Patent Application
20230172061
This application claims priority to and the benefit of Korean Patent Application No. 10-2021-0117784 filed in the Korean Intellectual Property Office on Sep. 03, 2021, and Korean Patent Application No. 10-2022-0108580 filed in the Korean Intellectual Property Office on Aug. 29, 2022, the entire contents of which are incorporated herein by reference.
Embodiments relate to 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 that converts electrical energy into photoenergy, and vice versa.
An organic optoelectronic device may be classified as follows in accordance with its driving principles. One is a photoelectric device where excitons generated by photoenergy are separated into electrons and holes and the electrons and holes are transferred to different electrodes respectively and electrical energy is generated, and the other is a light emitting device to generate photoenergy from electrical energy by supplying a voltage or a current to 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 photo conductor drum.
Among them, the organic light emitting diode (OLED) has recently drawn attention due to an increase in demand for flat panel displays. The organic light emitting diode converts electrical energy into light, and the performance of organic light emitting diode is greatly influenced by the organic materials disposed between electrodes.
The embodiments may be realized by providing a composition for an organic optoelectronic device, the composition including a first compound; a second compound; and a third compound, wherein the first compound is represented by Chemical Formula I or Chemical Formula II, the second compound is represented by Chemical Formula III, and the third compound is represented by Chemical Formula IV:
in Chemical Formula I and Chemical Formula II, Z1 to Z6 are each independently N or C—La—Ra, at least two of Z1 to Z3 are N, at least two of Z4 to Z6 are N, X1 is O or S, La and L1 to L6 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, R1, R2, R6, and R7 are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof, Ra, R3 to R5, and R8 are each independently hydrogen, deuterium, 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, a substituted or unsubstituted thioaryl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof, n1 and n4 are each independently an integer of 1 to 3, and n2 and n3 are each independently an integer of 1 to 4, in Chemical Formula I, each Ra is separately present or is linked to R1 or R2 to form a substituted or unsubstituted heteroaromatic polycyclic ring, and R3 to R5 are separately present or adjacent ones thereof are linked to each other to form a substituted or unsubstituted heteroaromatic polycyclic ring, in Chemical Formula II, each Ra is separately present or is linked to R6 or R7 to form a substituted or unsubstituted heteroaromatic polycyclic ring, and ring A is represented by one of Chemical Formula II-1 to Chemical Formula II-14,
in Chemical Formula II-1 to Chemical Formula II-14, X2 is O or S, R9 to R24 are each independently hydrogen, deuterium, 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, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof, n5, n7, n10, n13 to n15, n17, n18, and n20 are each independently an integer of 1 to 4, n6, n8, n9, n11, n12, n16, and n19 are each independently 1 or 2, and * is a linking carbon;
in Chemical Formula III, L7 is a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, Ar1 is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, each R25 is independently hydrogen, deuterium, 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, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof, n21 is an integer of 1 to 4, and ring B is represented by one of Chemical Formula III-1 to Chemical Formula III-4:
in Chemical Formula III-1 to Chemical Formula III-4, L8 and L9 are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, L10 is a single bond or a substituted or unsubstituted C6 to C20 arylene group, Ar2 and Ar3 are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, R26 to R30 are each independently hydrogen, deuterium, 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, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof, n22 and n23 are each independently an integer of 1 to 3, n25 is 1 or 2, n24 and n26 are each independently one of integers from 1 to 4, and * is a linking carbon;
in Chemical Formula IV, L11 is a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, R31 to R37 are each independently hydrogen, deuterium, 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, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof, n27, n28, and n31 to n33 are each independently an integer of 1 to 4, and n29 and n30 are each independently an integer of 1 to 3.
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 for an organic optoelectronic device according to an embodiment.
The embodiments may be realized by providing a display device including 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
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. 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, “substituted” refers to replacement of at least one hydrogen of a substituent or a compound by deuterium, a cyano group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylamine group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, or a C2 to C30 heteroaryl group. In addition, in specific examples, “substituted” refers to replacement of at least one hydrogen of a substituent or a compound by deuterium, a cyano group, a C1 to C20 alkyl group, a C6 to C30 arylamine group, a C6 to C30 aryl group, or a C2 to C30 heteroaryl group. In addition, in specific examples, “substituted” refers to replacement of at least one hydrogen of a substituent or a compound by deuterium, a cyano group, a C1 to C5 alkyl group, a C6 to C20 arylamine group, a C6 to C18 aryl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, or a pyridinyl group. In addition, in specific examples, “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 C6 to C20 arylamine group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a triphenyl group, a fluorenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, or a pyridinyl group.
As used herein, “unsubstituted” refers to non-replacement of a hydrogen atom by another substituent and remaining of the hydrogen atom.
As used herein, “hydrogen substitution (-H)” may include “deuterium substitution (-D)” or “tritium substitution (-T).”
As used herein, when a definition is not otherwise provided, “hetero” refers to one including one to three heteroatoms selected from N, O, S, P, and Si, and remaining carbons in one functional group.
As used herein, “aryl group” refers to a group including at least one hydrocarbon aromatic moiety, and may include a group in which all elements of the hydrocarbon aromatic moiety have p-orbitals which form conjugation, for example a phenyl group, a naphthyl group, and the like, a group in which two or more hydrocarbon aromatic moieties may be linked by a sigma bond, for example a biphenyl group, a terphenyl group, a quarterphenyl group, and the like, and a group in which two or more hydrocarbon aromatic moieties are fused directly or indirectly to provide a non-aromatic fused ring, for example, a fluorenyl group, and the like.
