ORTHO-SUBSTITUTED THERMALLY ACTIVATED DELAYED FLUORESCENCE MATERIAL AND ORGANIC LIGHT-EMITTING DEVICE COMPRISING SAME

TECHNICAL FIELD

Example embodiments of the present disclosure relate to compounds for an organic light emitting diode and more specifically to thermally activated delayed fluorescence materials as the compounds for the organic light emitting diode.

BACKGROUND ART

OLED (organic light emitting device) is a self-emitting device, and has advantages of fast response time, excellent or suitable brightness, driving voltage and response rate characteristics, and implementing multi-color, as well as wide viewing angle and excellent or suitable contrast.

General organic light emitting diode may include an anode, a cathode, and an organic layer interposed between the anode and the cathode. The organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer and/or the like. When a voltage is applied between the anode and the cathode, holes injected from the anode are moved to the light emitting layer via the hole transport layer, and electrons injected from the cathode moves to the light emitting layer via the electron transport layer. Carriers, such as the holes and electrons, recombine in the light emitting layer to generate excitons, and the excitons transition to a ground state to emit light.

The excitons generated when the organic light emitting diode is driven are stochastically in a singlet state of 25% and a triplet state of 75%. In the case of a fluorescent light emitting material, only excitons in the singlet state which is 25% of total excitons participate in luminescence, and the internal quantum efficiency remains at maximum 25%. In order to improve these properties, iridium or platinum complexes facilitating emitting from the triplet excitons can be utilized, and thereby allowing excellent or suitable quantum efficiency characteristics. However, these materials are expensive, and their applications are limited due to the instability of the blue light emitting material.

In order to solve this problem, recently, a thermally activated delayed fluorescent organic material are being developed. The thermally activated delayed fluorescent organic material has an energy difference of 0.3 eV or less between the singlet state and the triplet state of excitons. In this case, the up-conversion from the triplet state into the singlet state is allowed by heat corresponding to room temperature or device driving temperature, and the theoretical quantum efficiency of nearly 100% can be achieved.

DISCLOSURE
Technical Problem

However, it is known that the actual quantum efficiency of currently developed thermally activated delayed fluorescent organic materials is very different from the theoretical quantum efficiency and still needs to be improved.

Technical Solution

It is an object of example embodiments of the present disclosure to provide a thermally activated delayed fluorescent material and an organic light emitting diode including the same, which can improve quantum efficiency as the transition from a triplet state to a single state can be more efficiently performed.

In some example embodiments, a thermally activated delayed fluorescent (TADF) material is provided. The TADF material has a form in which an electron donating group and an electron withdrawing group are connected to benzene and the electron withdrawing group is position in an ortho position to the electron donating group.

Advantageous Effects

According to example embodiments of the present disclosure, as the compound introduced with the electron donating group and the electron withdrawing group at the ortho positions of the benzene ring can have reduced energy difference between the singlet and triplet excited states, up-conversion of the triplet excited states to the singlet excited states through reverse intersystem crossing by heat at room temperature or device operating temperature can easily occurs, which may result in delayed fluorescence.

DESCRIPTION OF DRAWINGS

Example embodiments of the present disclosure will become more apparent by describing in more detail example embodiments of the present disclosure with reference to the accompanying drawings, in which:

FIG. 1 is a cross-sectional view illustrating an organic light emitting diode according to an example embodiment of the present disclosure;

FIG. 2 shows distribution of molecular orbital of Compound 1 prepared according to Synthesis Example 1, Comparative Compound 2, and Comparative Compound 3;

FIG. 3 is a schematic cross-sectional view of a light-emitting device according to an embodiment;

FIGS. 4 and 5 are cross-sectional views of an electronic device according to an embodiment;

FIG. 6 is a schematic perspective view of an electronic apparatus including a light-emitting device according to an embodiment;

FIG. 7 is a schematic diagram illustrating an exterior of a vehicle as an electronic apparatus including a light-emitting device according to an embodiment; and

FIGS. 8A, 8B, and 8C are schematic diagrams illustrating an interior of a vehicle according to an embodiment.

MODES OF THE INVENTION

Hereinafter, the present disclosure will be described in further detail with reference to several aspects and one or more suitable example embodiments. Hereinafter, example embodiments of the present disclosure will be described in more detail with reference to the accompanying drawings. The embodiments to be described may be modified in several different forms, and the scope of the present disclosure is not limited to the embodiments. Rather, the embodiments are provided to further faithfully and fully explain this disclosure and to fully convey the scope of the present disclosure to those skilled in the art. Like reference numerals in the drawings denote like elements.

As utilized herein, the term “alkyl group” refers to an aliphatic hydrocarbon group, unless otherwise defined. The alkyl group may be a saturated alkyl group which does not contain any double or triple bonds. Or the alkyl group may be an unsaturated alkyl group including at least one double bond or triple bond. The alkyl group, whether saturated or unsaturated, may be branched, straight chain or cyclic. The alkyl group may be a C1 to C30 alkyl group. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, the C1 to C4 alkyl groups may be selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl and t-butyl.

As utilized herein, the term “aryl group” refers to a monocyclic aromatic compound or a polycyclic aromatic compound composed of fused aromatic rings unless otherwise defined, and includes a heteroaryl group.

As utilized herein, “heteroaryl group”, unless otherwise defined, is a monocyclic aromatic compound or a polycyclic aromatic compound composed of fused aromatic rings, which contains at least one heteroatom selected from the group consisting of N, O, S, Se, and P in at least one ring.

As utilized herein, the term “halogen group” refers to a group 7 element, for example, F, Cl, Br, or I, unless otherwise defined. As an example, the halogen group may be F.

When “Cx-Cy” is described in the present specification, the number of carbon atoms corresponding to all the integers between x and y is also to be interpreted as described.

Thermally Activated Delayed Fluorescent (TADF) Material

The following Chemical Formula 1 represents a compound according to one example embodiment of the present disclosure.

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In the Chemical Formula 1,

R_EDGmay be an electron donating group,

R_EWGmay be an electron withdrawing group,

R₅to R₈may be, independently of each other, a hydrogen atom, a heavy hydrogen atom, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 alkylaryl group, a substituted or unsubstituted C6-C30 aralkyl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted fused arylamine group, a substituted or unsubstituted phosphine or phosphine oxide group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide or sulfone group.

The electron donating group may be a substituted or unsubstituted amine group, and the electron withdrawing group may be a substituted or unsubstituted triazine group.

The compound represented by Chemical Formula 1 may be a light emitting material. For example, it may be a thermally activated delayed fluorescent (TADF) material exhibiting thermally activated delayed fluorescence. More specifically, it can be utilized as a light emitting dopant in an organic light emitting device. However, it is not limited to this, and it may be utilized in any layer in the organic light emitting device, or may also be utilized as a host material in the light emitting layer.

The compound represented by Chemical Formula 1 has the form in which the electron donating group and the electron withdrawing group are bonded to benzene, and the electron withdrawing group is positioned in an adjacent position (ortho position) to the electron donating group. Thus, through the effect of steric hindrance by introducing the electron withdrawing group and the electron withdrawing group at ortho positions of benzene to each other, it is possible to control the overlapping of HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) and reduce the difference between the singlet energy (S1) and the triplet energy (T1). For example, as the compound introduced with the electron withdrawing group and the electron withdrawing group at ortho positions of the benzene ring has a minimized or reduced energy difference between the singlet excited state and the triplet excited state (less than 0.3 eV), up-conversion of the triplet excited state to the singlet excited state through reverse intersystem crossing by heat at room temperature or device operating temperature can easily occurs, which may result in delayed fluorescence.

Specific examples of the compound represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 2 to 4.

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In Chemical Formulas 2 to 4, R₁to R₁₂may, independently of each other, represent a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 alkylaryl group, a substituted or unsubstituted C6-C30 aralkyl group, or a substituted or unsubstituted C3-C30 heteroaryl group; R₁and R₂, R₃and R₄, R₅and R₆, R₇and R₈, R₉and R₁₀, or R₁₁and R₁₂may be optionally combined together with the nitrogen to which they are attached to form a substituted or unsubstituted heterocyclyl or a substituted or unsubstituted heteroaryl group.

In Chemical Formulas 2 to 4, R₁₇to R₁₉may be functional groups connected to the triazine group through carbon, nitrogen, oxygen, silicon, sulfur, or phosphorus, and, independently of each other, a cyano group, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 alkylaryl group, a substituted or unsubstituted C6-C30 aralkyl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C1-C30 alkyloxy group, a substituted or unsubstituted C3-C30 aryloxy group, a C1-C9 alkylsilyl group, or a substituted or unsubstituted —NR_aR_b. The R_aand R_bmay be independently selected from the group consisting of hydrogen, heavy hydrogen, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aralkyl group, or a substituted or unsubstituted C3-C30 heteroaryl group. The R_aand R_bmay optionally be combined together with the nitrogen to which they are attached to form a substituted or unsubstituted heterocyclyl or a substituted or unsubstituted heteroaryl group.

Each of R₂₂to R₄₅may be the same as any one of R₅to R₈defined in the above Chemical Formula 1. For example, R₂₂to R₄₅may be, independently of each other, hydrogen, deuterium, a halogen group, a substituted or unsubstituted C4-C6 aryl group, or a substituted or unsubstituted C1-C3 alkyl group. Here, the substituted C1-C3 alkyl group may be a halogen-substituted C1-C3 alkyl group, and the halogen group may be F.

The electron donating group in Chemical Formula 1, or —NR₁R₂, —NR₃R₄, —NR₅R₆, —NR₇R₈, —NR₉R₁₀, or —NR₁₁R₁₂in Chemical Formulas 2 to 4 may be, independently of each other, any one of Structural Formulas A1 to A19, for example, A6, A8, A9 or A10.

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In Structural Formulas A1 to A19,

R₁is the same as R₁in the above Chemical Formula 2,

R₁₁to R₁₄may be, independently of each other, hydrogen, deuterium, a substituted or unsubstituted C1-C2 alkyl group, or a substituted or unsubstituted C6-C30 aryl group,

Sub₁and Sub₂may be, independently of each other, hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 alkylaryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C1-C9 alkyloxy group, a substituted or unsubstituted —NR_cR_d, a substituted or unsubstituted silyl group, a substituted or unsubstituted phosphine group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide group, a substituted or unsubstituted sulfone group, a substituted or unsubstituted C5-C30 arylsilyl group, a substituted or unsubstituted C5-C30 arylthio group, a substituted or unsubstituted C5-C30 aryloxy group, a substituted or unsubstituted C5-C30 arylamine group, or a substituted or unsubstituted C5-C30 aralkyl group. R_cand R_dmay be, independently of each other, selected from the group consisting of a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aralkyl group, or a substituted or unsubstituted C3-C30 heteroaryl group. R_cand R_dmay optionally be joined together with the nitrogen to which they are attached to form a substituted or unsubstituted heterocyclyl or a substituted or unsubstituted heteroaryl. Also, Sub₁and Sub₂may be, regardless of each other, optionally fused to a main body to which they are bonded to form a substituted or unsubstituted cyclic or a substituted or unsubstituted aryl. In particular, when at least one of Sub₁and Sub₂is a substituted or unsubstituted C5-C30 arylsilyl, a substituted or unsubstituted C5-C30 arylthio, a substituted or unsubstituted C5-C30 aryloxy, a substituted or unsubstituted C5-C30 arylamine group, or a substituted or unsubstituted C5-C30 aralkyl group, the aryl group contained therein may be fused to the main body to form a substituted or unsubstituted heterocyclyl or a substituted or unsubstituted heteroaryl.

The electron donating group in Chemical Formula 1, or —NR₁R₂, —NR₃R₄, —NR₅R₆, —NR₇R₈, —NR₉R₁₀, and —NR₁₁R₁₂in Chemical Formulas 2 to 4 may be any of Structural Formulas A20 to A38, independently of each other. In particular, the Structural Formula A9 may be any one of the following Structural Formulas A20 to A38.

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In Structural Formulas A20 to A38,

R₁₁to R₁₄may be, independently of each other, hydrogen, deuterium, a substituted or unsubstituted C1-C2 alkyl group, or a substituted or unsubstituted C6-C30 aryl group,

Sub₁to Sub₄may be, independently of each other, hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 alkylaryl group, a substituted or unsubstituted C6-C30 aralkyl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C1-C9 alkyloxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted silyl group, a substituted or unsubstituted phosphine group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide group, or a substituted or unsubstituted sulfone group.

The electron donating group in Chemical Formula 1, or —NR₁R₂, —NR₃R₄, —NR₅R₆, —NR₇R₈, —NR₉R₁₀, and —NR₁₁R₁₂in Chemical Formulas 2 to 4 may be any of Structural Formulas A39 to A45, independently of each other. In particular, the Structural Formula A10 may be any one of the following Structural Formulas A39 to A45.

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In Structural Formulas A39 to A45,

R₁₁to R₁₄may be, independently of each other, hydrogen, deuterium, a substituted or unsubstituted C1-C2 alkyl group, or a substituted or unsubstituted C6-C30 aryl group,

Examples of the electron withdrawing group in Chemical Formula 1 or the triazine group in Chemical Formula 2 may be the same as the following Structural Formulas B1 to B14.

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In Structural Formulas B1 to B14,

R₁₁and R₁₂may be, independently of each other, hydrogen, deuterium, or a substituted or unsubstituted C1-C2 alkyl group,

Sub₅and Sub₆may be, independently of each other, hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C1-C9 alkyloxy group, a substituted or unsubstituted —NR_eR_f, a substituted or unsubstituted silyl group, a substituted or unsubstituted phosphine group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide group, a substituted or unsubstituted sulfone group, a substituted or unsubstituted C5-C30 arylthio group, a substituted or unsubstituted C5-C30 aryloxy group, a substituted or unsubstituted C5-C30 arylamine group, or a substituted or unsubstituted C5-C30 aralkyl group. Also, Sub₅and Sub₆may be, regardless of each other, optionally fused to a main body to which they are bonded to form a substituted or unsubstituted cyclic or a substituted or unsubstituted aryl. In particular, when Sub₅or Sub₆is a substituted or unsubstituted C5-C30 arylthio, a substituted or unsubstituted C5-C30 aryloxy, a substituted or unsubstituted C5-C30 arylamine group, or a substituted or unsubstituted C5-C30 aralkyl group, the aryl group contained therein may be fused to the main body to form a substituted or unsubstituted heterocyclyl or a substituted or unsubstituted heteroaryl.

R_eand R_fmay be independently selected from the group consisting of a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 alkylaryl group, a substituted or unsubstituted C6-C30 aralkyl group, or a substituted or unsubstituted C3-C30 heteroaryl group. R_eand R_fmay optionally be joined together with the nitrogen to which they are attached to form a substituted or unsubstituted heterocyclyl or a substituted or unsubstituted heteroaryl.

Examples of the electron withdrawing group in the above Chemical Formula 1 or the triazine group substituted with R₁₇and R₁₈in the above Chemical Formula 2 may be the same as the following Structural Formulas B15 to B27. In particular, the Structural Formula B12 may be any one of the following Structural Formulas B15 to B27.

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In Structural Formulas B15 to B27,

R₁₁and R₁₂may be, independently of each other, hydrogen, deuterium, or a substituted or unsubstituted C1-C2 alkyl group.

Examples of the triazine group substituted with R₁₉in the above Chemical Formula 3 may be the same as the following Structural Formulas B28 to B49.

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In Structural Formulas B28 to B49,

R₁₁and R₁₂independently represent hydrogen, deuterium, or a substituted or unsubstituted C1-C2 alkyl group.

Specific examples of the compound represented by Chemical Formula 2 may be represented by the following Chemical Formula 5, and specific examples of the compound represented by Chemical Formula 3 may be represented by the following Chemical Formula 6.

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In Chemical Formula 5, R₁, R₂, and R₂₂to R₂₅are as defined in Chemical Formula 2, and specifically, —NR₁R₂can be any one of Structural Formulas A1 to A45, for example, A6, A8, A9, or A10.

In Chemical Formula 5, Sub₅and Sub₆may be as defined in Structural Formula B12. As an example, at least one of Sub₅and Sub₆may be —NR_eR_f. For example, when either Sub₅and Sub₆is —NR_eR_fand the —NR_eR_fis located at the ortho position with respect to the triazine group, the compound of Chemical Formula 5 may be the same as the compound represented by Chemical Formula 6. When both of Sub₅and Sub₆are —NR_eR_fand both of these —NR_eR_fare located at ortho positions with respect to the triazine group, the compound of Chemical Formula 5 may be the same as the compound represented by Chemical Formula 4.

As an example, examples of the triazine group in the above Chemical Formula 5 may be the same as any of the above Structural Formula B12, and B15 to B27.

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in Chemical Formula 6, R₃, R₄, R₅, R₆, R₂₆to R₂₉, and R₃₀to R₃₃are as defined in Chemical Formula 3 above. For example, the NR₃R₄and NR₅R₆may, regardless of each other, be any of Structural Formulas A1 to A45, for example, A6, A8, A9, or A10.

In Chemical Formula 6, Sub₅is the same as defined in Structural Formula B11. As an example, examples of the triazine group in the above Chemical Formula 6 may be the same as any of the above Structural Formulas B34 to B47.

Specific examples of the compound represented by Chemical Formula 2 may be represented by any one of the following Chemical Formulas 7 to 10.

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Specific examples of the compound represented by Chemical Formula 3 may be represented by the following Chemical Formula 11.

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Specific examples of the compound represented by Chemical Formula 4 may be represented by the following Chemical Formula 12.

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Sub₁and Sub₂of the above Chemical Formulas 7, 11, and 12 may be as defined in Structural Formula A9. As an example, the carbazole group including Sub₁and Sub₂in the above Chemical Formulas 7, 11 and 12 may be any one of the above Structural Formulas A20 to A38. Sub₁and Sub₂of Chemical Formula 8 may be as defined in Structural Formula A8. Sub₁and Sub₂in Chemical Formula 9 may be as defined in Structural Formula A6. Sub₁and Sub₂of Chemical Formula 10 may be as defined in Structural Formula A10. As an example, the acridane group containing Sub₁and Sub₂in Chemical Formula 10 may be any of Structural Formula A39 to A45.

