Patent Application
20220407021
This application claims priority from and the benefit of Korean Patent Application No. 10-2021-0070962, filed on Jun. 1, 2021, which is hereby incorporated by reference for all purposes as if fully set forth herein.
Embodiments of the invention relate generally to display devices, and more particularly to, an organometallic compound, a light-emitting device including the same, and an electronic apparatus including the light-emitting device.
Some light-emitting devices are self-emission devices that, as compared with devices of the related art, have wide viewing angles, high contrast ratios, short response times, and excellent characteristics in terms of luminance, driving voltage, and response speed, and produce full-color images.
In a light-emitting device, a first electrode is located on a substrate, and a hole transport region, an emission layer, an electron transport region, and a second electrode are sequentially formed on the first electrode. Holes provided from the first electrode move toward the emission layer through the hole transport region, and electrons provided from the second electrode move toward the emission layer through the electron transport region. Carriers, such as holes and electrons, recombine in the emission layer to produce excitons. These excitons transition from an excited state to a ground state to thereby generate light.
The above information disclosed in this Background section is only for understanding of the background of the inventive concepts, and, therefore, it may contain information that does not constitute prior art.
Light-emitting devices including a novel organometallic compound made according to the principles and illustrative implementations of the invention can provide the light-emitting device with a low driving voltage, high efficiency, and a long lifespan compared to the related art. For example, a light-emitting device with high emission efficiency, high color purity and long lifespan can be achieved when the formation of exciplexes between a first compound made according to one or more embodiments disclosed herein, which may be comprise the dopant, and either a second compound or a third compound made according to one or more embodiments disclosed herein, which may be comprise the host, is effectively suppressed.
In one or more embodiments, the organometallic compound may be a 4-coordination organometallic compound having a rigid structure by the introduction of a bulky group, which is believed to inhibit the formation of exciplex between the organometallic compound and the host compound, and as a result, the light-emitting device may have high efficiency and high color purity.
Additional features of the inventive concepts will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the inventive concepts.
According to one aspect of the invention, a light-emitting device includes: a first electrode; a second electrode facing the first electrode; an interlayer between the first electrode and the second electrode and comprising an emission layer; and at least one organometallic compound of Formula 1:
wherein, in Formula 1, the variables are described herein.
The emission layer may include the at least one organometallic compound of Formula 1.
The emission layer may include a host and a dopant, an amount of the host may be greater than an amount of the dopant, and the dopant may include the at least one organometallic compound of Formula 1.
The host may include hosts having different chemical formula.
The dopant may further include a fluorescence emitter or a thermally active delayed fluorescence emitter.
The host may include an electron transport host compound of Formula 5, and a hole transport host compound including a group of Formula 7, as described herein.
The electron transport host compound may be one or more of Compounds ETH1 to ETH84, and the hole transport host compound may be one or more of Compounds HTH1 to HTH52, are described herein.
The fluorescence emitter or the TADF emitter may include a compound of Formula 9-1, a compound of Formula 9-2, or any combination thereof, as described herein.
The fluorescence emitter may be one or more of Compounds DFD1 to DFD12, as described herein.
An electronic apparatus may include the light-emitting device as described above.
According to another aspect of the invention, an organometallic compound is of Formula 1:
wherein, in Formula 1, the variables are described herein.
The variables Y10, Y20, Y30, and Y40 may each be C; Y10, Y30, and Y40 may each be C and Y20 may be N; Y10, Y20, and Y40 may each be C and Y30 may be N; or Y30 and Y40 may each be C and Y10 and Y20 may each be N.
The variables Y11 and Y12 may each be N; Y11 and Y12 may each be C; or Y11 may be C and Y12 may be N.
The variables A1 to A4 may be independently from one another a group as described herein.
At least one of A1 and A2 may be a ring including nitrogen, and A3 and A4 may each be, independently from one another, a 6-membered ring or a fused cyclic group including a 6-membered ring.
The variable A1 may be a group of one of Formulae 2A-1 to 2A-19, A2 may be a group of one of Formulae 2B-1 to 2B-19, A3 may be a group of one of Formulae 2C-1 to 2C-13, and A4 may be a group of one of Formulae 2D-1 to 2D-13, as described herein.
The variables a2 and a4 may each be 1 and a3 is 0 or 1, and L2 may be a single bond or *—N(R7)—*′, L4 may be a single bond, and L3 may be *—C(R7)(R8)—*′; wherein R7 and R8 may have, independently from one another, the same meaning as described above.
The variables R1 to R8 may each be, independently from one another a group as described herein.
The organometallic compound may be of Formula 1-1 or 1-2, as described herein.
The organometallic compound of Formula 1 may be one or more of Compounds BD1 to BD90, as described herein.