The aryl group may include a monocyclic, polycyclic or fused ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional group.
As used herein, “heterocyclic group” is a generic concept of a heteroaryl group, and may include at least one heteroatom selected from N, O, S, P, and Si instead of carbon (C) in a cyclic compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof. When the heterocyclic group is a fused ring, the entire ring or each ring of the heterocyclic group may include one or more heteroatoms.
For example, “heteroaryl group” refers to an aryl group including at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryl groups are linked by a sigma bond directly, or when the heteroaryl group includes two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may include one to three heteroatoms.
More specifically, the substituted or unsubstituted C6 to C30 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof, but is not limited thereto.
More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzthiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, but is not limited thereto.
In the present specification, hole characteristics refer to an ability to donate an electron to form a hole when an electric field is applied and that a hole formed in the anode may be easily injected into the light emitting layer and transported in the light emitting layer due to conductive characteristics according to the highest occupied molecular orbital (HOMO) level.
In addition, electron characteristics refer to an ability to accept an electron when an electric field is applied and that electron formed in the cathode may be easily injected into the light emitting layer and transported in the light emitting layer due to conductive characteristics according to the lowest unoccupied molecular orbital (LUMO) level.
Hereinafter, a composition for an organic optoelectronic device according to an embodiment is described.
The composition for the organic optoelectronic device according to an embodiment may include a mixture including three types of compounds, e.g., a first compound having electron characteristics, a second compound having hole characteristics, and a third compound having buffer characteristics.
The third compound may be a compound having a wide HOMO-LUMO bandgap including all the HOMO-LUMO bandgaps of the first and second compounds and has lower hole mobility than that of the second compound having hole characteristics and thus may slow down hole injection characteristics, thereby having an effect of reducing hole traps.
In addition, the third compound may have lower electron mobility than that of the first compound, a light emitting region relatively also moves toward a hole transport auxiliary layer, and the third compound may have an effect of reducing exciton quenching on the interface of an electron transport auxiliary layer and deterioration caused by the exciton quenching, increasing life-span.
An example of the first compound having the electron characteristics is a structure in which a triphenylene skeleton is substituted with a nitrogen-containing 6-membered ring, e.g., represented by Chemical Formula I.
In Chemical Formula I, Z1 to Z3 may each independently be, e.g., N or C—La—Ra. In an implementation, at least two of Z1 to Z3 are N.
La and L1 to L3 may each independently be or include, e.g., a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof.
R1 and R2 may each independently be or include, e.g., a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.
Ra and R3 to R5 may each independently be or include, e.g., hydrogen, deuterium, 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, a substituted or unsubstituted thioaryl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof.
In an implementation, each Ra may be separately present or may be linked to R1 or R2 to form a substituted or unsubstituted heteroaromatic polycyclic ring.
n1 may be, e.g., an integer of 1 to 3.
n2 and n3 may each independently be, e.g., an integer of 1 to 4.
In an implementation, Z1 to Z3 of Chemical Formula I may each be N.
In an implementation, Z1 and Z2 may be N, Z3 may be C—La—Ra, La may be a single bond, and Ra may be linked to adjacent R2 to form a substituted or unsubstituted heteroaromatic polycyclic ring, for example, a substituted or unsubstituted benzothiophenepyrimidine.
In an implementation, Z1 and Z3 may be N, Z2 may be C—La—Ra, La may be a single bond, and Ra may be linked to adjacent R1 to form a substituted or unsubstituted heteroaromatic polycyclic ring, for example a substituted or unsubstituted benzothiophenepyrimidine.
In an implementation, Chemical Formula I may be represented by, e.g., one of Chemical Formula I-1 to Chemical Formula I-3.
In Chemical Formula I-1 to Chemical Formula I-3, R1 to R5, L1 to L3 and n1 to n3 may be defined the same as those described above.
R40 and R41 may each independently be, e.g., hydrogen, deuterium, 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, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof.
n40 and n41 may each independently be, e.g., an integer of 1 to 4.
In an implementation, R40 and R41 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group, and n40 and n41 may each independently be, e.g., 1 or 2.
In an implementation, in Chemical Formula I, L1 to L3 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, in Chemical Formula I, R1 and R2 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 carbazolyl group, a substituted or unsubstituted indolocarbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fused carbazolyl group, a substituted or unsubstituted fused dibenzofuranyl group, a substituted or unsubstituted fused dibenzothiophenyl group, a substituted or unsubstituted fused indolocarbazolyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted quinazolinyl group, or a substituted or unsubstituted benzoquinazolinyl group.
In an implementation, in Chemical Formula I, R1 and R2 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 fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.
In an implementation, in Chemical Formula I, R3 to R5 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.
In an implementation, in Chemical Formula I, R3 to R5 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted C1 to C5 alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group, and n1 to n3 may each independently be, e.g., 1 or 2.
In an implementation, adjacent groups of R3 to R5 may be linked to each other to form a substituted or unsubstituted heteroaromatic polycyclic ring, for example, a substituted or unsubstituted benzofuranpyrimidine or a substituted or unsubstituted benzothiophenepyrimidine.
In an implementation, Chemical Formula I may be represented by, e.g., one of Chemical Formula I-4 to Chemical Formula I-6.
In Chemical Formula I-4 to Chemical Formula I-6, Z1 to Z3, R1 to R5, L1 to L3 and n1 to n3 may be defined the same as those described above.
X4 may be, e.g., O or S.
In an implementation, Chemical Formula I may be, e.g., represented by Chemical Formula I-A or Chemical Formula I-B according to the substitution position of the 6-membered ring including Z1 to Z3.