In the above Chemical Formulas 7 to 10, R₁₇and R₁₈may be as defined in the above Chemical Formula 2. As an example, the triazine group including R₁₇to R₁₈may be any of the above-mentioned Structural Formulas B1 to B27. In particular, the triazine group containing R₁₇to R₁₈may be the above-mentioned Structural Formula B12, and specifically, it may be any of the above-mentioned Structural formulas B15 to B27. In the Chemical Formula 11, R₁₉may be the same as defined in the Chemical Formula 3. As another example, the triazine group containing R₁₉may be any of the above Structural Formulas B28 to B49.

In the Chemical Formulas 7 to 12, R₂₂to R₄₅may be, independently of each other, the same as any one of R₅to R₈defined in the above Chemical Formula 1, but specifically, R₂₂to R₄₅independently represent hydrogen, deuterium, a halogen group, a substituted or unsubstituted C4-C6 aryl group, or a substituted or unsubstituted C1-C3 alkyl group. Here, the substituted C1-C3 alkyl group may be a halogen-substituted C1-C3 alkyl group, and the halogen group may be F.

In the above Chemical Formula 10, R₁₁and R₁₂may, regardless of each other, be hydrogen, deuterium, or a substituted or unsubstituted C1-C2 alkyl group.

The thermally activated delayed fluorescent material can implement red, green, and blue luminescent colors by appropriate or suitable introduction of the electron donating group and the electron withdrawing group and reduce the difference between the singlet energy and the triplet energy to 0.3 eV or less.

Specific compounds of such thermally activated delayed fluorescent materials are represented by the following Compounds 1 to 92, but are not limited thereto.

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Compounds 1-21, 31-45, 52, 53, 55-60, 67-74, and 81-86 may be examples of the compounds shown in Chemical Formula 7, Compounds 22-30, 46-48, 75-78, and 89-92 may be examples of the compounds shown in Chemical Formula 8, Compounds 49, 50, 61-66, 87, and 88 may be examples of the compounds shown in Chemical Formula 9, Compounds 51, 54, 79, and 80 may be examples of the compounds shown in Chemical Formula 10, Compounds 67-74 may be examples of the compounds shown in Chemical Formula 11, and Compounds 83-86 may be examples of the compounds shown in Chemical Formula 12.

Description of FIG. 1

FIG. 1 is a schematic cross-sectional view of a light-emitting device 10 according to an embodiment. The light-emitting device 10 may include a first electrode 110, an interlayer 130, and a second electrode 150.

Hereinafter, a structure of the light-emitting device 10 according to an embodiment and a method of manufacturing the light-emitting device 10 will be described with reference to FIG. 1.

First Electrode 110

In FIG. 1, a substrate may be further included under the first electrode 110 and/or on the second electrode 150. In an embodiment, the substrate may be a glass substrate and/or a plastic substrate. In an embodiment, the substrate may be a flexible substrate. For example, the flexible substrate may include plastic(s) with excellent or suitable heat resistance and durability, such as polyimide, polyethylene terephthalate (PET), polycarbonate, polyethylene naphthalate, polyarylate (PAR), polyetherimide, or any combination thereof.

The first electrode 110 may be formed by applying a material for forming the first electrode 110 onto the substrate by utilizing a deposition or sputtering method. When the first electrode 110 is an anode, a material for forming the first electrode 110 may be a high work function material to facilitate injection of holes.

The first electrode 110 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. When the first electrode 110 is a transmissive electrode, a material for forming the first electrode 110 may include indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO₂), zinc oxide (ZnO), or any combination thereof. When the first electrode 110 is a semi-transmissive electrode or a reflective electrode, a material for forming the first electrode 110 may include magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), or any combination thereof.

The first electrode 110 may have a structure including (e.g., consisting of) a single layer or a structure including multiple layers. For example, the first electrode 110 may have a three-layered structure of ITO/Ag/ITO.

Interlayer 130

The interlayer 130 may be disposed on the first electrode 110. The interlayer 130 may include an emission layer.

The interlayer 130 may further include a hole transport region between the first electrode 110 and the emission layer and an electron transport region between the emission layer and the second electrode 150.

The interlayer 130 may further include, in addition to one or more suitable organic materials, a metal-containing compound such as an organometallic compound, an inorganic material such as quantum dots, and/or the like.

The interlayer 130 may include two or more emitting units stacked between the first electrode 110 and the second electrode 150, and at least one charge generation layer located between the two or more emitting units. When the interlayer 130 includes the two or more emitting units and the at least one charge generation layer as described herein, the light-emitting device 10 may be a tandem light-emitting device.

Hole Transport Region in Interlayer 130

The hole transport region may have a structure including (e.g., consisting of) a layer including (e.g., consisting of) a single material, a structure including (e.g., consisting of) a layer including different materials, or a structure including multiple layers including different materials.

The hole transport region may include a hole injection layer, a hole transport layer, an emission auxiliary layer, an electron blocking layer, or any combination thereof.

In embodiments, the hole transport region may have a multi-layered structure including a hole injection layer/hole transport layer structure, a hole injection layer/hole transport layer/emission auxiliary layer structure, a hole injection layer/emission auxiliary layer structure, a hole transport layer/emission auxiliary layer structure, or a hole injection layer/hole transport layer/electron blocking layer structure, wherein the layers of each structure may be stacked from the first electrode 110 in its respective stated order, but the structure of the hole transport region is not limited thereto.

The hole transport region may include a compound represented by Formula 201, a compound represented by Formula 202, or any combination thereof:

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In Formulae 201 and 202,

L₂₀₁to L₂₀₄may each independently be a C₃-C₆₀carbocyclic group that is unsubstituted or substituted with at least one R_10aor a C₁-C₆₀heterocyclic group that is unsubstituted or substituted with at least one R_10a,

L₂₀₅may be *—O—*′, *—N(Q₂₀₁)-*′, a C₁-C₂₀alkylene group unsubstituted or substituted with at least one R_10a, a C₂-C₂₀alkenylene group unsubstituted or substituted with at least one R_10a, a C₃-C₆₀carbocyclic group unsubstituted or substituted with at least one R_10a, or a C₁-C₆₀heterocyclic group unsubstituted or substituted with at least one R_10a,

xa1 to xa4 may each independently be an integer from 0 to 5,

xa5 may be an integer from 1 to 10,

R₂₀₁to R₂₀₄and Q₂₀₁may each independently be a C₃-C₆₀carbocyclic group unsubstituted or substituted with at least one R_10a, or a C₁-C₆₀heterocyclic group unsubstituted or substituted with at least one R_10a,

R₂₀₁and R₂₀₂may optionally be linked to each other via a single bond, a C₁-C₅alkylene group unsubstituted or substituted with at least one R_10a, or a C₂-C₅alkenylene group unsubstituted or substituted with at least one R_10ato form a C₈-C₆₀polycyclic group (for example, a carbazole group and/or the like) unsubstituted or substituted with at least one R_10a(for example, see Compound HT16),

R₂₀₃and R₂₀₄may optionally be linked to each other via a single bond, a C₁-C₅alkylene group unsubstituted or substituted with at least one R_10a, or a C₂-C₅alkenylene group unsubstituted or substituted with at least one R_10ato form a C₈-C₆₀polycyclic group unsubstituted or substituted with at least one R_10a, and

na1 may be an integer from 1 to 4.

In embodiments, the compound represented by Formula 201 and the compound represented by Formula 202 may each independently include at least one of groups represented by Formulae CY201 to CY217:

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In Formulae CY201 to CY217, R_10band R_10cmay each independently be the same as described with respect to R_10a, ring CY₂₀₁to ring CY₂₀₄may each independently be a C₃-C₂₀carbocyclic group or a C₁-C₂₀heterocyclic group, and at least one hydrogen in Formulae CY201 to CY217 may be unsubstituted or substituted with R_10aas described herein.

In an embodiment, in Formulae CY201 to CY217, ring CY₂₀₁to ring CY₂₀₄may each independently be a benzene group, a naphthalene group, a phenanthrene group, or an anthracene group.

In embodiments, the compound represented by Formula 201 and the compound represented by Formula 202 may each independently include at least one of groups represented by Formulae CY201 to CY203.

In embodiments, the compound represented by Formula 201 may include at least one of the groups represented by Formulae CY201 to CY203 and at least one of groups represented by Formulae CY204 to CY217.

In embodiments, in Formula 201, xa1 may be 1, R₂₀₁may be a group represented by one of Formulae CY201 to CY203, xa2 may be 0, and R₂₀₂may be a group represented by one of Formulae CY204 to CY207.

In embodiments, the compound represented by Formula 201 and the compound represented by Formula 202 may each not include a group represented by one of Formulae CY201 to CY203.

In embodiments, the compound represented by Formula 201 and the compound represented by Formula 202 may each not include a group represented by one of Formulae CY201 to CY203, and may each independently include at least one of groups represented by Formulae CY204 to CY217.

In embodiments, the compound represented by Formula 201 and the compound represented by Formula 202 may each not include a group represented by one of Formulae CY201 to CY217.

In an embodiment, the hole transport region may include at least one selected from Compounds HT1 to HT46, m-MTDATA, TDATA, 2-TNATA, NPB(NPD), β-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (PANI/CSA), polyaniline/poly(4-styrenesulfonate) (PANI/PSS), and/or any combination thereof:

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A thickness of the hole transport region may be in a range of about 50 Å to about 10,000 Å. For example, the thickness of the hole transport region may be in a range of about 100 Å to about 4,000 Å. When the hole transport region includes a hole injection layer, a hole transport layer, or any combination thereof, a thickness of the hole injection layer may be in a range of about 100 Å to about 9,000 Å, and a thickness of the hole transport layer may be in a range of about 50 Å to about 2,000 Å. For example, the thickness of the hole injection layer may be in a range of about 100 Å to about 1,000 Å. For example, the thickness of the hole transport layer may be in a range of about 100 Å to about 1,500 Å. When the thicknesses of the hole transport region, the hole injection layer, and the hole transport layer are within these ranges, satisfactory hole transporting characteristics may be obtained without a substantial increase in driving voltage.

The emission auxiliary layer may compensate for an optical resonance distance according to a wavelength of light emitted from the emission layer, so that light emitting efficiency may be improved. The electron blocking layer may prevent or reduce electron leakage from the emission layer to the hole transport region. Materials that may be included in the hole transport region may be included in the emission auxiliary layer and the electron blocking layer.

p-Dopant

The hole transport region may further include, in addition to these materials, a charge-generation material for the improvement of conductive properties. The charge-generation material may be uniformly or non-uniformly dispersed in the hole transport region (for example, in the form of a single layer consisting of a charge-generation material).

The charge-generation material may be, for example, a p-dopant.

For example, a lowest unoccupied molecular orbital (LUMO) energy level of the p-dopant may be equal to or less than about −3.5 eV.

In embodiments, the p-dopant may include a quinone derivative, a cyano group-containing compound, a compound including element EL1 and element EL2, or any combination thereof.

Examples of the quinone derivative may include TCNQ, F4-TCNQ, etc.

Examples of the cyano group-containing compound may include HAT-CN and a compound represented by Formula 221:

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In Formula 221,

R₂₂₁to R₂₂₃may each independently be a C₃-C₆₀carbocyclic group unsubstituted or substituted with at least one R_10aor a C₁-C₆₀heterocyclic group unsubstituted or substituted with at least one R_10a, and

at least one of R₂₂₁to R₂₂₃may each independently be a C₃-C₆₀carbocyclic group or a C₁-C₆₀heterocyclic group, each substituted with: a cyano group; —F; —Cl; —Br; —I; a C₁-C₂₀alkyl group substituted with a cyano group, —F, —Cl, —Br, —I, or any combination thereof; or any combination thereof.

In the compound including element EU and element EL2, element EL1 may be a metal, a metalloid, or any combination thereof, and element EL2 may be a non-metal, a metalloid, or any combination thereof.

Examples of the metal may include: an alkali metal (for example, lithium (Li), sodium (Na), potassium (K), rubidium (R_b), cesium (Cs), etc.); an alkaline earth metal (for example, beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.); a transition metal (for example, titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), etc.); a post-transition metal (for example, zinc (Zn), indium (In), tin (Sn), etc.); and a lanthanide metal (for example, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), etc.).

Examples of the metalloid may include silicon (Si), antimony (Sb), and tellurium (Te).

Examples of the non-metal may include oxygen (O) and a halogen (for example, F, Cl, Br, I, etc.).

Examples of the compound including element EL1 and element EL2 may include a metal oxide, a metal halide (for example, a metal fluoride, a metal chloride, a metal bromide, or a metal iodide), a metalloid halide (for example, a metalloid fluoride, a metalloid chloride, a metalloid bromide, or a metalloid iodide), a metal telluride, or any combination thereof.

Examples of the metal oxide may include tungsten oxide (for example, WO, W₂O₃, WO₂, WO₃, W₂O₅, etc.), vanadium oxide (for example, VO, V₂O₃, VO₂, V₂O₅, etc.), molybdenum oxide (MoO, Mo₂O₃, MoO₂, MoO₃, Mo₂O₅, etc.), and rhenium oxide (for example, ReO₃, etc.).

Examples of the metal halide may include an alkali metal halide, an alkaline earth metal halide, a transition metal halide, a post-transition metal halide, and a lanthanide metal halide.

Examples of the alkali metal halide may include LiF, NaF, KF, RbF, CsF, LiCl, NaCl, KCl, RbCl, CsCl, LiBr, NaBr, KBr, RbBr, CsBr, LiI, NaI, KI, RbI, and CsI.

Examples of the alkaline earth metal halide may include BeF₂, MgF₂, CaF₂, SrF₂, BaF₂, BeCl₂, MgCl₂, CaCl₂), SrCl₂, BaCl₂, BeBr₂, MgBr₂, CaBr₂, SrBr₂, BaBr₂, BeI₂, MgI₂, CaI₂, SrI₂, and BaI₂.

Examples of the transition metal halide may include a titanium halide (for example, TiF₄, TiCl₄, TiBr₄, TiI₄, etc.), a zirconium halide (for example, ZrF₄, ZrCl₄, ZrBr₄, ZrI₄, etc.), a hafnium halide (for example, HfF₄, HfCl₄, HfBr₄, HfI₄, etc.), a vanadium halide (for example, VF₃, VCl₃, VBr₃, VI₃, etc.), a niobium halide (for example, NbF₃, NbCl₃, NbBr₃, NbI₃, etc.), a tantalum halide (for example, TaF₃, TaCl₃, TaBr₃, TaI₃, etc.), a chromium halide (for example, CrF₃, CrCl₃, CrBr₃, CrI₃, etc.), a molybdenum halide (for example, MoF₃, MoCl₃, MoBr₃, MoI₃, etc.), a tungsten halide (for example, WF₃, WCl₃, WBr₃, WI₃, etc.), a manganese halide (for example, MnF₂, MnCl₂, MnBr₂, MnI₂, etc.), a technetium halide (for example, TcF₂, TcCl₂, TcBr₂, TcI₂, etc.), a rhenium halide (for example, ReF₂, ReCl₂, ReBr₂, ReI₂, etc.), an iron halide (for example, FeF₂, FeCl₂, FeBr₂, FeI₂, etc.), a ruthenium halide (for example, RuF₂, RuCl₂, RuBr₂, RuI₂, etc.), an osmium halide (for example, OsF₂, OsCl₂, OsBr₂, OsI₂, etc.), a cobalt halide (for example, CoF₂, CoCl₂, CoBr₂, CoI₂, etc.), a rhodium halide (for example, RhF₂, RhCl₂, RhBr₂, RhI₂, etc.), an iridium halide (for example, IrF₂, IrCl₂, IrBr₂, IrI₂, etc.), a nickel halide (for example, NiF₂, NiCl₂, NiBr₂, NiI₂, etc.), a palladium halide (for example, PdF₂, PdCl₂, PdBr₂, PdI₂, etc.), a platinum halide (for example, PtF₂, PtCl₂, PtBr₂, PtI₂, etc.), a copper halide (for example, CuF, CuCl, CuBr, CuI, etc.), a silver halide (for example, AgF, AgCl, AgBr, AgI, etc.), and a gold halide (for example, AuF, AuCl, AuBr, AuI, etc.).

Examples of the post-transition metal halide may include a zinc halide (for example, ZnF₂, ZnCl₂, ZnBr₂, ZnI₂, etc.), an indium halide (for example, InI₃, etc.), and a tin halide (for example, SnI₂, etc.).

Examples of the lanthanide metal halide may include YbF, YbF₂, YbF₃, SmF₃, YbCl, YbCl₂, YbCl₃SmCl₃, YbBr, YbBr₂, YbBr₃, SmBr₃, YbI, YbI₂, YbI₃, SmI₃, and/or the like.

Examples of the metalloid halide may include an antimony halide (for example, SbCl₅, etc.).

Examples of the metal telluride may include an alkali metal telluride (for example, Li₂Te, Na₂Te, K₂Te, Rb₂Te, Cs₂Te, etc.), an alkaline earth metal telluride (for example, BeTe, MgTe, CaTe, SrTe, BaTe, etc.), a transition metal telluride (for example, TiTe₂, ZrTe₂, HfTe₂, V₂Te₃, Nb₂Te₃, Ta₂Te₃, Cr₂Te₃, Mo₂Te₃, W₂Te₃, MnTe, TcTe, ReTe, FeTe, RuTe, OsTe, CoTe, RhTe, IrTe, NiTe, PdTe, PtTe, Cu₂Te, CuTe, Ag₂Te, AgTe, Au₂Te, etc.), a post-transition metal telluride (for example, ZnTe, etc.), and a lanthanide metal telluride (for example, LaTe, CeTe, PrTe, NdTe, PmTe, EuTe, GdTe, TbTe, DyTe, HoTe, ErTe, TmTe, YbTe, LuTe, etc.).

Emission Layer in Interlayer 130

When the light-emitting device 10 is a full-color light-emitting device, the emission layer may be patterned into a red emission layer, a green emission layer, and/or a blue emission layer, according to a subpixel. In embodiments, the emission layer may have a stacked structure of two or more layers of a red emission layer, a green emission layer, and a blue emission layer, in which the two or more layers may contact each other or may be separated from each other to emit white light. In embodiments, the emission layer may include two or more materials of a red light-emitting material, a green light-emitting material, and a blue light-emitting material, in which the two or more materials may be mixed with each other in a single layer to emit white light.