It is to be understood that both the foregoing general description and the following detailed description are illustrative and explanatory and are intended to provide further explanation of the invention as claimed.
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate illustrative embodiments of the invention, and together with the description serve to explain the inventive concepts.
In the following description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of various embodiments or implementations of the invention. As used herein “embodiments” and “implementations” are interchangeable words that are non-limiting examples of devices or methods employing one or more of the inventive concepts disclosed herein. It is apparent, however, that various embodiments may be practiced without these specific details or with one or more equivalent arrangements. In other instances, well-known structures and devices are shown in block diagram form in order to avoid unnecessarily obscuring various embodiments. Further, various embodiments may be different, but do not have to be exclusive. For example, specific shapes, configurations, and characteristics of an embodiment may be used or implemented in another embodiment without departing from the inventive concepts.
Unless otherwise specified, the illustrated embodiments are to be understood as providing illustrative features of varying detail of some ways in which the inventive concepts may be implemented in practice. Therefore, unless otherwise specified, the features, components, modules, layers, films, panels, regions, and/or aspects, etc. (hereinafter individually or collectively referred to as “elements”), of the various embodiments may be otherwise combined, separated, interchanged, and/or rearranged without departing from the inventive concepts.
The use of cross-hatching and/or shading in the accompanying drawings is generally provided to clarify boundaries between adjacent elements. As such, neither the presence nor the absence of cross-hatching or shading conveys or indicates any preference or requirement for particular materials, material properties, dimensions, proportions, commonalities between illustrated elements, and/or any other characteristic, attribute, property, etc., of the elements, unless specified. Further, in the accompanying drawings, the size and relative sizes of elements may be exaggerated for clarity and/or descriptive purposes. When an embodiment may be implemented differently, a specific process order may be performed differently from the described order. For example, two consecutively described processes may be performed substantially at the same time or performed in an order opposite to the described order. Also, like reference numerals denote like elements, and duplicative explanations are omitted to avoid redundancy.
When an element, such as a layer, is referred to as being “on,” “connected to,” or “coupled to” another element or layer, it may be directly on, connected to, or coupled to the other element or layer or intervening elements or layers may be present. When, however, an element or layer is referred to as being “directly on,” “directly connected to,” or “directly coupled to” another element or layer, there are no intervening elements or layers present. To this end, the term “connected” may refer to physical, electrical, and/or fluid connection, with or without intervening elements. Further, the D1-axis, the D2-axis, and the D3-axis are not limited to three axes of a rectangular coordinate system, such as the x, y, and z-axes, and may be interpreted in a broader sense. For example, the D1-axis, the D2-axis, and the D3-axis may be perpendicular to one another, or may represent different directions that are not perpendicular to one another. For the purposes of this disclosure, “at least one of X, Y, and Z” and “at least one selected from the group consisting of X, Y, and Z” may be construed as X only, Y only, Z only, or any combination of two or more of X, Y, and Z, such as, for instance, XYZ, XYY, YZ, and ZZ. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
Although the terms “first,” “second,” etc. may be used herein to describe various types of elements, these elements should not be limited by these terms. These terms are used to distinguish one element from another element. Thus, a first element discussed below could be termed a second element without departing from the teachings of the disclosure.
Spatially relative terms, such as “beneath,” “below,” “under,” “lower,” “above,” “upper,” “over,” “higher,” “side” (e.g., as in “sidewall”), and the like, may be used herein for descriptive purposes, and, thereby, to describe one elements relationship to another element(s) as illustrated in the drawings. Spatially relative terms are intended to encompass different orientations of an apparatus in use, operation, and/or manufacture in addition to the orientation depicted in the drawings. For example, if the apparatus in the drawings is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the term “below” can encompass both an orientation of above and below. Furthermore, the apparatus may be otherwise oriented (e.g., rotated 90 degrees or at other orientations), and, as such, the spatially relative descriptors used herein interpreted accordingly.
The terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting. As used herein, the singular forms, “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. Moreover, the terms “comprises,” “comprising,” “includes,” and/or “including,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, components, and/or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. It is also noted that, as used herein, the terms “substantially,” “about,” and other similar terms, are used as terms of approximation and not as terms of degree, and, as such, are utilized to account for inherent deviations in measured, calculated, and/or provided values that would be recognized by one of ordinary skill in the art.
Various embodiments are described herein with reference to sectional and/or exploded illustrations that are schematic illustrations of idealized embodiments and/or intermediate structures. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments disclosed herein should not necessarily be construed as limited to the particular illustrated shapes of regions, but are to include deviations in shapes that result from, for instance, manufacturing. In this manner, regions illustrated in the drawings may be schematic in nature and the shapes of these regions may not reflect actual shapes of regions of a device and, as such, are not necessarily intended to be limiting.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure is a part. Terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and should not be interpreted in an idealized or overly formal sense, unless expressly so defined herein.