In Chemical Formula I-A and Chemical Formula I-B, Z1 to Z3, L1 to L3, R1 to R5, and n1 to n3 may be defined the same as those described above.
Another example of the first compound having the electronic characteristics is a structure in which a nitrogen-containing 6-membered ring has a structure in which dibenzofuran (dibenzothiophene) or dibenzofuran (dibenzothiophene) derivatives is bound to a nitrogen-containing 6-membered ring, and, e.g., may be represented by Chemical Formula II.
In Chemical Formula II, Z4 to Z6 may each independently be, e.g., N or C—La—Ra. In an implementation, at least two of Z4 to Z6 may be N.
X1 may be, e.g., O or S.
La and L4 to L6 may each independently be or include, e.g., a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof.
R6 and R7 may each independently be or include, e.g., a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.
Ra and R8 may each independently be or include, e.g., hydrogen, deuterium, 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, a substituted or unsubstituted thioaryl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof.
In an implementation, each Ra may be separately present or may be linked to R6 or R7 to form a substituted or unsubstituted heteroaromatic polycyclic ring.
n4 may be, e.g., an integer of 1 to 3.
Ring A may be, e.g., represented by one of Chemical Formula II-1 to Chemical Formula II-14.
In Chemical Formula II-1 to Chemical Formula II-14, X2 may be, e.g., O or S.
R9 to R24 may each independently be or include, e.g., hydrogen, deuterium, 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, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof.
n5, n7, n10, n13 to n15, n17, n18, and n20 may each independently be, e.g., an integer of 1 to 4.
n6, n8, n9, n11, n12, n16, and n19 may each independently be, e.g., 1 or 2.
* is a linking carbon. As used herein, the term “linking carbon” refers to a shared carbon at which fused rings are linked.
In an implementation, Z4 to Z6 in Chemical Formula II may each be N.
In an implementation, Z4 and Z5 may be N, Z6 may be C—La—Ra, La may be a single bond, and Ra may be linked to adjacent R7 to form a substituted or unsubstituted heteroaromatic polycyclic ring, e.g., a substituted or unsubstituted benzothiophenepyrimidine.
In an implementation, Z4 and Z6 may be N, Z5 may be C—La—Ra, La may be a single bond, and Ra may be linked to adjacent R6 to form a substituted or unsubstituted heteroaromatic polycyclic ring, e.g., a substituted or unsubstituted benzothiophenepyrimidine.
In an implementation, the compound represented by Chemical Formula II may be represented by, e.g., one of Chemical Formula II-15 to Chemical Formula II-17.
In Chemical Formula II-15 to Chemical Formula II-17, R6 to R8, L4 to L6, n4, ring A, and X1 may be defined the same as those described above.
R42 and R43 may each independently be, e.g., hydrogen, deuterium, 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, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof.
n42 and n43 may each independently be, e.g., an integer of 1 to 4.
In an implementation , R42 and R43 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C12 aryl group, and n42 and n43 may each independently be, e.g., 1 or 2.
In Chemical Formula II, L4 to L6 may each independently be, e.g., a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.
In Chemical Formula II, R6 and R7 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 carbazolyl group, a substituted or unsubstituted indolocarbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fused carbazolyl group, a substituted or unsubstituted fused dibenzofuranyl group, a substituted or unsubstituted fused dibenzothiophenyl group, a substituted or unsubstituted fused indolocarbazolyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted quinazolinyl group, or a substituted or unsubstituted benzoquinazolinyl group.
In an implementation, in Chemical Formula II, R6 and R7 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 fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.
In an implementation, the compound represented by Chemical Formula II may be, e.g., represented by one of Chemical Formula II-A to Chemical Formula II-W according to the specific structures of the dibenzofuran (dibenzothiophene) and dibenzofuran (dibenzothiophene) derivatives.
In Chemical Formula II-A to Chemical Formula II-W, the variable groups may be defined the same as those described above.
In an implementation, Chemical Formula II may be represented by, e.g., Chemical Formula II-A, Chemical Formula II-E, Chemical Formula II-O, or Chemical Formula II-U.
In an implementation, Chemical Formula II-A may be represented by, e.g., one of Chemical Formula II-A-1 to Chemical Formula II-A-4.
In an implementation, Chemical Formula II-E may be represented by, e.g., one of Chemical Formula II-E-1 to Chemical Formula II-E-4.
In Chemical Formula II-E-1 to Chemical Formula II-E-4, the variable groups may be defined the same as those described above.
In an implementation, Chemical Formula II-O may be represented by, e.g., one of Chemical Formula II-O-1 to Chemical Formula II-O-4.
In Chemical Formula II-O-1 to Chemical Formula II-O-4, the variable groups may be defined the same as those described above.
In an implementation, Chemical Formula II-U may be represented by, e.g., one of Chemical Formula II-U-1 to Chemical Formula II-U-4.
In Chemical Formula II-U-1 to Chemical Formula II-U-4, the variable groups may be defined the same as those described above.
In implementation, the first compound may be represented by, e.g., Chemical Formula I-A, Chemical Formula II-A-3, Chemical Formula II-E-4, Chemical Formula II-O-4, or Chemical Formula II-U-3, and the variable groups may be defined the same as those described above.
In an implementation, the first compound may be, e.g., a compound of Group 1. [Group 1]
The second compound having the hole characteristics may have a structure in which a carbazole or carbazole derivative is substituted with a substituted or unsubstituted C6 to C30 aryl 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 III.