The emission layer may include a host and a dopant. The dopant may include a phosphorescent dopant, a fluorescent dopant, or any combination thereof.

An amount of the dopant in the emission layer may be in a range of about 0.01 parts by weight to about 15 parts by weight, based on 100 parts by weight of the host.

In embodiments, the emission layer may include a quantum dot.

In embodiments, the emission layer may include a delayed fluorescence material. The delayed fluorescence material may serve as a host or as a dopant in the emission layer.

A thickness of the emission layer may be in a range of about 100 Å to about 1,000 Å. For example, the thickness of the emission layer may be in a range of about 200 Å to about 600 Å. When the thickness of the emission layer is within these ranges, excellent or suitable light-emission characteristics may be obtained without a substantial increase in driving voltage.

Host

In embodiments, the host may include a compound represented by Formula 301:

[Ar₃₀₁]_xb11-[(L₃₀₁)_xb1-R₃₀₁]_xb21 Formula 301

In Formula 301,

Ar₃₀₁and L₃₀₁may each independently be a C₃-C₆₀carbocyclic group unsubstituted or substituted with at least one R_10aor a C₁-C₆₀heterocyclic group unsubstituted or substituted with at least one R_10a,

xb11 may be 1, 2, or 3,

xb1 may be an integer from 0 to 5,

R₃₀₁may be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C₁-C₆₀alkyl group unsubstituted or substituted with at least one R_10a, a C₂-C₆₀alkenyl group unsubstituted or substituted with at least one R_10a, a C₂-C₆₀alkynyl group unsubstituted or substituted with at least one R₁₀a, a C₁-C₆₀alkoxy group unsubstituted or substituted with at least one R_10a, a C₃-C₆₀carbocyclic group unsubstituted or substituted with at least one R_10a, a C₁-C₆₀heterocyclic group unsubstituted or substituted with at least one R_10a, —Si(Q₃₀₁)(Q₃₀₂)(Q₃₀₃), —N(Q₃₀₁)(Q₃₀₂), —B(Q₃₀₁)(Q₃₀₂), —C(═O)(Q₃₀₁), —S(═O)₂(Q₃₀₁), or —P(═O)(Q₃₀₁)(Q₃₀₂),

xb21 may be an integer from 1 to 5, and

Q₃₀₁to Q₃₀₃may each independently be the same as described herein with respect to Q₁.

In an embodiment, in Formula 301, when xb11 is 2 or more, two or more of Ar₃₀₁may be linked to each other via a single bond.

In embodiments, the host may include a compound represented by Formula 301-1, a compound represented by Formula 301-2, or any combination thereof:

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In Formulae 301-1 and 301-2,

ring A₃₀₁to ring A₃₀₄may each independently be a C₃-C₆₀carbocyclic group unsubstituted or substituted with at least one R_10aor a C₁-C₆₀heterocyclic group unsubstituted or substituted with at least one R_10a,

X₃₀₁may be O, S, N-[(L₃₀₄)_xb4-R₃₀₄], C(R₃₀₄)(R₃₀₅), or Si(R₃₀₄)(R₃₀₅),

xb22 and xb23 may each independently be 0, 1, or 2,

L₃₀₁, xb1, and R₃₀₁may each be the same as described herein,

L₃₀₂to L₃₀₄may each independently be the same as described herein with respect to with L₃₀₁,

xb2 to xb4 may each independently be the same as described herein with respect to xb1, and

R₃₀₂to R₃₀₅and R₃₁₁to R₃₁₄may each independently be the same as described herein with respect to R₃₀₁.

In embodiments, the host may include an alkali earth metal complex, a post-transition metal complex, or any combination thereof. For example, the host may include a Be complex (for example, Compound H55), an Mg complex, a Zn complex, or any combination thereof.

In embodiments, the host may include at least one selected from Compounds H1 to H128, 9,10-di(2-naphthyl)anthracene (ADN), 2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN), 9,10-di-(2-naphthyl)-2-t-butyl-anthracene (TBADN), 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP), 1,3-di-9-carbazolylbenzene (mCP), 1,3,5-tri(carbazol-9-yl)benzene (TCP), and/or any combination thereof:

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Phosphorescent Dopant

In embodiments, the phosphorescent dopant may include at least one transition metal as a central metal.

The phosphorescent dopant may include a monodentate ligand, a bidentate ligand, a tridentate ligand, a tetradentate ligand, a pentadentate ligand, a hexadentate ligand, or any combination thereof.

The phosphorescent dopant may be electrically neutral.

In embodiments, the phosphorescent dopant may include an organometallic compound represented by Formula 401:

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In Formulae 401 and 402,

M may be a transition metal (for example, iridium (Ir), platinum (Pt), palladium (Pd), osmium (Os), titanium (Ti), gold (Au), hafnium (Hf), europium (Eu), terbium (Tb), rhodium (Rh), rhenium (Re), or thulium (Tm)),

L₄₀₁may be a ligand represented by Formula 402, and xc1 may be 1, 2, or 3, wherein when xc1 is two or more, two or more of L₄₀₁may be identical to or different from each other,

L₄₀₂may be an organic ligand, and xc2 may be 0, 1, 2, 3, or 4, wherein when xc2 is 2 or more, two or more of L₄₀₂may be identical to or different from each other,

X₄₀₁and X₄₀₂may each independently be nitrogen or carbon,

ring A₄₀₁and ring A₄₀₂may each independently be a C₃-C₆₀carbocyclic group or a C₁-C₆₀heterocyclic group,

T₄₀₁may be a single bond, *—O—*′, *—S—*I, *—C(═O)—*′, *—N(Q₄₁₁)-*′, *—C(Q₄₁₁)(Q₄₁₂)-*′, *—C(Q₄₁₁)=C(Q₄₁₂)-*′, *—C(Q₄₁₁)=*′, or *=C═*′,

X₄₀₃and X₄₀₄may each independently be a chemical bond (for example, a covalent bond or a coordination bond), O, S, N(Q₄₁₃), B(Q₄₁₃), P(Q₄₁₃), C(Q₄₁₃)(Q₄₁₄), or Si(Q₄₁₃)(Q₄₁₄),

Q₄₁₁to Q₄₁₄may each independently be the same as described herein with respect to Q₁,

R₄₀₁and R₄₀₂may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C₁-C₂₀alkyl group unsubstituted or substituted with at least one R_10a, a C₁-C₂₀alkoxy group unsubstituted or substituted with at least one R_10a, a C₃-C₆₀carbocyclic group unsubstituted or substituted with at least one R_10a, a C₁-C₆₀heterocyclic group unsubstituted or substituted with at least one R_10a, —Si(Q₄₀₁)(Q₄₀₂)(Q₄₀₃), —N(Q₄₀₁)(Q₄₀₂), —B(Q₄₀₁)(Q₄₀₂), —C(═O)(Q₄₀₁), —S(═O)₂(Q₄₀₁), or —P(═O)(Q₄₀₁)(Q₄₀₂),

Q₄₀₁to Q₄₀₃may each independently be the same as described herein with respect to Q₁,

xc11 and xc12 may each independently be an integer from 0 to 10, and

* and *′ in Formula 402 each indicate a binding site to M in Formula 401.

In an embodiment, in Formula 402, X₄₀₁may be nitrogen and X₄₀₂may be carbon, or X₄₀₁and X₄₀₂may each be nitrogen.

In embodiments, in Formula 401, when xc1 is 2 or more, two ring A₄₀₁(5) in two or more of L₄₀₁may optionally be linked to each other via T₄₀₂, which is a linking group, and two ring A₄₀₂(s) may optionally be linked to each other via T₄₀₃, which is a linking group (see Compounds PD1 to PD4 and PD7). T₄₀₂and T₄₀₃may each independently be the same as described herein with respect to T₄₀₁.

In Formula 401, L₄₀₂may be an organic ligand. In an embodiment, L₄₀₂may include a halogen group, a diketone group (for example, an acetylacetonate group), a carboxylic acid group (for example, a picolinate group), —C(═O), an isonitrile group, a —CN group, a phosphorus group (for example, a phosphine group, a phosphite group, etc.), or any combination thereof.

The phosphorescent dopant may include, for example, at least one selected from Compounds PD1 to PD39, and/or any combination thereof:

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Fluorescent Dopant

The fluorescent dopant may include an amine group-containing compound, a styryl group-containing compound, or any combination thereof.

In an embodiment, the fluorescent dopant may include a compound represented by Formula 501:

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In Formula 501,

Ar₅₀₁, L₅₀₁to L₅₀₃, R₅₀₁, and R₅₀₂may each independently be a C₃-C₆₀carbocyclic group unsubstituted or substituted with at least one R_10aor a C₁-C₆₀heterocyclic group unsubstituted or substituted with at least one R_10a,

xd1 to xd3 may each independently be 0, 1, 2, or 3, and

xd4 may be 1, 2, 3, 4, 5, or 6.

In an embodiment, in Formula 501, Ar₅₀₁may be a condensed cyclic group (for example, an anthracene group, a chrysene group, or a pyrene group) in which three or more monocyclic groups are condensed together.

In embodiments, in Formula 501, xd4 may be 2.

In an embodiment, the fluorescent dopant may include at least one selected from Compounds FD1 to FD37, DPVBi, DPAVBi, and/or any combination thereof:

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Delayed Fluorescence Material

The emission layer may include a delayed fluorescence material.

In the disclosure, the delayed fluorescence material may be selected from compounds capable of emitting delayed fluorescent light based on a delayed fluorescence emission mechanism.

The delayed fluorescence material included in the emission layer may serve as a host or as a dopant, depending on the types (kinds) of other materials included in the emission layer.

In an embodiment, a difference between a triplet energy level (eV) of the delayed fluorescence material and a singlet energy level (eV) of the delayed fluorescence material may be in a range of about 0 eV to about 0.5 eV. When the difference between the triplet energy level (eV) of the delayed fluorescence material and the singlet energy level (eV) of the delayed fluorescence material satisfies the above-described range, up-conversion from the triplet state to the singlet state of the delayed fluorescence materials may effectively occur, and thus, the luminescence efficiency of the light-emitting device 10 may be improved.

In an embodiment, the delayed fluorescence material may include: a material including at least one electron donor (for example, a π electron-rich C₃-C₆₀cyclic group and/or the like, such as a carbazole group) and at least one electron acceptor (for example, a sulfoxide group, a cyano group, a π electron-deficient nitrogen-containing C₁-C₆₀cyclic group, and/or the like); a material including a C₈-C₆₀polycyclic group in which at least two cyclic groups are condensed to each other while sharing boron (B); and/or the like.

Examples of the delayed fluorescence material may include at least one of Compounds DF1 to DF14:

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Quantum Dot

The emission layer may include a quantum dot.

In the specification, a quantum dot may be a crystal of a semiconductor compound, and may include any material capable of emitting light of one or more suitable emission wavelengths according to a size of the crystal.

A diameter of the quantum dot may be, for example, in a range of about 1 nm to about 10 nm.

The quantum dot may be synthesized by a wet chemical process, a metal organic chemical vapor deposition process, a molecular beam epitaxy process, or any process similar thereto.

The wet chemical process is a method including mixing a precursor material with an organic solvent and growing a quantum dot particle crystal. When the crystal grows, the organic solvent naturally acts as a dispersant coordinated on the surface of the quantum dot crystal and controls the growth of the crystal so that the growth of quantum dot particles can be controlled or selected through a process which costs less, and may be more readily performed than vapor deposition methods, such as metal organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE),

The quantum dot may include a Group II-VI semiconductor compound, a Group III-V semiconductor compound, a Group III-VI semiconductor compound, a

Group semiconductor compound, a Group IV-VI semiconductor compound, a Group IV element or compound, or any combination thereof.

Examples of the Group II-VI semiconductor compound may include: a binary compound, such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, or MgS; a ternary compound, such as CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, or MgZnS; a quaternary compound, such as CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, or HgZnSTe; or any combination thereof.

Examples of the Group III-V semiconductor compound may include: a binary compound, such as GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, or InSb; a ternary compound, such as GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AINP, AINAs, AINSb, AIPAs, AIPSb, InGaP, InNP, InAIP, InNAs, InNSb, InPAs, or InPSb; a quaternary compound, such as GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAINP, InAINAs, InAINSb, InAIPAs, or InAIPSb; or any combination thereof. In an embodiment, the Group III-V semiconductor compound may further include a Group II element. Examples of the Group III-V semiconductor compound further including a Group II element may include InZnP, InGaZnP, InAlZnP, etc.

Examples of the Group III-VI semiconductor compound may include: a binary compound, such as GaS, GaSe, Ga₂Se₃, GaTe, InS, InSe, In₂S₃, In₂Se₃, or InTe; a ternary compound, such as InGaS₃, or InGaSe₃; and any combination thereof.

Examples of the Group semiconductor compound may include: a ternary compound, such as AgInS, AgInS₂, CuInS, CuInS₂, CuGaO₂, AgGaO₂, or AgAlO₂; or any combination thereof.

Examples of the Group IV-VI semiconductor compound may include: a binary compound, such as SnS, SnSe, SnTe, PbS, PbSe, or PbTe; a ternary compound, such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, or SnPbTe; a quaternary compound, such as SnPbSSe, SnPbSeTe, or SnPbSTe; or any combination thereof.

Examples of the Group IV element or compound may include: a single element material, such as Si or Ge; a binary compound, such as SiC or SiGe; or any combination thereof.

Each element included in a multi-element compound such as a binary compound, a ternary compound, or a quaternary compound may be present in a particle at a substantially uniform concentration or at a non-substantially uniform concentration.

In embodiments, the quantum dot may have a single structure in which the concentration of each element in the quantum dot is substantially uniform, or the quantum dot may have a core-shell structure. In an embodiment, in case that the quantum dot has a core-shell structure, a material included in the core and a material included in the shell may be different from each other.

The shell of the quantum dot may serve as a protective layer that prevents chemical degeneration of the core to maintain semiconductor characteristics, and/or may serve as a charging layer that imparts electrophoretic characteristics to the quantum dot. The shell may be a single layer or a multi-layer. An interface between the core and the shell may have a concentration gradient in which the concentration of a material that is present in the shell decreases toward the core.

Examples of the shell of the quantum dot may include a metal oxide, a metalloid oxide, a non-metal oxide, a semiconductor compound, or any combination thereof. Examples of the metal oxide, the metalloid oxide, or the non-metal oxide may include: a binary compound, such as SiO₂, Al₂O₃, TiO₂, ZnO, MnO, Mn₂O₃, Mn₃O₄, CuO, FeO, Fe₂O₃, Fe₃O₄, CoO, Co₃O₄, or NiO; a ternary compound, such as MgAl₂O₄, CoFe₂O₄, NiFe₂O₄, or CoMn₂O₄; or any combination thereof.

Examples of the semiconductor compound may include, as described herein, a Group II-VI semiconductor compound, a Group III-V semiconductor compound, a Group III-VI semiconductor compound, a Group I-III-VI semiconductor compound, a Group IV-VI semiconductor compound, or any combination thereof. Examples of the semiconductor compound may include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnSeS, ZnTeS, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InGaP, InSb, AlAs, AlP, AlSb, or any combination thereof.

A full width at half maximum (FWHM) of an emission wavelength spectrum of the quantum dot may be equal to or less than about 45 nm. For example, a FWHM of an emission wavelength spectrum of the quantum dot may be equal to or less than about 40 nm. For example, a FWHM of an emission wavelength spectrum of the quantum dot may be equal to or less than about 30 nm. Within these ranges, color purity or color reproducibility may be increased. Light emitted through a quantum dot may be emitted in all directions, so that a wide viewing angle may be improved.

In embodiments, the quantum dot may be in the form of a spherical particle, a pyramidal particle, a multi-arm particle, a cubic nanoparticle, a nanotube particle, a nanowire particle, a nanofiber particle, or a nanoplate particle.

Because the energy band gap may be adjusted by controlling the size of the quantum dot, light having one or more suitable wavelength bands may be obtained from a quantum dot emission layer. Accordingly, by utilizing quantum dots of different sizes, a light-emitting device that emits light of one or more suitable wavelengths may be implemented. In embodiments, the size of the quantum dot may be selected to emit red, green, and/or blue light. In an embodiment, the size of the quantum dot may be configured to emit white light by combination of light of one or more suitable colors.

Electron Transport Region in Interlayer 130

The electron transport region may have a structure including (e.g., consisting of) a layer including (e.g., consisting of) a single material, a structure consisting of a layer including different materials, or a structure including multiple layers including different materials.

The electron transport region may include a buffer layer, a hole blocking layer, an electron control layer, an electron transport layer, an electron injection layer, or any combination thereof.

In embodiments, the electron transport region may have an electron transport layer/electron injection layer structure, a hole blocking layer/electron transport layer/electron injection layer structure, an electron control layer/electron transport layer/electron injection layer structure, or a buffer layer/electron transport layer/electron injection layer structure, wherein the layers of each structure may be stacked from an emission layer in its respective stated order, but the structure of the electron transport region is not limited thereto.

In an embodiment, the electron transport region (for example, a buffer layer, a hole blocking layer, an electron control layer, or an electron transport layer in the electron transport region) may include a metal-free compound including at least one π electron-deficient nitrogen-containing C₁-C₆₀cyclic group.

In embodiments, the electron transport region may include a compound represented by Formula 601:

[Ar₆₀₁]_xe11-[(L₆₀₁)_xe1-R₆₀₁]_xe21 Formula 601

In Formula 601,

Ar₆₀₁and L₆₀₁may each independently be a C₃-C₆₀carbocyclic group unsubstituted or substituted with at least one R_10aor a C₁-C₆₀heterocyclic group unsubstituted or substituted with at least one R₁₀a,

xe11 may be 1, 2, or 3,

xe1 may be 0, 1, 2, 3, 4, or 5,

R₆₀₁may be a C₃-C₆₀carbocyclic group unsubstituted or substituted with at least one R_10a, a C₁-C₆₀heterocyclic group unsubstituted or substituted with at least one R_10a, —Si(Q₆₀₁)(Q₆₀₂)(Q₆₀₃), —C(═O)(Q₆₀₁), —S(═O)₂(Q₆₀₁), or —P(═O)(Q₆₀₁)(Q₆₀₂),

Q₆₀₁to Q₆₀₃may each independently be the same as described herein with respect to Q₁,

xe21 may be 1, 2, 3, 4, or 5, and

at least one of Ar₆₀₁, L₆₀₁, and R₆₀₁may each independently be a u electron-deficient nitrogen-containing C₁-C₆₀cyclic group unsubstituted or substituted with at least one R_10a.

