 100 Å-thick hole injection layer, and Compound E was deposited to on the hole injection layer to form a 1,350 Å-thick hole transport layer. On the hole transport layer, a 350 Å-thick hole transport auxiliary layer was formed by depositing Compound F. On the hole transport auxiliary layer, a 330 Å-thick light emitting layer was formed by simultaneously vacuum-depositing Compound 1-6 obtained in Synthesis Example 1 and Compound B-139 obtained in Synthesis Example 2 as a host, which was doped with 10 wt % of PhGD as a dopant. Subsequently, Compound G was deposited on the light emitting layer to form a 50 Å-thick electron transport auxiliary layer, and Compound H and LiQ were simultaneously vacuum-deposited at a ratio of 1:1 to form a 300 Å-thick electron transport layer. LiQ (15 Å) and Al (1,200 Å) were sequentially vacuum-deposited on the electron transport layer to form a cathode, thereby manufacturing an organic light emitting diode.
ITO/Compound A (3% NDP-9 doping, 100 Å)/Compound E (1,350 Å)/Compound F (350 Å)/EML [90 wt % of host (Compound 1-6: Compound B-139=3:7 w/w): 10 wt % of PhGD] (330 Å)/Compound G (50 Å)/Compound H:LiQ (300 Å)/LiQ (15 Å)/Al (1,200 Å).
As shown in Tables 1 and 2, the diodes according to Comparative Examples 1 and 2 were manufactured in the same manner as in Example 1, except that the host was changed, and the diode according to Comparative Example 3 was manufactured in the same manner as in Example 2, except that the composition was changed.
Evaluation: Measurement of Life-Span
T97 life-spans of the organic light emitting diodes were measured as a time when their luminance decreased down to 97% relative to the initial luminance (cd/m2) after emitting light with 24,000 cd/m2 as the initial luminance (cd/m2) and measuring their luminance decreases depending on a time with a Polanonix life-span measurement system.
Relative values based on T97 life-spans of Comparative Example 1 and Comparative Example 3 are shown in Tables 1 and 2.
Referring to Table 1, the organic light emitting diodes of Example 1 exhibited significantly improved life-span characteristics, compared to the organic light emitting diodes according to the Comparative Examples.
Referring to Table 2, life-span characteristics of the organic light emitting diode of Example 2 were applied were also improved.
One or more embodiments may provide a compound for an organic optoelectronic device capable of realizing an organic optoelectronic device having high efficiency and long life-span.
An organic optoelectronic device having high efficiency and a long life-span may be realized.
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 |
|---|---|---|---|
| 10-2022-0111658 | Sep 2022 | KR | national |