In Chemical Formula III, L7 may be or may include, e.g., a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof.
Ar1 may be or may include, e.g., a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof.
Each R25 may independently be or include, e.g., hydrogen, deuterium, 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, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof.
n21 may be, e.g., an integer of 1 to 4.
Ring B may be represented by, e.g., one of Chemical Formula III-1 to Chemical Formula III-4.
In Chemical Formula III-1 to Chemical Formula III-4, L8 and L9 may each independently be or include, e.g., a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof
L10 may be or may include, e.g., a single bond or a substituted or unsubstituted C6 to C20 arylene group.
Ar2 and Ar3 may each independently be or include, e.g., a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof.
R26 to R30 may each independently be or include, e.g., hydrogen, deuterium, 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, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof.
n22 and n23 may each independently be, e.g., an integer of 1 to 3.
n25 may be, e.g., 1 or 2,
n24 and n26 may each independently be, e.g., an integer of 1 to 4.
* is a linking carbon.
In an implementation, in Chemical Formula III, L7 may be, e.g., a single bond or a substituted or unsubstituted C6 to C12 arylene group.
In an implementation, in Chemical Formula III, L7 may be, e.g., a single bond or a substituted or unsubstituted phenyl group.
In Chemical Formula III, 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 fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.
In an implementation, in Chemical Formula III, Ar1 may be, e.g., a substituted or unsubstituted meta-biphenyl group or a substituted or unsubstituted para-biphenyl group.
In an implementation, Chemical Formula III may be represented by, e.g., one of Chemical Formula III-A to Chemical Formula III-F, according to the specific structures of the carbazole and carbazole derivative.
In Chemical Formula III-A to Chemical Formula III-F, the variable groups may be defined the same as those described above.
In an implementation, in Chemical Formula III-A, R25 toR28 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group, and n21 to n24 may each independently be, e.g., 1 or 2.
In an implementation, in Chemical Formula III-A, L7 and L8 may each independently be, e.g., a single bond or a substituted or unsubstituted C6 to C12 arylene group.
In an implementation, in Chemical Formula III-A, L10 may be, e.g., a single bond or a substituted or unsubstituted C6 to C12 arylene group.
In an implementation, in Chemical Formula III-A, Ar1 and Ar2 may each independently be, e.g., a substituted or unsubstituted phenyl group or 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, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.
In an implementation, in Chemical Formula III-B to Chemical Formula III-F, R25, R29 and R30 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted carbazolyl group.
In an implementation, in Chemical Formula III-B to Chemical Formula III-F, L7 and L9 may each independently be, e.g., a single bond or a substituted or unsubstituted phenylene group.
In an implementation, in Chemical Formula III-B to Chemical Formula III-F, Ar1 and Ar3 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 triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.
In an implementation, in Chemical Formula III-A, R25 to R28 may each independently be, e.g., hydrogen, deuterium, or a substituted or unsubstituted phenyl group.
In an implementation, in Chemical Formula III-A, L7 and L8 may each independently be, e.g., single bond or a substituted or unsubstituted phenylene group.
In an implementation, in Chemical Formula III-A, L10 may be, e.g., a single bond or a substituted or unsubstituted phenylene group.
In an implementation, in Chemical Formula III-A, Ar1 and Ar2 may each independently be, e.g., a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group.
In an implementation, in Chemical Formula III-B to Chemical Formula III-F, R25, R29 and R30 may each independently be, e.g., hydrogen, deuterium, or a substituted or unsubstituted phenyl group.
In an implementation, in Chemical Formula III-B to Chemical Formula III-F, L7 and L9 may each independently be, e.g., a single bond or a substituted or unsubstituted phenylene group.
In an implementation, in Chemical Formula III-B to Chemical Formula III-F, Ar1 and Ar3 may each independently be, e.g., a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group.
In an implementation, the second compound may be represented by, e.g., Chemical Formula III-A or Chemical Formula III-F.
In an implementation, Chemical Formula III-A may be represented by, e.g., one of Chemical Formula III-A-1 to Chemical Formula III-A-3.
In Chemical Formula III-A-1 to Chemical Formula III-A-3, the variable groups may be defined the same as those described above.
In an implementation, the second compound may be represented by, e.g., Chemical Formula III-A-1, Chemical Formula III-A-2, or Chemical Formula III-F.
In an implementation, in Chemical Formula III-A-1 and Chemical Formula III-A-2, L7 and L8 may each independently be, e.g., a single bond or a substituted or unsubstituted phenylene group.
In an implementation, in Chemical Formula III-A-1 and Chemical Formula III-A-2, 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 carbazolyl group, a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothiophenyl group.
In an implementation, in Chemical Formula III-A-1 and Chemical Formula III-A-2, R25 to R28 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., a compound of Group 2. [Group 2]
In an implementation, the third compound having the buffer characteristics may have a structure in which triphenylene is substituted with or bound to a spirofluorene and may be represented by, e.g., Chemical Formula IV.
In Chemical Formula IV, L11 may be or may include, e.g., a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof.
R31 to R37 may each independently be or include, e.g., hydrogen, deuterium, 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, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof.
n27, n28, and n31 to n33 may each independently be, e.g., an integer of 1 to 4.
n29 and n30 may each independently be, e.g., an integer of 1 to 3.
In an implementation, the compound represented by Chemical Formula IV may be, e.g., represented by one of Chemical Formula IV-1 to Chemical Formula IV-4, depending on the specific substitution point of spirofluorene substituted for triphenylene.