In an embodiment, in Formula 601, when xe11 is 2 or more, two or more of Ar₆₀₁may be linked to each other via a single bond.

In embodiments, in Formula 601, Ar₆₀₁may be an anthracene group unsubstituted or substituted with at least one R_10a

In embodiments, the electron transport region may include a compound represented by Formula 601-1:

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In Formula 601-1,

X₆₁₄may be N or C(R₆₁₄), X₆₁₅may be N or C(R₆₁₅), X₆₁₆may be N or C(R₆₁₆), and at least one of X₆₁₄to X₆₁₆may each be N,

L₆₁₁to L₆₁₃may each independently be the same as described herein with respect to L₆₀₁,

xe611 to xe613 may each independently be the same as described herein with respect to xe1,

R₆₁₁to R₆₁₃may each independently be the same as described herein with respect to R₆₀₁, and

R₆₁₄to R₆₁₆may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C₁-C₂₀alkyl group, a C₁-C₂₀alkoxy group, a C₃-C₆₀carbocyclic group unsubstituted or substituted with at least one R_10a, or a C₁-C₆₀heterocyclic group unsubstituted or substituted with at least one R_10a.

In embodiments, in Formulae 601 and 601-1, xe1 and xe611 to xe613 may each independently be 0, 1, or 2.

In embodiments, the electron transport region may include at least one selected from Compounds ET1 to ET45, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), Alq₃, BAlq, TAZ, NTAZ, and/or any combination thereof:

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A thickness of the electron transport region may be in a range of about 100 Å to about 5,000 Å. For example, the thickness of the electron transport region may be 25 in a range of about 160 Å to about 4,000 Å. When the electron transport region includes a buffer layer, a hole blocking layer, an electron control layer, an electron transport layer, or any combination thereof, a thickness of the buffer layer, the hole blocking layer, or the electron control layer may each independently be in a range of about 20 Å to about 1,000 Å, and a thickness of the electron transport layer may be in a range of about 100 Å to about 1,000 Å, for example. For example, the thickness of the buffer layer, the hole blocking layer, or the electron control layer may each independently be in a range of about 30 Å to about 300 Å. For example, the thickness of the electron transport layer may be in a range of about 150 Å to about 500 Å. When the thickness of the buffer layer, the hole blocking layer, the electron control layer, the electron transport layer, and/or the electron transport region are within these ranges, satisfactory electron transporting characteristics may be obtained without a substantial increase in driving voltage.

The electron transport region (for example, an electron transport layer in the electron transport region) may further include, in addition to the materials described above, a metal-containing material.

The metal-containing material may include an alkali metal complex, an alkaline earth metal complex, or any combination thereof. A metal ion of an alkali metal complex may be a Li ion, a Na ion, a K ion, a Rb ion, or a Cs ion, and a metal ion of an alkaline earth metal complex may be a Be ion, a Mg ion, a Ca ion, a Sr ion, or a Ba ion.

A ligand coordinated with the metal ion of the alkali metal complex or with the metal ion of the alkaline earth-metal complex may each independently include a hydroxyquinoline, a hydroxyisoquinoline, a hydroxybenzoquinoline, a hydroxyacridine, a hydroxyphenanthridine, a hydroxyphenyloxazole, a hydroxyphenylthiazole, a hydroxyphenyloxadiazole, a hydroxyphenylthiadiazole, a hydroxyphenylpyridine, a hydroxyphenylbenzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or any combination thereof.

For example, the metal-containing material may include a lithium (Li) complex. The Li complex may include, for example, Compound ET-D1 (LiQ) or Compound ET-D2:

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The electron transport region may include an electron injection layer that facilitates the injection of electrons from the second electrode 150. The electron injection layer may directly contact the second electrode 150.

The electron injection layer may have a structure consisting of a layer consisting of a single material, a structure consisting of a layer including different materials, or a structure including multiple layers including different materials.

The electron injection layer may include an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal-containing compound, an alkaline earth metal-containing compound, a rare earth metal-containing compound, an alkali metal complex, an alkaline earth metal complex, a rare earth metal complex, or any combination thereof.

The alkali metal may include Li, Na, K, Rb, Cs, or any combination thereof. The alkaline earth metal may include Mg, Ca, Sr, Ba, or any combination thereof. The rare earth metal may include Sc, Y, Ce, Tb, Yb, Gd, or any combination thereof.

The alkali metal-containing compound, the alkaline earth metal-containing compound, and the rare earth metal-containing compound may be oxides, halides (for example, fluorides, chlorides, bromides, or iodides), or tellurides of the alkali metal, the alkaline earth metal, and the rare earth metal, or any combination thereof.

The alkali metal-containing compound may include: alkali metal oxides, such as Li₂O, Cs₂O, or K₂O; alkali metal halides, such as LiF, NaF, CsF, KF, LiI, NaI, CsI, or KI; or any combination thereof. The alkaline earth metal-containing compound may include an alkaline earth metal compound, such as BaO, SrO, CaO, Ba_xSr_1-xO (wherein x is a real number satisfying the condition of 0<x<1), Ba_xCa_1-xO (wherein x is a real number satisfying the condition of 0<x<1), and/or the like. The rare earth metal-containing compound may include YbF₃, ScF₃, Sc₂O₃, Y₂O₃, Ce₂O₃, GdF₃, TbF₃, YbI₃, ScI₃, TbI₃, or any combination thereof. In embodiments, the rare earth metal-containing compound may include a lanthanide metal telluride. Examples of the lanthanide metal telluride may include LaTe, CeTe, PrTe, NdTe, PmTe, SmTe, EuTe, GdTe, TbTe, DyTe, HoTe, ErTe, TmTe, YbTe, LuTe, La₂Te₃, Ce₂Te₃, Pr₂Te₃, Nd₂Te₃, Pm₂Te₃, Sm₂Te₃, Eu₂Te₃, Gd₂Te₃, Tb₂Te₃, Dy₂Te₃, Ho₂Te₃, Er₂Te₃, Tm₂Te₃, Yb₂Te₃, and Lu₂Te₃.

The alkali metal complex, the alkaline earth-metal complex, and the rare earth metal complex may include one of an alkali metal ion, an alkaline earth metal ion, and a rare earth metal ion, and a ligand bonded to the metal ion (for example, a hydroxyquinoline, a hydroxyisoquinoline, a hydroxybenzoquinoline, a hydroxyacridine, a hydroxyphenanthridine, a hydroxyphenyloxazole, a hydroxyphenylthiazole, a hydroxyphenyloxadiazole, a hydroxyphenylthiadiazole, a hydroxyphenylpyridine, a hydroxyphenyl benzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or any combination thereof).

The electron injection layer may include (e.g., consist of) an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal-containing compound, an alkaline earth metal-containing compound, a rare earth metal-containing compound, an alkali metal complex, an alkaline earth metal complex, a rare earth metal complex, or any combination thereof, as described above. In embodiments, the electron injection layer may further include an organic material (for example, a compound represented by Formula 601).

In embodiments, the electron injection layer may include (e.g., consist of) an alkali metal-containing compound (for example, an alkali metal halide); or the electron injection layer may include (e.g., consist of) an alkali metal-containing compound (for example, an alkali metal halide), and an alkali metal, an alkaline earth metal, a rare earth metal, or any combination thereof. For example, the electron injection layer may be a KI:Yb co-deposited layer, an RbI:Yb co-deposited layer, a LiF:Yb co-deposited layer, and/or the like.

When the electron injection layer further includes an organic material, an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal-containing compound, an alkaline earth metal-containing compound, a rare earth metal-containing compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or any combination thereof may be uniformly or non-uniformly dispersed in a matrix including the organic material.

A thickness of the electron injection layer may be in a range of about 1 Å to about 100 Å. For example, the thickness of the electron injection layer may be in a range of about 3 Å to about 90 Å. When the thickness of the electron injection layer is within the ranges described above, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.

Second Electrode 150

The second electrode 150 may be disposed on the interlayer 130. The second electrode 150 may be a cathode, which is an electron injection electrode. A material for forming the second electrode 150 may be a material with a low work function, such as a metal, an alloy, an electrically conductive compound, or any combination thereof.

The second electrode 150 may include lithium (Li), silver (Ag), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), ytterbium (Yb), silver-ytterbium (Ag—Yb), ITO, IZO, or any combination thereof. The second electrode 150 may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode.

The second electrode 150 may have a single-layered structure or a multi-layered structure.

Capping Layer

The light-emitting device 10 may include a first capping layer outside the first electrode 110, and/or a second capping layer outside the second electrode 150. For example, the light-emitting device 10 may have a structure in which the first capping layer, the first electrode 110, the interlayer 130, and the second electrode 150 are stacked in this stated order, a structure in which the first electrode 110, the interlayer 130, the second electrode 150, and the second capping layer are stacked in this stated order, or a structure in which the first capping layer, the first electrode 110, the interlayer 130, the second electrode 150, and the second capping layer are stacked in this stated order.

Light generated by an emission layer in the interlayer 130 of the light-emitting device 10 may be extracted to the outside through the first electrode 110, which may be a semi-transmissive electrode or a transmissive electrode, and through the first capping layer. Light generated by an emission layer in the interlayer 130 of the light-emitting device 10 may be extracted to the outside through the second electrode 150, which may be a semi-transmissive electrode or a transmissive electrode, and through the second capping layer.

The first capping layer and the second capping layer may each increase external emission efficiency according to the principle of constructive interference. Accordingly, the light extraction efficiency of the light-emitting device 10 is increased, so that the luminescence efficiency of the light-emitting device 10 may be improved.

The first capping layer and the second capping layer may each include a material having a refractive index equal to or greater than about 1.6 (with respect to a wavelength of about 589 nm).

The first capping layer and the second capping layer may each independently be an organic capping layer including an organic material, an inorganic capping layer including an inorganic material, or an organic-inorganic composite capping layer including an organic material and an inorganic material.

At least one selected from the first capping layer and the second capping layer may each independently include carbocyclic compounds, heterocyclic compounds, amine group-containing compounds, porphine derivatives, phthalocyanine derivatives, a naphthalocyanine derivatives, alkali metal complexes, alkaline earth metal complexes, or any combination thereof. In an embodiment, the carbocyclic compound, the heterocyclic compound, and the amine group-containing compound may be optionally substituted with a substituent including O, N, S, Se, Si, F, Cl, Br, I, or any combination thereof.

In embodiments, at least one selected from the first capping layer and the second capping layer may each independently include an amine group-containing compound.

For example, at least one selected from the first capping layer and the second capping layer may each independently include a compound represented by Formula 201, a compound represented by Formula 202, or any combination thereof.

In embodiments, at least one of the first capping layer and the second capping layer may each independently include at least one selected from Compounds HT28 to HT33, at least one selected from Compounds CP1 to CP6, β-NPB, and/or any combination thereof:

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Film

The amine-containing compound represented by Formula 1 may be included in one or more suitable films. Accordingly, another embodiment provides a film that includes the amine-containing compound represented by Formula 1. The film may be, for example, an optical member (or a light control refers to) (for example, a color filter, a color conversion member, a capping layer, a light extraction efficiency enhancement layer, a selective light absorbing layer, a polarizing layer, a quantum dot-containing layer, or like), a light-blocking member (for example, a light reflective layer, a light absorbing layer, and/or the like), or a protective member (for example, an insulating layer, a dielectric layer, and/or the like).

Electronic Apparatus

The light-emitting device may be included in one or more suitable electronic apparatuses. In an embodiment, an electronic apparatus including the light-emitting device may be a light-emitting apparatus, an authentication apparatus, and/or the like.

The electronic apparatus (for example, a light-emitting apparatus) may further include, in addition to the light-emitting device, a color filter, a color conversion layer, or a color filter and a color conversion layer. The color filter and/or the color conversion layer may be located in at least one direction in which light emitted from the light-emitting device travels. In an embodiment, the light emitted from the light-emitting device may be blue light or white light. The light-emitting device may be the same as described herein. In embodiments, the color conversion layer may include a quantum dot. The quantum dot may be, for example, a quantum dot as described herein.

The electronic apparatus may include a first substrate. The first substrate may include subpixels, the color filter may include color filter areas respectively corresponding to the subpixels, and the color conversion layer may include color conversion areas respectively corresponding to the subpixels.

A pixel-defining film may be located between the subpixels to define each subpixel.

The color filter may further include color filter areas and light-shielding patterns located between the color filter areas, and the color conversion layer may further include color conversion areas and light-shielding patterns located between the color conversion areas.

The color filter areas (or the color conversion areas) may include a first area emitting first color light, a second area emitting second color light, and a third area emitting third color light. The first color light, the second color light, and/or the third color light may have different maximum emission wavelengths from one another. For example, the first color light may be red light, the second color light may be green light, and the third color light may be blue light. In an embodiment, the color filter areas (or the color conversion areas) may include quantum dots. For example, the first area may include a red quantum dot, the second area may include a green quantum dot, and the third area may not include (e.g., may exclude) a quantum dot. The quantum dot may be the same as described herein. The first area, the second area, and/or the third area may each include a scatterer.

In embodiments, the light-emitting device may be to emit first light, the first area may be to absorb the first light to emit first-first color light, the second area may be to absorb the first light to emit second-first color light, and the third area may be to absorb the first light to emit third-first color light. The first-first color light, the second-first color light, and the third-first color light may have different maximum emission wavelengths from one another. For example, the first light may be blue light, the first-first color light may be red light, the second-first color light may be green light, and the third-first color light may be blue light.

The electronic apparatus may further include a thin-film transistor, in addition to the light-emitting device as described herein. The thin-film transistor may include a source electrode, a drain electrode, and an active layer, wherein one of the source electrode and the drain electrode may be electrically connected to one of the first electrode and the second electrode of the light-emitting device.

The thin-film transistor may further include a gate electrode, a gate insulating film, and/or the like.

The active layer may include crystalline silicon, amorphous silicon, an organic semiconductor, an oxide semiconductor, and/or the like.

The electronic apparatus may further include a sealing portion for sealing the light-emitting device. The sealing portion may be located between the color filter and/or the color conversion layer, and the light-emitting device. The sealing portion may allow light from the light-emitting device to be extracted to the outside, and may concurrently (e.g., simultaneously) prevent or reduce ambient air and moisture from penetrating into the light-emitting device. The sealing portion may be a sealing substrate including a transparent glass substrate or a plastic substrate. The sealing portion may be a thin-film encapsulation layer including an organic layer and/or an inorganic layer. When the sealing portion is a thin-film encapsulation layer, the electronic apparatus may be flexible.

Various functional layers may be further included on the sealing portion, in addition to the color filter and/or the color conversion layer, according to the utilize of the electronic apparatus. Examples of functional layers may include a touch screen layer, a polarizing layer, and/or the like. The touch screen layer may be a pressure-sensitive touch screen layer, a capacitive touch screen layer, or an infrared touch screen layer. The authentication apparatus may be, for example, a biometric authentication apparatus that authenticates an individual by utilizing biometric information of a living body (for example, fingertips, pupils, etc.).

The authentication apparatus may further include, in addition to the light-emitting device as described above, a biometric information collector.

The electronic apparatus may be applied to one or more suitable displays, light sources, lighting, personal computers (for example, a mobile personal computer), mobile phones, digital cameras, electronic organizers, electronic dictionaries, electronic game machines, medical instruments (for example, electronic thermometers, sphygmomanometers, blood glucose meters, pulse measurement devices, pulse wave measurement devices, electrocardiogram displays, ultrasonic diagnostic devices, or endoscope displays), fish finders, one or more suitable measuring instruments, meters (for example, meters for a vehicle, an aircraft, and a vessel), projectors, and/or the like.

Electronic Device

The light-emitting device may be included in one or more suitable electronic devices.

In embodiments, the electronic device including the light-emitting device may be a flat panel display, a curved display, a computer monitor, a medical monitor, a television (TV), a billboard, an indoor light, an outdoor light, a signal light, a head-up display, a fully transparent display, a partially transparent display, a flexible display, a rollable display, a foldable display, a stretchable display, a laser printer, a telephone, a portable phone, a tablet personal computer, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro display, a three-dimensional (3D) display, a virtual reality display, an augmented reality display, a vehicle, a video wall with multiple displays tiled together, a theater screen, a stadium screen, a phototherapy device, or a signboard.

Because the light-emitting device has excellent or suitable luminescence efficiency and long lifespan, etc., the electronic device including the light-emitting device may have characteristics of high luminance, high resolution, and low power consumption.

Description of FIGS. 2 and 3

FIG. 2 is a schematic cross-sectional view of an electronic apparatus according to an embodiment.

The electronic apparatus (e.g., a light-emitting apparatus) of FIG. 2 may include a substrate 100, a thin-film transistor (TFT), a light-emitting device, and an encapsulation portion 300 that seals the light-emitting device.

The substrate 100 may be a flexible substrate, a glass substrate, or a metal substrate. A buffer layer 210 may be located on the substrate 100. The buffer layer 210 may prevent or reduce penetration of impurities through the substrate 100. The buffer layer 210 may provide a flat surface on the substrate 100.

A TFT may be located on the buffer layer 210. The TFT may include an active layer 220, a gate electrode 240, a source electrode 260, and a drain electrode 270.

The active layer 220 may include an inorganic semiconductor such as silicon or polysilicon, an organic semiconductor, or an oxide semiconductor. The active layer 220 may include a source region, a drain region, and a channel region.

A gate insulating film 230 for insulating the active layer 220 from the gate electrode 240 may be located on the active layer 220, and the gate electrode 240 may be located on the gate insulating film 230.

An interlayer insulating film 250 may be located on the gate electrode 240. The interlayer insulating film 250 may be located between the gate electrode 240 and the source electrode 260 to insulate the gate electrode 240 from the source electrode 260 and between the gate electrode 240 and the drain electrode 270 to insulate the gate electrode 240 from the drain electrode 270.

The source electrode 260 and the drain electrode 270 may be located on the interlayer insulating film 250. The interlayer insulating film 250 and the gate insulating film 230 may be formed to expose the source region and the drain region of the active layer 220, and the source electrode 260 and the drain electrode 270 may respectively contact the exposed portions of the source region and the drain region of the active layer 220.

The TFT is electrically connected to a light-emitting device to drive the light-emitting device, and is covered and protected by a passivation layer 280. The passivation layer 280 may include an inorganic insulating film, an organic insulating film, or any combination thereof. A light-emitting device is provided on the passivation layer 280. The light-emitting device may include a first electrode 110, an interlayer 130, and a second electrode 150.

The first electrode 110 may be located on the passivation layer 280. The passivation layer 280 may not completely cover the drain electrode 270. The passivation layer 280 may expose a portion of the drain electrode 270. The first electrode 110 may be electrically connected to the exposed portion of the drain electrode 270.

A pixel defining layer 290 including an insulating material may be located on the first electrode 110. The pixel defining layer 290 may expose a portion of the first electrode 110. The interlayer 130 may be formed on the exposed portion. The pixel defining layer 290 may be a polyimide or polyacrylic organic film. Although not shown in FIG. 2, at least some layers of the interlayer 130 may extend beyond the upper portion of the pixel defining layer 290 to be provided in the form of a common layer.

The second electrode 150 may be located on the interlayer 130, and a capping layer 170 may be further included on the second electrode 150. The capping layer 170 may be formed to cover the second electrode 150.

The encapsulation portion 300 may be located on the capping layer 170. The encapsulation portion 300 may be located on a light-emitting device to protect the light-emitting device from moisture and/or oxygen. The encapsulation portion 300 may include: an inorganic film including silicon nitride (SiNx), silicon oxide (SiOx), indium tin oxide, indium zinc oxide, or any combination thereof; an organic film including polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyethylene sulfonate, polyoxymethylene, polyarylate, hexamethyldisiloxane, an acrylic resin (for example, polymethyl methacrylate, polyacrylic acid, and/or the like), an epoxy-based resin (for example, aliphatic glycidyl ether (AGE), and/or the like), or any combination thereof; or any combination of the inorganic films and the organic films.

FIG. 3 is a schematic cross-sectional view of an electronic apparatus according to another embodiment.

The electronic apparatus (e.g., a light-emitting apparatus) of FIG. 3 may differ from the electronic apparatus of FIG. 2, at least in that a light-shielding pattern 500 and a functional region 400 are further included on the encapsulation portion 300. The functional region 400 may be a color filter area, a color conversion area, or a combination of the color filter area and the color conversion area. In embodiments, the light-emitting device included in the electronic apparatus of FIG. 3 may be a tandem light-emitting device.

Description of FIG. 4

FIG. 4 is a schematic perspective view of an electronic device 1 including a light-emitting device according to an embodiment.

The electronic device 1, which may be a device displaying a video or a still image, may be not only a portable electronic device (or a portion thereof) such as a mobile phone, a smartphone, a tablet personal computer (PC), a mobile telecommunication terminal, an electronic digital assistant, an electronic book, a portable multimedia player (PMP) or a navigation device, an ultra mobile PC (UMPC), but also one or more suitable products such as a television, a laptop computer, a monitor, an advertisement sign, or an internet of things (IOT).

The electronic device 1 may be a smart watch, a watch phone, or a wearable device such as a glasses-type or kind display or a head mounted display (HMD), or a portion thereof. However, embodiments are not limited thereto.

For example, the electronic device 1 may be a dashboard of a vehicle, a center information display (CID) arranged on a center fascia or dashboard of a vehicle, a room mirror display that replaces the side mirror of a vehicle, a display arranged for entertainment in the back seat of a vehicle or arranged on the back of the front seat, a head-up display (HUD) installed on the front of a vehicle or projected onto the front window glass, or a computer generated hologram augmented reality head up display (CGH AR HUD). FIG. 4 shows an embodiment in which the electronic device 1 is a smartphone, for convenience of explanation.

The electronic device 1 may include a display area DA and a non-display area NDA outside the display area DA. The display device may implement an image through a two-dimensional array of pixels in the display area DA.

The non-display area NDA, which is an area that does not display an image, may surround the display area DA. A driver for providing electrical signals or power to display elements located in the display area DA may be arranged in the non-display area NDA. A pad that is an area to which an electronic device or a printed circuit board may be electrically connected may be arranged in the non-display area NDA.

The electronic device 1 may have different lengths in an x-axis direction and a y-axis direction. For example, as shown in FIG. 4, a length in the x-axis direction may be less than a length in the y-axis direction. In another embodiment, a length in the x-axis direction and a length of the y-axis direction may be the same. In still another embodiment, a length in the x-axis direction may be greater than a length in the y-axis direction.

Description of FIGS. 5 and 6A to 6C

FIG. 5 is a schematic perspective view of the exterior of a vehicle 1000 as an electronic device including a light-emitting device according to an embodiment.

FIGS. 6A to 6C are each a schematic diagram of the interior of a vehicle 1000 according to embodiments.

Referring to FIGS. 5, 6A, 6B, and 6C, the vehicle 1000 may refer to one or more suitable devices that move a subject to be transported, such as a person, an object, or an animal, from a departure point to a destination. Examples of the vehicle 1000 may include a vehicle that drives on a road or track, a ship that moves over a sea or river, and an airplane that flies in the air utilizing the action of air.

The vehicle 1000 may travel on a road or track. The vehicle 1000 may move in a given direction according to the rotation of at least one wheel. Examples of the vehicle 1000 may include a three-wheeled or four-wheeled vehicle, a construction machine, a two-wheeled vehicle, an engine, a bicycle, and a train that runs on a track.

The vehicle 1000 may include a body having an interior and an exterior, and a chassis that is a portion excluding the body and includes mechanical devices installed therein that are necessary for driving the vehicle. The exterior of the body may include a front panel, a bonnet, a roof panel, a rear panel, a trunk, at least one door, and a pillar provided at a boundary between doors. The chassis of the vehicle 1000 may include a power generation device, a power transfer device, a driving device, a steering device, a braking device, a suspension, a transmission, a fuel device, and front, rear, left, and right wheels.

The vehicle 1000 may include a side window glass 1100, a front window glass 1200, a side mirror 1300, a cluster 1400, a center fascia 1500, a passenger seat dashboard 1600, and a display device 2.

The side window glass 1100 and the front windows glass 1200 may be partitioned by a pillar arranged between the side window glass 1100 and the front window glass 1200.

The side window glass 1100 may be installed on the side of the vehicle 1000. In an embodiment, the side window glass 1100 may be installed in the door of the vehicle 1000. The side window glass 1100 may be provided as multiple side window glasses that may face each other. In an embodiment, the side window glass 1100 may include a first side window glass 1110 and a second side window glass 1120. In an embodiment, the first side window glass 1110 may be arranged adjacent to the cluster 1400, and the second side window glass 1120 may be arranged adjacent to the passenger seat dashboard 1600.

In an embodiment, the side window glasses 1100 may be spaced apart from each other in an x direction or in a −x direction. For example, the first side window glass 1110 and the second side window glass 1120 may be spaced apart from each other in the x direction or in the −x direction. A virtual straight line L connecting the side window glasses 1100 may extend in the x direction or in the −x direction. For example, a virtual straight line L connecting the first side window glass 1110 and the second side window glass 1120 may extend in the x direction or in the −x direction.

The front window glass 1200 may be installed on the front of the vehicle 1000. The front window glass 1200 may be located between the side window glasses 1100 facing each other.

The side mirror 1300 may provide a rear view of the vehicle 1000. The side mirror 1300 may be installed on the exterior of the body. In an embodiment, multiple side mirrors 1300 may be provided. One of the side mirrors 1300 may be located outside of the first side window glass 1110. Another one of the side mirrors 1300 may be located outside of the second side window glass 1120.

The cluster 1400 may be located at the front of a steering wheel. A tachometer, a speedometer, a coolant thermometer, a fuel gauge, a turn signal indicator, a high beam indicator, a warning light, a seatbelt warning light, an odometer, a driving record system, an automatic shifting selection lever indicator, a door open warning light, an engine oil warning light, and/or fuel shortage warning light may be located on the cluster 1400.

The center fascia 1500 may include a control panel having buttons for adjusting an audio device, an air conditioning device, and a seat heater. The center fascia 1500 may be located on a side of the cluster 1400.

The passenger seat dashboard 1600 may be spaced apart from the cluster 1400 with the center fascia 1500 therebetween. In an embodiment, the cluster 1400 may be arranged to correspond to the driver's seat, and the passenger seat dashboard 1600 may be disposed to correspond to the passenger seat. In an embodiment, the cluster 1400 may be adjacent to the first side window glass 1110, and the passenger seat dashboard 1600 may be adjacent to the second side window glass 1120.

In an embodiment, the display device 2 may include a display panel 3, and the display panel 3 may display an image. The display device 2 may be located inside the vehicle 1000. In an embodiment, the display device 2 may be located between the side window glasses 1100 facing each other. The display device 2 may be located in at least one of the cluster 1400, the center fascia 1500, and the passenger seat dashboard 1600.

The display device 2 may include an organic light-emitting display, an inorganic light-emitting display, a quantum dot display, and/or the like. Hereinafter, an organic light-emitting display including the light-emitting device according to an embodiment is utilized as an example of the display device 2. However, one or more suitable display devices as described herein may be utilized as embodiments.

Referring to FIG. 6A, the display device 2 may be arranged in the center fascia 1500. In an embodiment, the display device 2 may display navigation information. In an embodiment, the display device 2 may display information about audio settings, video settings, or vehicle settings.

Referring to FIG. 6B, the display device 2 may be arranged in the cluster 1400. The cluster 1400 may show driving information and/or the like through the display device 2. Thus, the cluster 1400 may be digitally implement driving information. The digital cluster 1400 may digitally display vehicle information and driving information as images. For example, the needle and gauge of a tachometer and one or more suitable warning lights may be displayed by a digital signal.

Referring to FIG. 6C, the display device 2 may be arranged in the passenger seat dashboard 1600. The display device 2 may be embedded in the passenger seat dashboard 1600 or may be located on the passenger seat dashboard 1600. In an embodiment, the display device 2 arranged in the passenger seat dashboard 1600 may display an image regarding information displayed on the cluster 1400 and/or information displayed on the center fascia 1500. In another embodiment, the display apparatus 2 arranged in the passenger seat dashboard 1600 may display information that is different from the information displayed on the cluster 1400 and/or different from the information displayed on the center fascia 1500.

Manufacturing Method

Respective layers included in the hole transport region, the emission layer, and respective layers included in the electron transport region may be formed in a certain region by utilizing one or more suitable methods selected from vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) deposition, ink-jet printing, laser-printing, and laser-induced thermal imaging.

When layers constituting the hole transport region, an emission layer, and layers constituting the electron transport region are formed by vacuum deposition, the deposition may be performed at a deposition temperature of about 100° C. to about 500° C., a vacuum degree of about 10⁻⁸torr to about 10⁻³torr, and a deposition speed of about 0.01 Å/sec to about 100 Å/sec, depending on a material to be included in a layer to be formed and the structure of a layer to be formed.

Definitions of Terms

The term “C₃-C₆₀carbocyclic group” as utilized herein may be a cyclic group consisting of carbon atoms as the only ring-forming atoms and having 3 to 60 carbon atoms. The term “C₁-C₆₀heterocyclic group” as utilized herein may be a cyclic group having 1 to 60 carbon atoms and further including, in addition to a carbon atom, at least one heteroatom as a ring-forming atom. The C₃-C₆₀carbocyclic group and the C₁-C₆₀heterocyclic group may each be a monocyclic group consisting of one ring or a polycyclic group in which two or more rings are condensed with each other. For example, a C₁-C₆₀heterocyclic group may have 3 to 61 ring-forming atoms.

The term “cyclic group” as utilized herein may be a C₃-C₆₀carbocyclic group or a C₁-C₆₀heterocyclic group.

The term “π electron-rich C₃-C₆₀cyclic group” as utilized herein may be a cyclic group having 3 to 60 carbon atoms and may not include (e.g., may exclude) *—N═*′ as a ring-forming moiety. The term “π electron-deficient nitrogen-containing C₁-C₆₀cyclic group” as utilized herein may be a heterocyclic group having 1 to 60 carbon atoms and may include *—N═*′ as a ring-forming moiety.

In embodiments,

the C₃-C₆₀carbocyclic group may be a T1 group or a group in which two or more T1 groups are condensed with each other (for example, a cyclopentadiene group, an adamantane group, a norbornane group, a benzene group, a pentalene group, a naphthalene group, an azulene group, an indacene group, an acenaphthylene group, a phenalene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a perylene group, a pentaphene group, a heptalene group, a naphthacene group, a picene group, a hexacene group, a pentacene group, a rubicene group, a coronene group, an ovalene group, an indene group, a fluorene group, a spiro-bifluorene group, a benzofluorene group, an indenophenanthrene group, or an indenoanthracene group),

the C₁-C₆₀heterocyclic group may be a T2 group, a group in which at least two T2 groups are condensed with each other, or a group in which at least one T2 group and at least one T1 group are condensed with each other (for example, a pyrrole group, a thiophene group, a furan group, an indole group, a benzoindole group, a naphthoindole group, an isoindole group, a benzoisoindole group, a naphthoisoindole group, a benzosilole group, a benzothiophene group, a benzofuran group, a carbazole group, a dibenzosilole group, a dibenzothiophene group, a dibenzofuran group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, a benzoindolocarbazole group, a benzocarbazole group, a benzonaphthofuran group, a benzonaphthothiophene group, a benzonaphthosilole group, a benzofurodibenzofuran group, a benzofurodibenzothiophene group, a benzothienodibenzothiophene group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, an oxadiazole group, a thiazole group, an isothiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzoisoxazole group, a benzothiazole group, a benzoisothiazole group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a benzoisoquinoline group, a quinoxaline group, a benzoquinoxaline group, a quinazoline group, a benzoquinazoline group, a phenanthroline group, a cinnoline group, a phthalazine group, a naphthyridine group, an imidazopyridine group, an imidazopyrimidine group, an imidazotriazine group, an imidazopyrazine group, an imidazopyridazine group, an azacarbazole group, an azafluorene group, an azadibenzosilole group, an azadibenzothiophene group, an azadibenzofuran group, and/or the like),

the π electron-rich C₃-C₆₀cyclic group may be a T1 group, a group in which at least two T1 groups are condensed with each other, a T3 group, a group in which at least two T3 groups are condensed with each other, or a group in which at least one T3 group and at least one T1 group are condensed with each other (for example, a C₃-C₆₀carbocyclic group, a 1H-pyrrole group, a silole group, a borole group, a 2H-pyrrole group, a 3H-pyrrole group, a thiophene group, a furan group, an indole group, a benzoindole group, a naphthoindole group, an isoindole group, a benzoisoindole group, a naphthoisoindole group, a benzosilole group, a benzothiophene group, a benzofuran group, a carbazole group, a dibenzosilole group, a dibenzothiophene group, a dibenzofuran group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, a benzoindolocarbazole group, a benzocarbazole group, a benzonaphthofuran group, a benzonaphthothiophene group, a benzonaphthosilole group, a benzofurodibenzofuran group, a benzofurodibenzothiophene group, a benzothienodibenzothiophene group, and/or the like), and

the π electron-deficient nitrogen-containing C₁-C₆₀cyclic group may be a T4 group, a group in which at least two T4 groups are condensed with each other, a group in which at least one T4 group and at least one T1 group are condensed with each other, a group in which at least one T4 group and at least one T3 group are condensed with each other, or a group in which at least one T4 group, at least one T1 group, and at least one T3 group are condensed with one another (for example, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, an oxadiazole group, a thiazole group, an isothiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzoisoxazole group, a benzothiazole group, a benzoisothiazole group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a benzoisoquinoline group, a quinoxaline group, a benzoquinoxaline group, a quinazoline group, a benzoquinazoline group, a phenanthroline group, a cinnoline group, a phthalazine group, a naphthyridine group, an imidazopyridine group, an imidazopyrimidine group, an imidazotriazine group, an imidazopyrazine group, an imidazopyridazine group, an azacarbazole group, an azafluorene group, an azadibenzosilole group, an azadibenzothiophene group, an azadibenzofuran group, and/or the like).

The T1 group may be a cyclopropane group, a cyclobutane group, a cyclopentane group, a cyclohexane group, a cycloheptane group, a cyclooctane group, a cyclobutene group, a cyclopentene group, a cyclopentadiene group, a cyclohexene group, a cyclohexadiene group, a cycloheptene group, an adamantane group, a norbornane (or a bicyclo[2.2.1]heptane) group, a norbornene group, a bicyclo[1.1.1]pentane group, a bicyclo[2.1.1]hexane group, a bicyclo[2.2.2]octane group, or a benzene group.

The T2 group may be a furan group, a thiophene group, a 1H-pyrrole group, a silole group, a borole group, a 2H-pyrrole group, a 3H-pyrrole group, an imidazole group, a pyrazole group, a triazole group, a tetrazole group, an oxazole group, an isoxazole group, an oxadiazole group, a thiazole group, an isothiazole group, a thiadiazole group, an azasilole group, an azaborole group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a tetrazine group, a pyrrolidine group, an imidazolidine group, a dihydropyrrole group, a piperidine group, a tetrahydropyridine group, a dihydropyridine group, a hexahydropyrimidine group, a tetrahydropyrimidine group, a dihydropyrimidine group, a piperazine group, a tetrahydropyrazine group, a dihydropyrazine group, a tetrahydropyridazine group, or a dihydropyridazine group.

The T3 group may be a furan group, a thiophene group, a 1H-pyrrole group, a silole group, or a borole group.

The T4 group may be a 2H-pyrrole group, a 3H-pyrrole group, an imidazole group, a pyrazole group, a triazole group, a tetrazole group, an oxazole group, an isoxazole group, an oxadiazole group, a thiazole group, an isothiazole group, a thiadiazole group, an azasilole group, an azaborole group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, or a tetrazine group.

The terms “cyclic group”, “C₃-C₆₀carbocyclic group”, “C₁-C₆₀heterocyclic group”, “π electron-rich C₃-C₆₀cyclic group”, or “π electron-deficient nitrogen-containing C₁-C₆₀cyclic group” as utilized herein may each be a group condensed to any cyclic group, a monovalent group, or a polyvalent group (for example, a divalent group, a trivalent group, a tetravalent group, and/or the like) according to the structure of a formula for which the corresponding term is utilized. For example, a “benzene group” may be a benzo group, a phenyl group, a phenylene group, and/or the like, which may be readily understand by one of ordinary skill in the art according to the structure of a formula including the “benzene group.”