In Chemical Formula IV-1 to Chemical Formula IV-4, the variable groups may be defined the same as those described above.
In an implementation, Chemical Formula IV may be represented by Chemical Formula IV-4.
In an implementation, in Chemical Formula IV-4, L11 may be, e.g., a single bond or a substituted or unsubstituted phenylene group.
In an implementation, in Chemical Formula IV-4, R31 to R37 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted carbazolyl group.
In an implementation, in Chemical Formula IV-4, L11 may be, e.g., a substituted or unsubstituted meta-phenylene group or a substituted or unsubstituted para-phenylene group.
In an implementation, in Chemical Formula IV-4, R31 to R37 may each independently be, e.g., hydrogen or deuterium.
In an implementation, the third compound may be, e.g., a compound of Group 3. [Group 3]
The first compound may include a nitrogen-containing 6-membered ring having high electron transport characteristics and may effectively stably and effectively transport electrons and thus lower a driving voltage but increase current efficiency, realizing long life-span characteristics of a device.
The second compound may have a structure including carbazole having high HOMO energy and may effectively inject and transport holes and thus contribute to improving device characteristics.
The third compound may have a wide HOMO-LUMO bandgap, controlling hole and electron movement rates of the first and second compounds and thus may have an effect of preventing hole-trapping and exciton-quenching through relative movement of the light emitting region and thereby contribute to improving life-span characteristics of a device.
In an implementation, the composition for an organic optoelectronic device may include, e.g., the first compound represented by Chemical Formula I-1, the second compound represented by Chemical Formula III-F, and the third compound represented by Chemical Formula IV-4.
In an implementation, the composition for an organic optoelectronic device may include, e.g., the first compound represented by Chemical Formula II-Aa, the second compound represented by Chemical Formula III-A-1, and the third compound represented by Chemical Formula IV-4.
In Chemical Formula II-Aa, L4 to L6 may each independently be, e.g., a single bond, a substituted or unsubstituted phenylene group or a substituted or unsubstituted biphenylene group.
R6 and R7 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 fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.
R8 and R9 may each independently be, e.g., hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.
X1 may be, e.g., O or S.
n4 may be, e.g., an integer of 1 to 3.
n5 may be, e.g., an integer of 1 to 4.
A 3-host composition, e.g., including the first compound, the second compound, and the third compound, compared with a 2-host composition, e.g., a composition including the first and second compounds or a composition including the first and third compounds, may be used to further finely tune electron/hole characteristics within a device stack to achieve an optimal balance, greatly improving device characteristics due to the appropriate charge balance.
The composition, in which the first compound, the second compound, and the third compound are mixed, may be included in a light emitting layer of an organic light emitting diode, which is described below, e.g., as a phosphorescent host.
In the composition for the organic optoelectronic device. the first compound may be included in an amount of, e.g., about 20 wt% to about 50 wt% based on the total weight of the first compound, the second compound, and the third compound, the second compound may be included in an amount of, e.g., about 40 wt% to about 60 wt% based on the total weight of the first compound, the second compound, and the third compound, and the third compound, and the third compound may be included in an amount of, e.g., about 10 wt% to about 30 wt% based on the total weight of the first compound, the second compound, and the third compound, and the third compound.
Within the above ranges, e.g., the first compound for the organic optoelectronic device may be included in an amount of about 25 wt% to about 45 wt% based on the total weight of the first compound for the organic optoelectronic device, the second compound for the organic optoelectronic device, and the third compound for then organic optoelectronic device, the second compound for the organic optoelectronic device may be included in an amount of about 45 wt% to about 60 wt% based on the total weight of the first compound for the organic optoelectronic device, the second compound for the organic optoelectronic device, and the third compound for then organic optoelectronic device, and the third compound for the organic optoelectronic device may be included in an amount of about 10 wt% to about 25 wt% based on the total weight of the first compound for the organic optoelectronic device, the second compound for the organic optoelectronic device, and the third compound for then organic optoelectronic device.
In an implementation, the first compound may be included in an amount of, e.g., about 30 wt% to about 40 wt% based on the total weight of the first compound, the second compound, and the third compound, the second compound may be included in an amount of, e.g., about 45 wt% to about 55 wt% based on the total weight of the first compound, the second compound, and the third compound, and the third compound may be included in an amount of, e.g., about 10 wt% to about 20 wt% based on the total weight of the first compound, the second compound, and the third compound.
In an implementation, the composition for an organic optoelectronic device may include the first compound: the second compound: the third compound in a weight ratio of, e.g., about 35:55:10, or about 32:48:20. Within the above ranges, the electron transport ability of the first compound, the hole transport ability of the second compound, and the buffering ability of the third compound are properly harmonized to improve the efficiency and life-span of the device.
In an implementation, the composition for an organic optoelectronic device may further include one or more compounds in addition to the first compound, the second compound, and the third compound.
In an implementation, the composition for the organic optoelectronic device may further include a dopant. The dopant may be, e.g., a phosphorescent dopant, such as a phosphorescent dopant of red, green or blue, e.g., a green phosphorescent dopant.
The dopant is a material mixed with the composition including the first compound, second compound, and third compound in a small amount to cause light emission and may be 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 include 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.
In Chemical Formula Z, M may be, e.g., a metal, L12 and X3 are the same as or different from each other, and may be, e.g., ligands forming 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 L12 and X3 may be, e.g., a bidentate ligand.
Examples of the ligands represented by L12 and X3 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, and
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, it may include a dopant 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,
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 electrons of carbon or heteroatom,
n1 and n2 may each independently be, e.g., an integer of 0 to 3, and n1 + n2 may be, e.g., an integer of 1 to 3.