Examples of a monovalent C₃-C₆₀carbocyclic group and a monovalent C₁-C₆₀heterocyclic group may include a C₃-C₁₀cycloalkyl group, a C₁-C₁₀heterocycloalkyl group, a C₃-C₁₀cycloalkenyl group, a C₁-C₁₀heterocycloalkenyl group, a C₆-C₆₀aryl group, a C₁-C₆₀heteroaryl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group.

Examples of a divalent C₃-C₆₀carbocyclic group and a divalent C₁-C₆₀heterocyclic group include a C₃-C₁₀cycloalkylene group, a C₁-C₁₀heterocycloalkylene group, a C₃-C₁₀cycloalkenylene group, a C₁-C₁₀heterocycloalkenylene group, a C₆-C₆₀arylene group, a C₁-C₆₀heteroarylene group, a divalent non-aromatic condensed polycyclic group, and a divalent non-aromatic condensed heteropolycyclic group.

The term “C₁-C₆₀alkyl group” as utilized herein may be a linear or branched aliphatic hydrocarbon monovalent group having 1 to 60 carbon atoms. Examples of a C₁-C₆₀alkyl group may include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, or a tert-decyl group.

The term “C₁-C₆₀alkylene group” as utilized herein may be a divalent group having a same structure as the C₁-C₆₀alkyl group.

The term “C₂-C₆₀alkenyl group” as utilized herein may be a monovalent hydrocarbon group having at least one carbon-carbon double bond in the middle or at a terminus of a C₂-C₆₀alkyl group. Examples of a C₂-C₆₀alkenyl group may include an ethenyl group, a propenyl group, and a butenyl group.

The term “C₂-C₆₀alkenylene group” as utilized herein may be a divalent group having a same structure as the C₂-C₆₀alkenyl group.

The term “C₂-C₆₀alkynyl group” as utilized herein may be a monovalent hydrocarbon group having at least one carbon-carbon triple bond in the middle or at a terminus of a C₂-C₆₀alkyl group. Examples of a C₂-C₆₀alkynyl group may include an ethynyl group and a propynyl group.

The term “C₂-C₆₀alkynylene group” as utilized herein may be a divalent group having a same structure as the C₂-C₆₀alkynyl group.

The term “C₁-C₆₀alkoxy group” as utilized herein may be a monovalent group represented by —O(A₁₀₁) (wherein Awl may be a C₁-C₆₀alkyl group). Examples of a C₁-C₆₀alkoxy group may include a methoxy group, an ethoxy group, and an isopropyloxy group.

The term “C₃-C₁₀cycloalkyl group” as utilized herein may be a monovalent saturated hydrocarbon cyclic group having 3 to 10 carbon atoms. Examples of a C₃-C₁₀cycloalkyl group may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl, cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group (or a bicyclo[2.2.1]heptyl group), a bicyclo[1.1.1]pentyl group, a bicyclo[2.1.1]hexyl group, and a bicyclo[2.2.2]octyl group.

The term “C₃-C₁₀cycloalkylene group” as utilized herein may be a divalent group having a same structure as the C₃-C₁₀cycloalkyl group.

The term “C₁-C₁₀heterocycloalkyl group” as utilized herein may be a monovalent cyclic group having 1 to 10 carbon atoms that further includes, in addition to a carbon atom, at least one heteroatom as a ring-forming atom. Examples of a C₁-C₁₀heterocycloalkyl group may include a 1,2,3,4-oxatriazolidinyl group, a tetrahydrofuranyl group, and a tetrahydrothiophenyl group.

The term “C₁-C₁₀heterocycloalkylene group” as utilized herein may be a divalent group having a same structure as the C₁-C₁₀heterocycloalkyl group.

The term “C₃-C₁₀cycloalkenyl group” as utilized herein may be a monovalent cyclic group that has 3 to 10 carbon atoms and at least one carbon-carbon double bond in its ring, and is not aromatic. Examples of a C₃-C₁₀cycloalkenyl group may include a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group.

The term “C₃-C₁₀cycloalkenylene group” as utilized herein may be a divalent group having a same structure as the C₃-C₁₀cycloalkenyl group.

The term “C₁-C₁₀heterocycloalkenyl group” as utilized herein may be a monovalent cyclic group having 1 to 10 carbon atoms, that further includes, in addition to a carbon atom, at least one heteroatom, as a ring-forming atom, and having at least one carbon-carbon double bond in the cyclic structure thereof. Examples of a C₁-C₁₀heterocycloalkenyl group may include a 4,5-dihydro-1,2,3,4-oxatriazolylgroup, a 2,3-dihydrofuranyl group, and a 2,3-dihydrothiophenyl group.

The term “C₁-C₁₀heterocycloalkenylene group” as utilized herein may be a divalent group having a same structure as the C₁-C₁₀heterocycloalkenyl group.

The term “C₆-C₆₀aryl group” as utilized herein may be a monovalent group having a carbocyclic aromatic system of 6 to 60 carbon atoms. Examples of a C₆-C₆₀aryl group may include a phenyl group, a pentalenyl group, a naphthyl group, an azulenyl group, an indacenyl group, an acenaphthyl group, a phenalenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a pentaphenyl group, a heptalenyl group, a naphthacenyl group, a picenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group, and an ovalenyl group.

The term “C₆-C₆₀arylene group” as utilized herein may be a divalent group having a carbocyclic aromatic system of 6 to 60 carbon atoms.

When the C₆-C₆₀aryl group and the C₆-C₆₀arylene group each include two or more rings, the respective rings may be condensed with each other.

The term “C₁-C₆₀heteroaryl group” as utilized herein may be a monovalent group having a heterocyclic aromatic system of 1 to 60 carbon atoms that further includes, in addition to a carbon atom, at least one heteroatom as a ring-forming atom. Examples of a C₁-C₆₀heteroaryl group may include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, a benzoquinolinyl group, an isoquinolinyl group, a benzoisoquinolinyl group, a quinoxalinyl group, a benzoquinoxalinyl group, a quinazolinyl group, a benzoquinazolinyl group, a cinnolinyl group, a phenanthrolinyl group, a phthalazinyl group, and a naphthyridinyl group.

The term “C₁-C₆₀heteroarylene group” as utilized herein may be a divalent group having a heterocyclic aromatic system of 1 to 60 carbon atoms that further includes, in addition to a carbon atom, at least one heteroatom as a ring-forming atom.

When the C₁-C₆₀heteroaryl group and the C₁-C₆₀heteroarylene group each include two or more rings, the respective rings may be condensed with each other.

The term “monovalent non-aromatic condensed polycyclic group” as utilized herein may be a monovalent group (for example, having 8 to 60 carbon atoms) having two or more rings condensed to each other, only carbon atoms as ring-forming atoms, and no aromaticity in its entire molecular structure. Examples of a monovalent non-aromatic condensed polycyclic group may include an indenyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, an indenophenanthrenyl group, and an indenoanthracenyl group.

The term “divalent non-aromatic condensed polycyclic group” as utilized herein may be a divalent group having a same structure as the monovalent non-aromatic condensed polycyclic group described above.

The term “monovalent non-aromatic condensed heteropolycyclic group” as utilized herein may be a monovalent group (for example, having 1 to 60 carbon atoms) having two or more rings condensed to each other, further including, in addition to carbon atoms, at least one heteroatom, as ring-forming atoms, and having non-aromaticity in its entire molecular structure. Examples of a monovalent non-aromatic condensed heteropolycyclic group may include a pyrrolyl group, a thiophenyl group, a furanyl group, an indolyl group, a benzoindolyl group, a naphthoindolyl group, an isoindolyl group, a benzoisoindolyl group, a naphthoisoindolyl group, a benzosilolyl group, a benzothiophenyl group, a benzofuranyl group, a carbazolyl group, a dibenzosilolyl group, a dibenzothiophenyl group, a dibenzofuranyl group, an azacarbazolyl group, an azafluorenyl group, an azadibenzosilolyl group, an azadibenzothiophenyl group, an azadibenzofuranyl group, a pyrazolyl group, an imidazolyl group, a triazolyl group, a tetrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzopyrazolyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a benzoxadiazolyl group, a benzothiadiazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an imidazotriazinyl group, an imidazopyrazinyl group, an imidazopyridazinyl group, an indeno carbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzosilolocarbazolyl group, a benzoindolocarbazolyl group, a benzocarbazolyl group, a benzonaphthofuranyl group, a benzonaphthothiophenyl group, a benzonaphthosilolyl group, a benzofurodibenzofuranyl group, a benzofurodibenzothiophenyl group, and a benzothienodibenzothiophenyl group.

The term “divalent non-aromatic condensed heteropolycyclic group” as utilized herein may be a divalent group having a same structure as the monovalent non-aromatic condensed heteropolycyclic group described above.

The term “C₆-C₆₀aryloxy group” as utilized herein may be a group represented by —O(A₁₀₂) (wherein A₁₀₂may be a C₆-C₆₀aryl group).

The term “C₆-C₆₀arylthio group” as utilized herein may be a group represented by —S(A₁₀₃) (wherein A₁₀₃may be a C₆-C₆₀aryl group).

The term “C₇-C₆₀arylalkyl group” as utilized herein may be a group represented by -(A₁₀₄)(A₁₀₅) (wherein A₁₀₄may be a C₁-C₅₄alkylene group and A₁₀₅may be a C₆-C₅₉aryl group).

The term “C₂-C₆₀heteroarylalkyl group” as utilized herein may be a group represented by -(A₁₀₆)(A₁₀₇) (wherein A₁₀₆may be a C₁-C₅₉alkylene group and A₁₀₇may be a C₁-C₅₉heteroaryl group).

In the specification, the group “R_10a” may be:

deuterium (-D), —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, or a nitro group;

a C₁-C₆₀alkyl group, a C₂-C₆₀alkenyl group, a C₂-C₆₀alkynyl group, or a C₁-C₆₀alkoxy group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C₃-C₆₀carbocyclic group, a C₁-C₆₀heterocyclic group, a C₆-C₆₀aryloxy group, a C₆-C₆₀arylthio group, a C₇-C₆₀arylalkyl group, a C₂-C₆₀heteroarylalkyl group, —Si(Q₁₁)(Q₁₂)(Q₁₃), —N(Q₁₁)(Q₁₂), —B(Q₁₁)(Q₁₂), —C(═O)(Q₁₁), —S(═O)₂(Q₁₁), —P(═O)(Q₁₁)(Q₁₂), or any combination thereof;

a C₃-C₆₀carbocyclic group, a C₁-C₆₀heterocyclic group, a C₆-C₆₀aryloxy group, a C₆-C₆₀arylthio group, a C₇-C₆₀arylalkyl group, or a C₂-C₆₀heteroarylalkyl group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C₁-C₆₀alkyl group, a C₂-C₆₀alkenyl group, a C₂-C₆₀alkynyl group, a C₁-C₆₀alkoxy group, a C₃-C₆₀carbocyclic group, a C₁-C₆₀heterocyclic group, a C₆-C₆₀aryloxy group, a C₆-C₆₀arylthio group, a C₇-C₆₀arylalkyl group, a C₂-C₆₀heteroarylalkyl group, —Si(Q₂₁)(Q₂₂)(Q₂₃), —N(Q₂₁)(Q₂₂), —B(Q₂₁)(Q₂₂), —C(═O)(Q₂₁), —S(═O)₂(Q₂₁), —P(═O)(Q₂₁)(Q₂₂), or any combination thereof; or

Si(Q₃₁)(Q₃₂)(Q₃₃), —N(Q₃₁)(Q₃₂), —B(Q₃₁)(Q₃₂), —C(═O)(Q₃₁), —S(═O)₂(Q₃₁), or —P(═O)(Q₃₁)(Q₃₂).

In the specification, Q₁to Q₃, Q₁₁to Q₁₃, Q₂₁to Q₂₃and Q₃₁to Q₃₃may each independently be:

hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C₁-C₆₀alkyl group, a C₂-C₆₀alkenyl group, a C₂-C₆₀alkynyl group, or a C₁-C₆₀alkoxy group; or

a C₃-C₆₀carbocyclic group, a C₁-C₆₀heterocyclic group, a C₇-C₆₀arylalkyl group, or a C₂-C₆₀heteroarylalkyl group, each unsubstituted or substituted with deuterium, —F, a cyano group, a C₁-C₆₀alkyl group, a C₁-C₆₀alkoxy group, a phenyl group, a biphenyl group, or any combination thereof.

The term “heteroatom” as utilized herein may be any atom other than a carbon atom or a hydrogen atom. Examples of a heteroatom may include O, S, N, P, Si, B, Ge, Se, and any combinations thereof.

The term “third-row transition metal” as utilized herein may include hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and/or the like.

The term “Ph” as utilized herein refers to a phenyl group, the term “Me” as utilized herein refers to a methyl group, the term “Et” as utilized herein refers to an ethyl group, the terms “tert-Bu” or “But” as utilized herein each refer to a tert-butyl group, and the term “OMe” as utilized herein refers to a methoxy group.

The term “biphenyl group” as utilized herein may be a “phenyl group substituted with a phenyl group.” For example, the “biphenyl group” may be a substituted phenyl group having a C₆-C₆₀aryl group as a substituent.

The term “terphenyl group” as utilized herein may be a “phenyl group substituted with a biphenyl group”. For example, the “terphenyl group” may be a substituted phenyl group having, as a substituent, a C₆-C₆₀aryl group substituted with a C₆-C₆₀aryl group.

The symbols * and *′ as utilized herein, unless defined otherwise, each refer to a binding site to a neighboring atom in a corresponding formula or moiety.

In the specification, the terms “x-axis,” “y-axis,” and “z-axis” are not limited to three axes in a Cartesian coordinate system, and may have a broader meaning than the aforementioned three axes in a Cartesian coordinate system. For example, the x-axis, y-axis, and z-axis may describe axes that are orthogonal to each other, or may describe axes that are in different directions that are not orthogonal to each other.

Organic Light Emitting Diode

FIG. 1 is a cross-sectional view illustrating an organic light emitting diode according to an example embodiment of the present disclosure.

Referring to FIG. 1, an organic light emitting diode includes an anode 10, a cathode 70, a light emitting layer 40 disposed between the two electrodes, a hole conduction layer 20 disposed between the anode 10 and the light emitting layer 40, and an electron conduction layer 50 disposed between the light emitting layer 40 and the cathode 70. The hole conduction layer 20 may include a hole transport layer 25 for transporting holes and a hole injection layer 23 for facilitating injection of holes. The electron conduction layer 50 may include an electron transport layer 55 for transporting electrons and an electron injection layer 53 for facilitating injection of electrons. In some embodiments, a hole blocking layer may be disposed between the light emitting layer 40 and the electron transporting layer 55. Further, an electron blocking layer may be disposed between the light emitting layer 40 and the hole transporting layer 25. However, it is not limited thereto, and the electron transport layer 55 may serve as the hole blocking layer, or the hole transport layer 25 may serve as the electron blocking layer.

When a forward bias is applied to the organic light emitting diode, holes are injected into the light emitting layer 40 from the anode 10, and electrons are injected into the light emitting layer 40 from the cathode 70. Electrons and holes injected into the light emitting layer 40 are combined to form excitons, and light is emitted while the excitons transition to the ground state.

The light emitting layer 40 may be made of a single light emitting material, or may include a host material and a dopant material. The single light emitting material or the light emitting dopant material may be a compound represented by any one of the above-described Chemical Formulas 1 to 12 and Compounds 1 to 92, specifically, a thermally activated delayed fluorescent material. In this case, the efficiency of the organic light emitting diode can be greatly improved. The thermally activated delayed fluorescent material has a form in which an electron donating group and an electron withdrawing group are connected to benzene and the electron withdrawing group is positioned in an ortho position to the electron donating group. Thus, the difference between singlet energy and triplet energy can be reduced to less than 0.3 eV. The thermally activated delayed fluorescent material can more efficiently facilitate transition from the triplet excited state to the singlet excited state by heat (at room temperature or element operating temperature), thereby improving the quantum efficiency. In some embodiments, one or more suitable combinations of the red, green, and blue luminescent colors can be realized by the appropriate or suitable introduction of the electron donating group and the electron withdrawing group.

The host material may be selected from the group consisting of mCP (N,N-dicarbazolyl-3,5-benzene), Alq3, CBP (4,4′-N,N′-dicarbazole-biphenyl), 9,10-di(naphthalen-2-yl)anthracene, TPBI (1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene), TBADN (3-tert-butyl-9,10-di(naphth-2-yl)anthracene), E3 (see the following formula), and BeBq2 (see the followina formula).

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In some embodiments, the hole injection layer 23 and/or the hole transport layer 25 are layers having a HOMO level between the work function level of the anode 10 and the HOMO level of the light emitting layer 40, and has the function of enhancing the injection or transport efficiency of holes from the anode 10 to the light emitting layer 40. The electron injection layer 53 and/or the electron transport layer 55 are layers having a LUMO level between the work function level of the cathode 70 and the LUMO level of the light emitting layer 40, and has the function of enhancing the injection or transport efficiency of electrons from the cathode 70 to the light emitting layer 40.

The anode 10 may be a conductive metal oxide, a metal, a metal alloy, or a carbon material. The conductive metal oxide may be at least one selected from the group consisting of indium tin oxide (ITO), fluorine tin oxide (FTO), antimony tin oxide (ATO), SnO2, ZnO, or any combination thereof. The metal or metal alloy suitable as the anode 10 may be Au or CuI. The carbon material may be graphite, graphene, or carbon nanotubes.

The hole injecting layer 23 or the hole transporting layer 25 may include a material commonly utilized as a hole transporting material, and one layer may have a different hole transporting materials or a different hole transporting material layers. The hole transporting material may be, for example, mCP (N,N-dicarbazolyl-3,5-benzene); PEDOT:PSS (poly(3,4-ethylenedioxythiophene):polystyrenesulfonate); NPD (N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine); N,N′-diphenyl-N,N′-di(3-methylphenyl)-4,4′-diaminobiphenyl (TPD); N,N′-diphenyl-N,N′-dinaphthyl-4,4′-diaminobiphenyl; N, N, N′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; N, N, N′, N′-tetraphenyl-4,4′-diaminobiphenyl; porphyrin compound derivatives such as copper (II) 1,10,15,20-tetraphenyl-21H,23H-porphyrin and/or the like; TAPC (1,1-bis[4-[N,N′-di(p-tolyl)amino]phenyl]cyclohexane); triarylamine derivatives such as N,N,N-tri(p-tolyl)amine and 4,4′,4′-tris[N-(3-methylphenyl)-N-phenylam ino] triphenylamine; carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole; phthalocyanine derivatives such as metal-free phthalocyanine and copper phthalocyanine; starburst amine derivatives; enamine stilbene derivatives; derivatives of aromatic tertiary amine and styrylamine compounds; polysilane; and/or the like. Such a hole transporting material may also serve as the electron blocking layer.

The hole blocking layer serves to prevent or reduce triplet excitons or holes from diffusing toward the cathode 70, and may be arbitrarily selected from suitable hole blocking materials. For example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives and/or the like can be utilized.

The electron transporting layer 55 may be formed of a material selected from the group consisting of TSPO1(diphenylphosphine oxide-4-(triphenylsilyl)phenyl), tris(8-quinolinolate) aluminum (Alq3), 2,5-diarylsilole derivative (PyPySPyPy), perfluorinated compound (PF-6P), COTs (octasubstituted cyclooctatetraene), TAZ (see the following Chemical Formula), Bphen (4,7-diphenyl-1,10-phenanthroline), BCP (see the following formula), and BAlq (see the following formula).

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The electron injection layer 53 may be, for example, LiF, NaCl, CsF, Li2O, BaO, BaF2, or Liq (lithium quinolate).

The cathode 70 is a conductive film having a lower work function than the anode 70 and is made of a metal such as aluminum, magnesium, calcium, sodium, potassium, indium, yttrium, lithium, silver, lead, cesium, and/or the like, or a combination of two or more species among those metals.

The anode 10 and the cathode 70 may be formed utilizing a sputtering method, a vapor deposition method, or an ion beam deposition method. The hole injecting layer 23, the hole transporting layer 25, the light emitting layer 40, the hole blocking layer, the electron transporting layer 55 and the electron injecting layer 53 are, regardless of each other, formed by evaporation or coating methods such as spraying, spin coating, dipping, printing, doctor blading, or electrophoresis.

The organic light emitting diode may be disposed on a substrate, which may be disposed the anode 10 or above the cathode 70. In other words, the anode 10 may be formed on the substrate before the cathode 70, or the cathode 70 may be formed before the anode 10.

The substrate may be a light-transmissive substrate as a flat plate member, in which case the substrate may be glass; ceramics; or a polymer material such as polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polypropylene (PP). However, the present disclosure is not limited to this, and the substrate may be a metal substrate capable of light reflection.

Hereinafter, example embodiments of the present disclosure will be described in order to facilitate understanding of the present disclosure. It should be understood, however, that the following examples are for the purpose of promoting understanding of the present disclosure and are not intended to limit the scope of the present disclosure.

EXAMPLES

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In Scheme 1, the product is Compound 1 when both of R₁and R₂are hydrogen, Compound 2 when R₁is a methyl group and R₂is hydrogen, Compound 3 when R₁is a t-butyl group and R₂is hydrogen, and Compound 37 when R₁is hydrogen and R₂is a methyl group.

Synthesis Example 1: Synthesis of Compound 1

Step 1: Carbazole (10.0 g, 59.8 mmol), 1,2-dibromobenzene (21.16 g, 89.71 mmol), potassium carbonate (16.53 g, 119.61 mmol) and copper iodide (CuI) (5.69 g, 29.90 mmol) were dissolved in N,N-dimethylacetamide (250 mL) and then oxygen was removed from the solution through nitrogen bubbling. After oxygen was removed, the mixture was refluxed and stirred for 24 hours. The reaction solution was extracted with methylene chloride, and then subjected to column chromatography utilizing a methylene chloride/hexane mixed solvent as eluent to obtain 15.99 g of 9-(2-bromophenyl)carbazole. 9-(2-bromophenyl)carbazole: Mass Spec (EI) m/z 322 [(M+H)+]

Step 2: 9-(2-bromophenyl)carbazole (10 g, 31.03 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborane) (11.82 g, 46.55 mmol), potassium acetate (9.14 g, 93.11 mmol), and 1,1′-bis(diphenylphosphino) ferrocene-palladium (II) (0.76 g, 0.93 mmol) were dissolved in 1,4-dioxane (180 mL), and then oxygen in the solution was removed through nitrogen bubbling. After oxygen was removed, the mixture was refluxed and stirred for 24 hours. The reaction solution was extracted with methylene chloride and then subjected to column chromatography utilizing a methylene chloride/hexane mixed solvent as eluent to obtain 4.01 g of 9-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) carbazole. 9-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) carbazole: Mass Spec (EI) m/z 369 [(M+H)+]

Step 3: 9-(2-(4,4,5,5-tetramethyl-1,3,2-dioxabolan-2-yl)phenyl)carbazole (3 g, 8.12 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.61 g, 9.75 mmol), tetrakis (triphenylphosphine) palladium (0) (0.28 g, 0.24 mmol) were added to a mixed solvent of tetrahydrofuran (60 mL) and potassium carbonate 2M solution (20 mL), and then the mixture was refluxed for 24 hours. The reaction solution was extracted with methylene chloride, and then purified by column chromatography utilizing a methylene chloride/hexane mixed solvent as eluent, and finally 3.31 g of a pure white solid was obtained through sublimation purification.

Compound 1: yield 86%, Mass Spec (EI) m/z 474 [(M+H)+]. Elemental analysis theoretical value C₃₃H₂₂N₄: C, 83.52%; H, 4.67%; N, 11.81%. Measured: C, 83.52%; H, 4.74%; N, 11.69%. ¹H NMR (500 MHz, CDCl₃): δ 8.57 (d, 1H), 8.03 (t, 6H), 7.85 (t, 1H), 7.78 (t, 1H), 7.73 (d, 1H), 7.48 (t, 2H), 7.34 (t, 6H), 7.24˜7.19 (m, 4H).

Synthesis Example 2: Synthesis of Compound 2

Compound 2 was obtained in a yield of 83% utilizing the same method as in Synthesis Example 1 except that 3,6-dimethylcarbazole was utilized instead of carbazole in Step 1 of Synthesis Example 1.

Compound 2: Mass Spec (FAB) m/z 502 [(M+H)⁺]. Elemental analysis theoretical value C₃₅H₂₆N₄: C(83.64%) H(5.21%) N(11.15%) Measured: C, 83.69%; H, 5.26%; N, 11.09%. ¹H NMR (500 MHz, CDCl₃): 8.50 (d, 1H), 8.00 (d, 4H), 7.78 (t, 3H), 7.73 (t, 1H), 7.67 (d, 1H), 7.47 (t, 2H), 7.31 (t, 4H), 7.11 (d, 2H), 7.06 (d, 2H), 2.49 (s, 6H).

Synthesis Example 3: Synthesis of Compound 3

Compound 3 was obtained in a yield of 81% utilizing the same method as in Synthesis Example 1 except that 3,6-di-t-butylcarbazole was utilized instead of carbazole in Step 1 of Synthesis Example 1.

Compound 3: Mass Spec (EI) m/z 586 [(M+H)⁺]. Elemental analysis theoretical value C₄₁H₃₈N₄: C(83.92%) H(6.53%) N(9.55%) Measured: C, 83.85%; H, 6.61%; N, 9.53%. ¹H NMR (500 MHz, CDCl₃): 8.56 (d, 1H), 8.09 (d, 4H), 8.02 (d, 2H), 7.81 (t, 1H), 7.74 (t, 1H), 7.68 (d, 1H), 7.49 (t, 2H), 7.34 (t, 6H), 7.11 (d, 2H), 1.42 (s, 18H).

Synthesis Example 4: Synthesis of Compound 37

Compound 37 was obtained in a yield of 78% utilizing the same method as in Synthesis Example 1 except that 2-chloro-4,6-di-p-tolyl-1,3,5-triazine was utilized instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in Step 3 of Synthesis Example 1.

Compound 37: Mass Spec (FAB) m/z 502 [(M+H)⁺]. Elemental analysis theoretical value C₃₅H₂₆N₄: C(83.64%) H(5.21%) N(11.15%) Measured: C(83.53%) H(5.27%) N(11.18%). ¹H NMR (500 MHz, CDCl₃): 8.55 (d, 1H), 7.95 (d, 4H), 7.78˜7.72 (m, 3H), 7.48 (t, 2H), 7.11 (d, 4H), 7.05˜6.95 (m, 6H), 2.72 (s, 6H).

Synthesis Example 5: Synthesis of Compound 22

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Step 1: Diphenylamine (10.0 g, 59.09 mmol), 1,2-dibromobenzene (27.88 g, 118.19 mmol), sodium tert-butoxide (6.814 g, 70.908 mmol), palladium acetate (0.663 g, 2.95 mmol), and tri-tert-butylphosphine (1.19 g, 5.91 mmol) were dissolved in toluene (300 mL) and then oxygen was removed from the solution through nitrogen bubbling. After oxygen was removed, the mixture was refluxed and stirred for 24 hours. The reaction solution was extracted with methylene chloride, and then subjected to column chromatography utilizing a methylene chloride/hexane mixed solvent as eluent to obtain 12.21 g of intermediate 22-1.

Intermediate 22-1: Mass Spec (EI) m/z 324 [(M+H)⁺]

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Step 2: Intermediate 22-1 (10 g, 30.84 mmol), 4,4,4′, 4′, 5,5,5′, 5′-octamethyl-2,2′-bi(1,3,2-dioxaborane) (11.74 g, 46.26 mmol), potassium acetate (9.08 g, 92.52 mmol), and 1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (0.76 g, 0.93 mmol) were dissolved in 1,4-dioxane (180 mL) and then oxygen was removed from the solution through nitrogen bubbling. After oxygen was removed, the mixture was refluxed and stirred for 24 hours. The reaction solution was extracted with methylene chloride, and then subjected to column chromatography utilizing a methylene chloride/hexane mixed solvent as eluent to obtain 4.58 g of intermediate 22-2.

Intermediate 22-2: Mass Spec (EI) m/z 371 [(M+H)⁺]

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Step 3: Intermediate 22-2 (3 g, 8.08 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.59 g, 9.75 mmol), and tetrakis(triphenylphosphine)palladium (0) (0.28 g, 0.24 mmol) were added to a mixed solvent of tetrahydrofuran (60 mL) and potassium carbonate 2M solution (20 mL), and then the mixture was refluxed for 24 hours. The reaction solution was extracted with methylene chloride, and then purified by column chromatography utilizing a methylene chloride/hexane mixed solvent as eluent, and finally 3.08 g of compound 22 as a pure white solid was obtained through sublimation purification.

Compound 22: yield 86% Mass Spec (EI) m/z 476 [(M+H)⁺]. Elemental analysis theoretical value C₃₃H₂₄N₄: C, 83.17%; H, 5.08%; N, 11.76%. Measured: C, 82.16%; H, 5.12%; N, 11.77%. ¹H NMR (500 MHz, CDCl₃): δ 8.83 (d, 1H), 8.51 (d, 4H), 8.05 (d, 1H), 7.64˜7.61 (m, 2H), 7.57˜7.53 (m, 3H), 7.46 (t, 4H), 7.41 (d, 2H), 7.09˜7.04 (m, 5H), 6.83˜6.79 (m, 2H).

Synthesis Example 6: Synthesis of Compound 23

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Compound 23 was obtained in a yield of 78% utilizing the same method as in Synthesis Example 5 except that di-p-tolylamine was utilized instead of diphenylamine in Step 1 of Synthesis Example 5 to obtain 2-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)-N,N-di-p-tolylaniline in Step 2 and this was utilized in Step 3.

Compound 23: Mass Spec (EI) m/z 504 [(M+H)+]. Elemental analysis theoretical value C₃₅H₂₈N₄: C(83.30%) H(5.59%) N(11.10%) Measured: C, 83.32%; H, 5.66%; N, 11.05%. ¹H NMR (500 MHz, CDCl₃): 8.52 (d, 4H), 7.95 (d, 1H), 7.56 (t, 2H), 7.53˜7.45 (m, 5H), 7.38˜7.32 (m, 2H), 6.92 (d, 4H), 6.85 (d, 4H).

Synthesis Example 7: Synthesis of Compound 36

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(2-(carbazol-9-yl)phenyl)boronic acid (10 g, 34.83 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (7.87 g, 34.83 mmol), tetrakis(triphenylphosphine)palladium (0) (4.02 g, 3.48 mmol), and potassium carbonate (14.44 g, 104.49 mmol) were added to tetrahydrofuran (60 mL), distilled water (20 mL), and then the mixture was refluxed and stirred for 24 hours. The reaction solution was extracted with methylene chloride, and then subjected to column chromatography utilizing a methylene chloride/hexane mixed solvent as eluent to obtain 7.99 g of intermediate 36-1.

Intermediate 36-1: Mass Spec (EI) m/z 432 [(M+H)+]

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Intermediate 36-1 (3 g, 6.94 mmol) and copper cyanide (2.18 g, 24.31 mmol) were dissolved in N-methyl-2-pyrrolidone (50 mL) and then oxygen was removed from the solution through nitrogen bubbling. After oxygen was removed, the mixture was refluxed and stirred for 24 hours. The reaction solution was extracted with methylene chloride, and then subjected to column chromatography utilizing a methylene chloride/hexane mixed solvent as eluent to obtain 2.49 g of Compound 36.

Compound 36: Mass Spec (EI) m/z 423 [(M+H)+]. Elemental analysis theoretical value C₂₈H₁₇N₅: C(79.42%) H(4.05%) N(16.54%) Measured: C, 79.43%; H, 4.07%; N, 16.51%. ¹H NMR (500 MHz, CDCl₃): 8.41 (d, 1H), 8.02 (d, 2H), 7.85 (t, 1H), 7.75˜7.70 (m, 2H), 7.36˜7.29 (m, 5H), 7.22 (t, 2H), 7.15 (d, 2H), 7.10 (t, 2H).

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In Scheme 5, the product is Compound 61 when both of R₁and R₂are hydrogen, Compound 63 when R₁is hydrogen and R₂is a methyl group.

Synthesis Example 8: Synthesis of Compound 61

Step 1: 2-chloro-4,6-diphenyl-1,3,5-triazine (5.0 g, 18.67 mmol), (2-fluorophenyl) boronic acid (3.92 g, 28.01 mmol), tetrakis(triphenylphosphine) palladium (0) (2.15 g, 1.86 mmol), potassium carbonate (7.74 g, 56.03 mmol) were dissolved in toluene (120 mL), ethanol (60 mL), D.W (90 mL), and then oxygen was removed from the solution through nitrogen bubbling. After oxygen was removed, the mixture was stirred at room temperature for 1 hour and then refluxed and stirred at 130° C. for 15 hours. Then, the reaction solution was vacuum-dried by removing the solvent through a rotary evaporator. The dried mixture was extracted with methylene chloride and then subjected to column chromatography utilizing a methylene chloride/hexane mixed solvent as eluent to obtain 5.4 g of 2-(2-fluorophenyl)-4,6-diphenyl-1,3,5-triazine.

2-(2-fluorophenyl)-4,6-diphenyl-1,3,5-triazine: Mass Spec (EI) m/z 327 [(M+H)+]¹H NMR (500 MHz, CDCl₃): 8.76 (d, 4H), 8.48 (t, 1H), 7.62 (t, 3H), 7.56 (t, 4H), 7.35 (t, 1H), 7.27 (t, 1H).

Step 2: 2-(2-fluorophenyl)-4,6-diphenyl-1,3,5-triazine (1.00 g, 3.05 mmol), indole (0.89 g, 7.63 mmol), and sodium tertiary butoxide (0.73 g, 7.63 mmol) were mixed in a solvent of dimethylformamide (100 mL) and refluxed at 160° C. for 24 hours. The reaction solution was extracted with methylene chloride, and then purified by column chromatography utilizing a methylene chloride/hexane mixed solvent as eluent, and finally 0.63 g of Compound 61 as a yellow solid was obtained through sublimation purification.

Compound 61: yield 49.5% Mass Spec (EI) m/z 424 [(M+H)+]. Elemental analysis theoretical value C₂₉H₂₀N₄: C(82.05%) H(4.75%) N(13.20%) Measured: C, 81.98%; H, 4.77%; N, 13.11%. ¹H NMR (500 MHz, CDCl₃): 8.42 (d, 1H), 8.16 (d, 4H), 7.73 (t, 1H), 7.66 (t, 2H), 7.61 (d, 1H), 7.50 (t, 2H), 7.38 (t, 4H), 7.31 (d, 1H), 7.19˜7.13 (m, 2H), 7.07 (d, 1H), 6.53 (d, 1H).

Synthesis Example 9: Synthesis of Compound 63

1.17 g of Compound 63 was obtained in a similar manner to that of Step 2 of Synthesis Example 8, except that 2-(2-fluorophenyl)-4,6-diphenyl-1,3,5-triazine (1.50 g, 4.58 mmol) obtained in Step 1 of Synthesis Example 8, 3-methylindole (1.50 g, 11.45 mmol), and sodium tertiary butoxide (1.10 g, 11.45 mmol) were added to a solvent of dimethylformamide (100 mL).

Compound 63: yield 58.07% Mass Spec (EI) m/z 438 [(M+H)+]. Elemental analysis theoretical value C₃₀H₂₂N₄: C(82.17%) H(5.06%) N(12.78%), Measured: C, 82.22%; H, 4.97%; N, 12.69%. ¹H NMR (500 MHz, CDCl₃): 8.43 (d, 1H), 8.20 (d, 4H), 7.71 (t, 1H), 7.62 (t, 2H), 7.52 (t, 3H), 7.39 (t, 4H), 7.19˜7.17 (m, 1H), 7.10˜6.94 (m, 2H), 6.94 (s, 1H), 2.26 (s, 3H).