In Chemical Formula II-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 (defined the same as that described above).
* is a linking point.
In an implementation, a dopant represented by, e.g., Chemical Formula Z-1 may be included.
In Chemical Formula Z-1, rings A, B, C, and D may each independently be, e.g., a 5-membered or 6-membered carbocyclic or heterocyclic ring;
RA, RB, RC, and RD may each independently represent a, e.g., 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;
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′, or a combination thereof; when nA is 0, LE does not exist; and
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, or 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 NR131,
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, e.g., a substituted or unsubstituted C1 to C6 alkyl group, and
at least one of R117 to R131 may be -SiR132R133R134 or a tert-butyl group.
Hereinafter, an organic optoelectronic device including the aforementioned composition for the 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 photo-conductor drum.
Herein, an organic light emitting diode as one example of an organic optoelectronic device is described referring to drawings.
The
Referring to the
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, 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 composition for the organic optoelectronic device.
The organic layer 105 may include a light emitting layer 130 and the light emitting layer 130 may include the aforementioned composition for the organic optoelectronic device.
The composition for the organic optoelectronic device further including the dopant may be, e.g., a red or green light emitting composition.
The light emitting layer 130 may include, e.g., the aforementioned composition for the organic optoelectronic device.
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 further increase hole injection and/or hole mobility between the anode 120 and the light emitting layer 130 and block electrons.
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 and a compound of Group B may be included in at least one of the hole transport layer and the hole transport auxiliary layer.
In the hole transport region 140, other suitable compounds may be used in addition to the compounds above.
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, and a compound 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
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, or 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 in no particular comment or were synthesized by known methods.
The compound was synthesized through the following steps.
Synthesis Example 1: Synthesis of Compound 1-2
In a round-bottomed flask, 20.00 g (48.16 mmol) of 4,4,5,5-tetramethyl-2-(3-(triphenylene-2-yl)phenyl)-1,3,2-dioxaborolane, 17.38 g (50.56 mmol) of 2-chloro-4-(biphenyl-4-yl)-6-phenyl-1,3,5-triazine, 16.6 g (120.39 mmol) of K2CO3, and 1.67 g (1.67 mmol) of Pd(PPh3)4 were suspended in 140 ml of THF and 60 ml of distilled water under a nitrogen flow and then, stirred under reflux for 8 hours. When a reaction was completed, a THF layer obtained by separating layers was concentrated. The concentrated layer was dissolved in DCB and recrystallized, obtaining 23 g (78%) of Compound 1-2 as a solid.
[Reaction Scheme 2]
1st step: Synthesis of Intermediate 1-3-1
40 g (92.95 mmol) of 4,4,5,5-tetramethyl-2-(3-(triphenylene-2-yl)phenyl)-1,3,2-dioxaborolane, 18.68 g (97.56 mmol) of 1-bromo-3-chlorobenzene, 32.12 g (232.37 mmol) of K2CO3, and 3.22 g (2.79 mmol) of Pd(PPh3)4 were suspended in 240 ml of THF and 120 ml of distilled water under a nitrogen flow and then, stirred under reflux for 8 hours. When a reaction was completed, a THF layer therefrom was concentrated, and a solid therefrom was dissolved in xylene and recrystallized, obtaining 23 g (60%) of Intermediate 1-3-1.
2nd step: Synthesis of Intermediate 1-3-2
23 g (55.43 mmol) of Intermediate 1-3-1, 21.11 g (83.15 mmol) of bis(pinacolato) diboron, 2.26 g (2.77 mmol) of Pd(dppf)Cl2, and 10.88 g (110.86 mmol) of potassium acetate were put in a round-bottomed flask and dissolved in 250 ml of DMF. The mixture was stirred under reflux at 120° C. for 12 hours. When a reaction was completed, the mixture was poured into an excess of distilled water and then, stirred for 1 hour. A solid therefrom was filtered and dissolved in xylene. After removing moisture therefrom with MgSO4, an organic solvent was filtered with a silica gel pad and removed a under a reduced pressure. The solid was recrystallized with xylene, obtaining 26.5 g (89%) of Intermediate 1-3-2.
3rd step: Synthesis of Compound 1-3
26.5 g (52.33 mmol) of Intermediate 1-3-2, 18.89 g (54.94 mmol) of 2-chloro-4-(biphenyl-4-yl)-6-phenyl-1,3,5-triazine, 18.08 g (130.82 mmol) of K2CO3, and 1.81 g (1.57 mmol) of Pd(PPh3)4 were suspended in 140 ml of THF and 70 ml of distilled water under a nitrogen flow and stirred under reflux for 8 hours. When a reaction was completed, MeOH was added thereto, and a solid obtained therefrom was filtered. Subsequently, the solid was dissolved in MCB and then, filtered with a silica gel pad, and an organic solvent therefrom was removed under a reduced pressure. The solid was recrystallized with MCB, obtaining 26.6 g (74%) of Compound 1-3.
Synthesis Example 3: Synthesis of Compound 1-4
In a round-bottomed flask, 26.50 g (96.67 mmol) of 3-p-terphenylboronic acid, 36.32 g (101.51 mmol) of 2-chloro-4-(3-dibenzofuranyl)-6-phenyl-1,3,5-triazine, 33.40 g (241.68 mmol) of K2CO3, and 3.35 g (2.9 mmol) of Pd(PPh3)4 were suspended in 260 ml of THF and 130 ml of distilled water under a nitrogen flow and then, stirred under reflux for 8 hours. When a reaction was completed, the resultant was concentrated and dissolved in toluene. An organic solvent was filtered therefrom with a silica gel pad and removed under a reduced pressure. The solid was recrystallized with toluene, obtaining 44.5 g (83%) of Compound 1-4.