Synthesis Example 10: Synthesis of Compound 52

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2-(2-fluorophenyl)-4,6-diphenyl-1,3,5-triazine (1.00 g, 3.05 mmol), 5H-benzofuro[3,2-c] carbazole (0.98 g, 3.82 mmol), sodium hydride (0.10 g, 3.90 mmol) were mixed in a solvent of dimethylformamide (100 mL) and refluxed at 160° C. for 24 hours. The reaction solution was extracted with methylene chloride, and then purified by column chromatography utilizing methylene chloride/hexane mixed solvent as eluent, and finally 1.35 g of a yellow solid Compound 52 was obtained through sublimation purification.

Compound 52: yield 78.4%, Mass Spec (EI) m/z 565 [(M+H)+]. ¹H NMR (300 MHz, DMSO): 7.16˜7.26 (m, 6H), 7.34˜7.51 (m, 6H), 7.82 (d, 1H), 7.88˜7.99 (m, 6H), 8.03˜8.31 (m, 3H), 8.30 (d, 1H), 8.60 (d, 1H).

Synthesis Example 11: Synthesis of Compound 67

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9-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)phenyl)carbazole (8.0 g, 27.9 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (3.0 g, 13.3 mmol), and tetrakis (triphenylphosphine) palladium (0) (1.53 g, 1.33 mmol) were added to a mixed solvent of tetrahydrofuran (100 mL) and potassium carbonate 2M solution (40 mL) and refluxed for 24 hours. The reaction solution was extracted with methylene chloride, and then purified by column chromatography utilizing methylene chloride/hexane mixed solvent as eluent, and finally a pure white solid was obtained in a yield of 71% through sublimation purification.

Compound 67: Mass Spec (EI) m/z 639 [(M+H)+]. Elemental analysis theoretical value C₄₅H₂₉N₅C (84.48%) H (4.57%) N (10.95%) Measured: C (84.48%) H (4.57%) N (10.86%). ¹H NMR (500 MHz, CDCl₃): δ 6.79 (d, 2H, J=8 Hz), 6.895 (t, 2H, J=15 Hz), 6.965 (d, 4H, J=8 Hz), 7.163˜7.217 (m, 5H), 7.263 (t, 4H, J=15 Hz), 7.478 (t, 2H, J=15 Hz), 7.563 (d, 2H, J=8 Hz), 7.659˜7.708 (m, 4H), 7.986 (d, 4H, J=8 Hz).

Synthesis Example 12: Synthesis of Compound 83

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9-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)phenyl)carbazole (15.4 g, 53.7 mmol), cyanuric chloride (3.0 g, 16.3 mmol), and tetrakis(triphenylphosphine)palladium (0) (2.82 g, 2.44 mmol) were added to a mixed solvent of tetrahydrofuran (100 mL) and potassium carbonate 2M solution (40 mL) and refluxed for 24 hours. The reaction solution was extracted with methylene chloride, and then purified by column chromatography utilizing methylene chloride/hexane mixed solvent as eluent, and finally a pure white solid was obtained in a yield of 37% through sublimation purification.

Compound 83: Mass Spec (EI) m/z 803 [(M+H)+]. Elemental analysis theoretical value C₅₇H₃₆N₆C (85.05%) H (4.51%) N (10.44%) Measured: C (85.07%) H (4.49%) N(10.45%). ¹H NMR (500 MHz, CDCl₃): δ 6.238 (d, 3H, J=8 Hz), 6.558 (d, 6H, J=8 Hz), 6.968 (t, 3H, J=15 Hz), 7.216˜7.261 (m, 12H), 7.341 (d, 3H, J=8 Hz), 7.485 (t, 3H, J=15 Hz), 8.10 (d, 6H, J=7 Hz)

Preparation Example 1: Preparation of Delayed Fluorescent Organic Light Emitting Diode

(ITO/PEDOT:PSS/TAPC/mCP/mCP:Compound 1/TSPO1/TPBi/LiF/Al)

A glass substrate on which an anode, ITO, was deposited was ultrasonically cleaned for 30 minutes utilizing pure water and isopropyl alcohol. The cleaned ITO substrate was surface-treated utilizing ultraviolet rays of short wavelength, and then a hole injection layer was formed by spin coating PEDOT: PSS (poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate)) to a thickness of 60 nm. Thereafter, TAPC (1,1-Bis [4-[N,N-Di(p-tolyl)Amino]Phenyl]Cyclohexane was vapor-deposited at a pressure of 1×10⁻⁶torr at a rate of 0.1 nm/s to form a hole transporting layer of 20 nm. Thereafter, mCP (N, N-dicarbazolyl-3,5-benzene) was vapor-deposited at a pressure of 1×10⁻⁶torr at a rate of 0.1 nm/s to form a exciton blocking layer of 10 nm. Subsequently, under a pressure of 1×10⁻⁶torr, mCP as a host material at a rate of 0.1 nm/s and Compound 1 as a delayed fluorescent dopant material synthesized through Synthesis Example 1 at a rate of 0.005 nm/s were co-evaporated to form a light emitting layer doped with 5% of the dopant in the host. TSPO1 (diphenylphosphine oxide-4-(triphenylsilyl)phenyl) and TPBi (1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene) were sequentially vapor-deposited at a pressure of 1×10⁻⁶torr at a rate of 0.1 nm/s to form an exciton blocking layer of 5 nm and an electron transport layer of 30 nm, respectively. Thereafter, LiF as an electron injecting material was vapor-deposited at a pressure of 1×10⁻⁶torr at a rate of 0.01 nm/s to form an electron injecting layer of 1 nm. Thereafter, Al was vapor-deposited at a rate of 0.5 nm/sec under a pressure of 1×10⁻⁶torr to form a cathode of 100 nm, thereby forming an organic light-emitting diode. After formation of the device, the device was sealed utilizing a CaO moisture absorbent and a glass cover glass.

The organic light emitting device utilizing Compound 1 as a fluorescent dopant material has a quantum efficiency of 9.3%, a current efficiency of 14.6 cd/A, a power efficiency of 7.6 lm/W at a voltage of 6 V, x=0.15 and y=0.22 based on CIE 1931 color coordinates, indicating excellent or suitable blue light emission characteristics. These results exceeded the limit of the maximum external quantum efficiency of 5% (20% of the light extraction efficiency) that can be obtained from a general fluorescent device, and it can be a direct proof that a triplet energy is converted into a single energy by intersystem crossing, which is the property of the thermally-activated delayed fluorescent material.

Preparation Example 2: Preparation of Delayed Fluorescent Organic Light Emitting Diode

(ITO/PEDOT:PSS/TAPC/mCP/mCP: Compound 2/TSPO1/TPBi/LiF/Al)

An organic light emitting diode was fabricated in substantially the same manner as in Preparation Example 1, except that Compound 2 synthesized through Synthesis Example 2 was utilized as a delayed fluorescent dopant material.

The organic light emitting diode according to Preparation Example 2 utilizing Compound 2 as a light emitting dopant material showed, at a voltage of 6 V, a quantum efficiency of 14.7%, a current efficiency of 30.9 cd/A, a power efficiency of 14.9 lm/W and x=0.17 and y=0.34 based on a CIE 1931 color coordinate, indicating excellent or suitable blue light emission characteristics.

Preparation Example 3: Preparation of Delayed Fluorescent Organic Light Emitting Diode

(ITO/PEDOT:PSS/TAPC/mCP/mCP:Compound 3/TSPO1/TPBi/LiF/Al)

An organic light emitting diode was fabricated in substantially the same manner as in Preparation Example 1, except that Compound 3 synthesized through Synthesis Example 3 was utilized as a delayed fluorescent dopant material.

The organic light emitting diode according to Preparation Example 3 utilizing Compound 3 as a light emitting dopant material showed, at a voltage of 6 V, a quantum efficiency of 12.3%, a current efficiency of 24.0 cd/A, a power efficiency of 12.6 lm/W and x=0.16 and y=0.30 based on a CIE 1931 color coordinate, indicating excellent or suitable blue light emission characteristics.

Preparation Example 4: Preparation of Delayed Fluorescent Organic Light Emitting Diode

(ITO/PEDOT:PSS/TAPC/mCP/mCP:Compound 37/TSPO1/TPBi/LiF/Al)

An organic light emitting diode was fabricated in substantially the same manner as in Preparation Example 1, except that Compound 37 synthesized through Synthesis Example 4 was utilized as a delayed fluorescent dopant material.

The organic light emitting diode according to Preparation Example 4 utilizing Compound 37 as a light emitting dopant material showed, at a voltage of 6 V, a quantum efficiency of 11.5%, a current efficiency of 29.1 cd/A, a power efficiency of 13.8 lm/W and x=0.16 and y=0.20 based on a CIE 1931 color coordinate, indicating excellent or suitable blue light emission characteristics.

Preparation Example 5: Preparation of Delayed Fluorescent Organic Light Emitting Diode

(ITO/PEDOT:PSS/TAPC/mCP/mCP:Compound 22/TSPO1/TPBi/LiF/Al)

An organic light emitting diode was fabricated in substantially the same manner as in Preparation Example 1, except that Compound 22 synthesized through Synthesis Example 5 was utilized as a delayed fluorescent dopant material.

The organic light emitting diode according to Preparation Example 5 utilizing Compound 22 as a light emitting dopant material showed, at a voltage of 9 V, a quantum efficiency of 17.2%, a current efficiency of 45.0 cd/A, a power efficiency of 31.4 lm/W and x=0.21 and y=0.45 based on a CIE 1931 color coordinate, indicating excellent or suitable blue-green light emission characteristics.

Preparation Example 6: Preparation of Delayed Fluorescent Organic Light Emitting Diode

(ITO/PEDOT:PSS/TAPC/mCP/mCP: Compound 52/TSPO1/TPBi/LiF/Al)

An organic light emitting diode was fabricated in substantially the same manner as in Preparation Example 1, except that Compound 52 synthesized through Synthesis Example 10 was utilized as a delayed fluorescent dopant material.

The organic light emitting diode according to Preparation Example 6 utilizing Compound 52 as a light emitting dopant material showed, at a voltage of 9 V, a quantum efficiency of 12.5%, a current efficiency of 19.8 cd/A, a power efficiency of 17.8 lm/W and x=0.15 and y=0.20 based on a CIE 1931 color coordinate, indicating excellent or suitable blue light emission characteristics.

Preparation Example 7: Preparation of Delayed Fluorescent Organic Light Emitting Diode

(ITO/PEDOT:PSS/TAPC/mCP/mCP:Compound 23/TSPO1/TPBi/LiF/Al)

An organic light emitting diode was fabricated in substantially the same manner as in Preparation Example 1, except that Compound 23 synthesized through Synthesis Example 6 was utilized as a delayed fluorescent dopant material.

The organic light emitting diode according to Preparation Example 7 utilizing Compound 23 as a light emitting dopant material showed, at a voltage of 9 V, a quantum efficiency of 16.3%, a current efficiency of 54.6 cd/A, a power efficiency of 32.8 lm/W and x=0.35 and y=0.58 based on a CIE 1931 color coordinate, indicating excellent or suitable green light emission characteristics.

Preparation Example 8: Preparation of Delayed Fluorescent Organic Light Emitting Diode

(ITO/PEDOT:PSS/TAPC/mCP/mCP:Compound 36/TSPO1/TPBi/LiF/Al)

An organic light emitting diode was fabricated in substantially the same manner as in Preparation Example 1, except that Compound 36 synthesized through Synthesis Example 7 was utilized as a delayed fluorescent dopant material.

The organic light emitting diode according to Preparation Example 8 utilizing Compound 36 as a light emitting dopant material showed, at a voltage of 6 V, a quantum efficiency of 11.7%, a current efficiency of 26.9 cd/A, a power efficiency of 10.4 lm/W and x=0.55 and y=0.45 based on a CIE 1931 color coordinate, indicating excellent or suitable orange light emission characteristics.

Preparation Example 9: Preparation of Delayed Fluorescent Organic Light Emitting Diode

(ITO/PEDOT:PSS/TAPC/mCP/mCP:Compound 67/TSPO1/TPBi/LiF/Al)

An organic light emitting diode was fabricated in substantially the same manner as in Preparation Example 1, except that Compound 67 synthesized through Synthesis Example 11 was utilized as a delayed fluorescent dopant material.

The organic light emitting diode according to Preparation Example 9 utilizing Compound 67 as a light emitting dopant material showed, at a voltage of 8 V, a quantum efficiency of 12.2%, a current efficiency of 18.5 cd/A, a power efficiency of 6.47 lm/W and x=0.17 and y=0.21 based on a CIE 1931 color coordinate, indicating excellent or suitable blue light emission characteristics.

Preparation Example 10: Preparation of Delayed Fluorescent Organic Light Emitting Diode

(ITO/PEDOT:PSS/TAPC/mCP/mCP:Compound 83/TSPO1/TPBi/LiF/Al)

An organic light emitting diode was fabricated in substantially the same manner as in Preparation Example 1, except that Compound 83 synthesized through Synthesis Example 12 was utilized as a delayed fluorescent dopant material.

The organic light emitting diode according to Preparation Example 9 utilizing Compound 83 as a light emitting dopant material showed, at a voltage of 8 V, a quantum efficiency of 14.9%, a current efficiency of 23.0 cd/A, a power efficiency of 9.57 lm/W and x=0.15 and y=0.22 based on a CIE 1931 color coordinate, indicating excellent or suitable blue light emission characteristics.

Comparative Example 1: Preparation of Delayed Fluorescent Organic Light Emitting Diode

(ITO/PEDOT:PSS/TAPC/mCP/mCP:CC2TA/TSPO1/TPBi/LiF/A1)

An organic light emitting diode was fabricated in substantially the same manner as in Preparation Example 1, except that 2,4-bis 3-(9H-carbazol-9-yl)-9H-carbazol-9-yl-6-phenyl-1,3,5-triazine (CC2TA) reported in the paper (APPLIED PHYSICS LETTERS 101, 093306 (2012)) was utilized as a delayed fluorescent dopant material.

The organic light emitting diode according to Comparative Example 1 utilizing CC2TA as a light emitting dopant material showed, at a voltage of 6 V, a quantum efficiency of 11.5%, a current efficiency of 29.1 cd/A, a power efficiency of 13.8 lm/W and x=0.20 and y=0.44 based on a CIE 1931 color coordinate.

Blue (Preparation Examples 1-4, 6, 9 and 10), green (Preparation Examples 5 and 7) and red (Preparation Example 8) organic light emitting diodes were prepared by utilizing the thermally activated delayed fluorescent compounds in the Preparation Examples 1-10. Each of these organic light emitting diodes exhibits a quantum efficiency exceeding 5% (a light extraction efficiency is 20%) which is the maximum external quantum efficiency that can be obtained from a general fluorescent device, indicating that the thermally activated delayed fluorescence compounds according to examples of the present disclosure facilitates efficient reverse intersystem crossing from triplet state to singlet state. In some embodiments, the organic light emitting diode according to Comparative Example 1 utilizing CC2TA, which is known as a conventional delayed fluorescent light emitting material, exhibits a quantum efficiency of 11.5%, whereas the organic light emitting diodes according to Examples 2 to 10 exhibit significantly higher or the same quantum efficiency. In particular, the green light emitting device (Preparation Example 5) exhibits a high quantum efficiency of 17% or more, showing excellent or suitable luminescence characteristics as compared with the conventional fluorescent device.

Table 1 shows the values calculated by the molecular calculation technique for Compound 1 prepared according to Synthesis Example 1, Comparative Compound A, and Comparative Compound B. Molecular calculations were performed utilizing the Gaussian 09 program through the B3LYP method according to density functional theory on a 6-31 G * basis set.

TABLE 1

Sample
Structural Formula

¹⁾B_g

²⁾S₁

³⁾T₁

⁴⁾ΔE_ST

⁵⁾HOMO

⁶⁾LUMO

Compound (ortho)

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3.49 eV
2.86 eV
2.79 eV
0.06 eV
−5.31 eV
−1.81 eV

Comparative Compound A (meta)

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3.39 eV
2.90 eV
2.75 eV
0.15 eV
−5.36 eV
−1.97 eV

Comparative Compound B (para)

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3.47 eV
3.04 eV
2.70 eV
0.34 eV
−5.42 eV
−1.95 eV

¹⁾Bandgap,

²⁾Singlet Energy,

³⁾Triplet Energy,

⁴⁾Difference between the singlet energy and the triplet energy,

⁵⁾Highest occupied molecular orbital Energy level,

⁶⁾Lowest unoccupied molecular orbital Energy level

Referring to Table 1, Comparative Compound A or B is in a form similar to Compound 1, but carbazole as an electron donating group and diphenyltriazine as an electron withdrawing group are in meta position in Comparative Compound A and in para position in Comparative Compound B. Calculation result shows that, as the position of the carbazole and diphenyltriazine were shifted from ortho to meta, and from metal to para, the singlet energy gradually increased and the triplet energy gradually decreased. As a result, the smallest energy different was found between the singlet state and the triplet state in the ortho form. The smaller energy difference between the singlet state and the triplet state is, the easier the Reverse Intersystem Crossing (RISC) is, and the better the thermally activated delay fluorescence property can be obtained.

FIG. 2 shows the molecular orbital distribution of Compound 1 prepared according to Synthesis Example 1, Comparative Compound A and Comparative Compound B. The molecular orbital distribution was calculated utilizing the Gaussian 09 program through the B3LYP method according to density functional theory with a 6-31 G * basis set.

In order to show the fluorescence property effectively, the overlapping between HOMO and LUMO should exist at a certain level. As a result of calculation, HOMO and LUMO of ortho, meta and para forms are overlapped on benzene which is the central connecting unit, the fluorescence property of the ortho-form material was expected to be similar to other-form materials. These results indicate that the ortho-form material can up-convert the triplet exciton formed during electroluminescence to the singlet exciton more effectively through RISC than the meta- and para-form materials, and the singlet exciton can show effective fluorescent light emitting.

The present disclosure is not limited to the above-described embodiments and the accompanying drawings. While the example embodiments of the present disclosure and their advantages have been described in more detail, it should be understood that one or more suitable changes, substitutions, and alterations may be made herein without departing from the scope of the present disclosure.

	Number	Date	Country
Parent	15562415	Jan 2018	US
Child	18166431		US

ORTHO-SUBSTITUTED THERMALLY ACTIVATED DELAYED FLUORESCENCE MATERIAL AND ORGANIC LIGHT-EMITTING DEVICE COMPRISING SAME

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