Synthesis Example 4: Synthesis of Compound 2-2
Compound 2-2 was synthesized as described in KR 10-2017-0037277A.
Synthesis Example 5: Synthesis of Compound 2-15
1st step: Synthesis of Intermediate 2-15-1
In a round-bottomed flask, 10.44 g (42.41 mmol) of 4-bromo-9H-carbazole, 11.88 g (42.41 mmol) of 4-iodo-1,1′-biphenyl (Sigma Aldrich Co., Ltd.), 0.388 g (0.424 mmol) of Pd2(dba)3, 0.206 g (0.848 mmol) of P(t-Bu)3, and 6.11 g (63.61 mmol) of NaO(t-Bu) were suspended in 420 ml of toluene and then, stirred at 60° C. for 12 hours. When a reaction was completed, distilled water was added thereto and then, stirred for 30 minutes, and an organic layer extracted therefrom was silica gel-columned (hexane/dichloromethane = 9:1 (v/v)), obtaining 14.70 g (yield: 87%) of Intermediate 2-15-1.
2nd step: Synthesis of Intermediate 2-15-2
In a round-bottomed flask, 15.50 g (38.92 mmol) of Intermediate 2-15-1, 7.15 g (42.81 mmol) of (2-nitrophenyl)-boronic acid, and 16.14 g (116.75 mmol) of potassium carbonate, and 1.35 g (1.17 mmol) of tetrakis(triphenylphosphine) palladium (0) (Pd(PPh3)4) were suspended in 150 ml of toluene and 70 ml of distilled water and then, stirred under reflux for 12 hours. Subsequently, an organic layer extracted therefrom with dichloromethane (DCM) and distilled water was silica gel-filtered. After removing an organic solution therefrom, a solid therefrom was recrystallized with dichloromethane and n-hexane, obtaining 13.72 g (yield: 80%) of Intermediate 2-15-2.
3rd step: Synthesis of Intermediate 2-15-3
22.46 g (51.00 mmol) of Intermediate 2-15-2 and 52.8 ml of triethyl phosphite were put in a round-bottomed flask, and after substituted the atmosphere with nitrogen, the mixture was stirred for 12 hours at 160° C. When a reaction was completed, after adding 3 L of MeOH thereto and then, stirring and filtering the mixture, a filtrate therefrom was volatilized. The residue was purified through column chromatography with hexane, obtaining 10.42 g (yield: 50%) of Intermediate 2-15-3.
4th step: Synthesis of Compound 2-15
Compound 2-15 (yield: 60%) was synthesized in the same manner as in the 1st step of Synthesis Example 7 except that Intermediate 2-15-3 and 1-iodo-3-phenylbenzene were used.
LC/MS (theoretical value: 560.23 g/mol, measured value: 561.57 g/mol)
[Reaction Scheme 5]
1st step: Synthesis of Intermediate Int-3-1
50.3 g (142.1 mmol) of 4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane, 40.2 g (142.1 mmol) of 1-bromo-3-iodobenzene, 29.5 g (213.2 mmol) of K2CO3, and 4.9 g (4.3 mmol) of Pd(PPh3)4 were suspended in 280 ml of THF and 110 ml of distilled water and then, stirred under reflux for 8 hours under a nitrogen flow. When a reaction was completed, the resultant was extracted with DCM and treated through column chromatography (hexane:DCM (20%)), obtaining 39.3 g (78%) of Intermediate Int-3-1 as a solid.
2nd step: Synthesis of Intermediate Int-3-2
77 g (203.3 mmol) of Intermediate Int 3-1, 59.4 g (233.8 mmol) of bis(pinacolato) diboron, 4.8 g (5.9 mmol) of Pd(dppf)Cl2, and 28.9 g (294.8 mmol) of potassium acetate were put in a round-bottomed flask and dissolved in 400 ml of DMF. The mixture was stirred under reflux at 120° C. for 12 hours. When a reaction was completed, the mixture was poured into an excess of distilled water and then, stirred for 1 hour. A solid was filtered therefrom and dissolved in DCM. After removing moisture with MgSO4 therefrom, an organic solvent was filtered therefrom with a silica gel pad and removed under a reduced pressure. A solid obtained therefrom was recrystallized with ethyl acetate and hexane, obtaining 41.8 g (70%) of Intermediate Int-3-2.
3rd step: Synthesis of Compound 3-1
61.2 g (142.1 mmol) of Intermediate Int-3-2, 56.2 g (142.1 mmol) of 4-bromo-9,9′-spirobi[9H-fluorene], 29.5 g (213.2 mmol) of K2CO3, and 4.9 g (4.3 mmol) of Pd(PPh3)4 were suspended in 280 ml of THF and 110 ml of distilled water and then, stirred under reflux for 8 hours for a nitrogen flow. When a reaction was completed, the resultant was extracted with DCM and treated column chromatography (hexane:DCM (20%)), obtaining 39.3 g (78%) of Compound 3-1 as a solid.
LC-Mass (theoretical value: 618.23 g/mol, measured value: M+ = 619.40 g/mol)
[Reaction Scheme 6]
1st step: Synthesis of Intermediate Int-3-3
50.3 g (142.1 mmol) of 4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane, 40.2 g (142.1 mmol) of 1-bromo-4-iodobenzene, 29.5 g (213.2 mmol) of K2CO3, 4.9 g (4.3 mmol) of Pd(PPh3)4 were suspended in 280 ml of THF and 110 ml of distilled water under a nitrogen flow and then, stirred under reflux for 8 hours. When a reaction was completed, the resultant was extracted with DCM and treated through column chromatography (hexane:DCM (20%)), obtaining 43.6 g (80%) of Intermediate Int-3-3 as a solid.
2nd step: Synthesis of Intermediate Int-3-4
77 g (203.3 mmol) of Intermediate Int-3-3, 59.4 g (233.8 mmol) of bis(pinacolato) diboron, 4.8 g (5.9 mmol) of Pd(dppf)Cl2, and 28.9 g (294.8 mmol) of potassium acetate were put in a round-bottomed flask and dissolved in 400 ml of DMF. The mixture was stirred under reflux at 120° C. for 12 hours. When a reaction was completed, the resultant was poured into an excess of distilled water and then, stirred for 1 hour. A solid was filtered therefrom and dissolved in DCM. After removing moisture with MgSO4, an organic solvent was filtered therefrom with a silica gel pad and removed under a reduced pressure. The solid was recrystallized with ethyl acetate and hexane, obtaining 65.6 g (75%) of Intermediate Int-3-4.
3rd step: Synthesis of Compound 3-2
61.2 g (142.1 mmol) of Intermediate Int-3-4, 56.2 g (142.1 mmol) of 4-bromo-9,9′-spirobi[9H-fluorene], 29.5 g (213.2 mmol) of K2CO3, and 4.9 g (4.3 mmol) of Pd(PPh3)4 were suspended in 280 ml of THF and 110 ml of distilled water under a nitrogen flow and then, stirred under reflux for 8 hours. When a reaction was completed, the resultant was extracted with DCM and treated through column chromatography (hexane:DCM (20%)), obtaining 39.3 g (78%) of Compound 3-2 as a solid.
LC-Mass (theoretical value: 618.23 g/mol, measured value: M+ = 619.39 g/mol)
[PtGD]
PtGD was synthesized as described in KR 1999337.
A glass substrate coated with a thin film of indium tin oxide (ITO) was washed with distilled water. 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 A-thick hole injection layer, and Compound A was deposited on the hole transport layer to form a 1,350 Å-thick hole transport layer. On the hole transport layer, Compound B was deposited at a thickness of 350 Å to form a hole transport auxiliary layer. On the hole transport auxiliary layer, a 400 Å-thick light emitting layer was formed by using Compound 1-2, Compound 2-15, and Compound 3-1 simultaneously as a host and doping 15 wt% of PhGD as a dopant by vacuum-deposition. Here, Compound 1-2, Compound 2-15, and Compound 3-1 were used in a weight ratio of 35:55:10 (ratios for the other Examples and Comparative Examples are described below). Subsequently, on the light emitting layer, Compound C was deposited at a thickness of 50 Å to form an electron transport auxiliary layer and Compound D and Liq were simultaneously vacuum-deposited in a weight ratio of 1:1 to form a 300 Å-thick electron transport layer. On the electron transport layer, LiQ and Al were sequentially vacuum-deposited to be 15 Å-thick and 1,200 Å-thick, 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 [{Host (1-2 : 2-15 : 3-1)(85 wt%)} + {Dopant (PtGD)(15 wt%)}] (400 Å)/ compound C 50 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′-(9,9-Dimethyl-9H-fluoren-2-yl)[1,1′-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine
Compound D: 2-[4-[4-(4′-Cyano-1,1′-biphenyl-4-yl)-1-naphthyl]phenyl]-4,6-diphenyl-1,3,5-triazine [PtGD]
Organic light emitting diodes were manufactured in the same manner as in Example 1 except that the composition was changed as shown in Tables 1 to 3.
Organic light emitting diodes were manufactured in the same manner as in Example 1 except that the composition was changed as shown in Tables 1 to 3.
The organic light emitting diodes according to Examples 1 to 3 and Comparative Examples 1 to 6 were measured with respect to efficiency and life-span.
The measurement was performed in the following method, and the results are shown in Tables 1 to 3.
The luminance (cd/m2) was maintained at 24,000 cd/m2 and the time for the current efficiency (cd/A) to decrease to 95% was measured. Relative life-span ratios were calculated based on each life-span of Comparative Examples 1, 3, and 5.
The obtained organic light emitting diodes were measured regarding a current value flowing in the unit device, while increasing the voltage from 0 V to 10 V using a current-voltage meter (Keithley 2400), and the measured current value was divided by area to provide the results.
Luminance was measured by using a luminance meter (Minolta Cs-1000A), while the voltage of the organic light emitting diodes was increased from 0 V to 10 V.
The luminance and the current density measured in the (1) and the (2) and a voltage were used to calculate current efficiency (cd/A) of required luminance 9000 nit. A relative efficiency ratio based on the current efficiency of Comparative Examples 1, 3, and 5 was shown.
Referring to Tables 1 to 3, the organic light emitting diodes according to Examples 1 to 3 exhibited significantly improved current efficiency, compared with the organic light emitting diodes according to Comparative Examples 1 to 6.
One or more embodiments may provide a composition for an organic optoelectronic device capable of realizing high-efficiency and long life-span organic optoelectronic device.
A high-efficiency and long life-span organic optoelectronic device 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 |
|---|---|---|---|
| 10-2021-0117784 | Sep 2021 | KR | national |
| 10-2022-0108580 | Aug 2022 | KR | national |