According to one aspect of the invention, an organometallic compound is represented by Formula 1 below:
M1 in Formula 1 may be selected from platinum (Pt), palladium (Pd), copper (Cu), silver (Ag), gold (Au), rhodium (Rh), iridium (Ir), ruthenium (Ru), osmium (Os), titanium (Ti), zirconium (Zr), hafnium (Hf), europium (Eu), terbium (Tb), and thulium (Tm). In an embodiment, M1 may be selected from Pt, Pd, Cu, Ag, Au, Rh, Ir, Ru, and Os. In an embodiment, M1 may be Pt, but embodiments are not limited thereto.
The variables Y10 to Y12, Y20 to Y22, Y30 to Y32, and Y40 to Y42 in Formula 1 may each independently be selected from a carbon atom (C) and a nitrogen atom (N). In an embodiment, Y10, Y20, Y30, and Y40 may each be C; Y10, Y30, and Y40 may each be C and Y20 may be N; Y10, Y20, and Y40 may each be C and Y30 may be N; or Y30 and Y40 may each be C and Y10 and Y20 may each be N. In an embodiment, Y11 and Y12 may each be N; Y11 and Y12 may each be C; or Y11 may be C and Y12 may be N. In an embodiment, Y21 and Y22 may each be N; Y21 and Y22 may each be C; or Y21 may be C and Y22 may be N. For example, Y10 may be C and Y11 and Y12 may each be N; Y10 may be N and Y11 and Y12 may each be C; or Y10 may be N, Y11 may be C, and Y12 may be N. For example, Y20 may be C and Y21 and Y22 may each be N; Y20 may be N and Y21 and Y22 may each be C; or Y20 may be N, Y21 may be C, and Y22 may be N. For example, Y31, Y32, Y41, and Y42 may each be C.
In Formula 1, two of a bond between Y10 and M1, a bond between Y20 and M1, a bond between Y30 and M1, and a bond between Y40 and M1 may be coordinate bonds, and the other two bonds may be covalent bonds. In an embodiment, at least one of a bond between Y10 and M1, and a bond between Y20 and M1 may be a coordinate bond. The variables A1 to A4 in Formula 1 may each independently be selected from a C5-C60 carbocyclic group and a C1-C60 heterocyclic group.
In an embodiment, A1 to A4 may each independently be selected from:
a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a cyclopentane group, a cyclopentadiene group, a cyclohexane group, a cyclohexene group, a 1,2,3,4-tetrahydronaphthalene group, a furan group, a thiophene group, a silole group, an indene group, a fluorene group, an indole group, a carbazole group, a benzofuran group, a dibenzofuran group, a benzothiophene group, a dibenzothiophene group, a benzosilole group, a dibenzosilole group, an indenopyridine group, an indolopyridine group, a benzofuropyridine group, a benzothienopyridine group, a benzosilolopyridine group, an indenopyrimidine group, an indolopyrimidine group, a benzofuropyrimidine group, a benzothienopyrimidine group, a benzosilolopyrimidine group, a dihydropyridine group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a 2,3-dihydroimidazole group, a triazole group, a 1,2,4-triazole group, a tetrazole group, a 2,3-dihydrotriazole group, an azasilole group, a diazasilole group, a triazasilole group, an oxazole group, an isooxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a 2,3-dihydrobenzimidazole group, an imidazopyridine group, a 2,3-dihydroimidazopyridine group, an imidazopyrimidine group, a 2,3-dihydroimidazopyrimidine group, an imidazopyrazine group, a 2,3-dihydroimidazopyrazine group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, and a 5,6,7,8-tetrahydroquinoline group.
In an embodiment, at least one of A1 to A4 may be a 5-membered ring having two or more N(s) or a condensed cyclic group including the 5-membered ring having two or more N(s). In an embodiment, at least one of A1 and A2 may be a nitrogen-containing ring, and A3 and A4 may each independently be a 6-membered ring or a condensed cyclic group including a 6-membered ring. For example, A1 and A2 may each independently be selected from an imidazole group, a benzimidazole group, a pyrazole group, a pyridine group, and a carbazole group. For example, A3 and A4 may each independently be selected from a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, and a carbazole group. According to an embodiment, A1 may be a group represented by one of Formulae 2A-1 to 2A-19, A2 may be a group represented by one of Formulae 2B-1 to 2B-19, A3 may be a group represented by one of Formulae 2C-1 to 2C-13, and A4 may be a group represented by one of Formulae 2D-1 to 2D-13:
wherein, in Formulae 2A-1 to 2A-19, Formulae 2B-1 to 2B-19, Formulae 2C-1 to 2C-13, and Formulae 2D-1 to 2D-13,
Z21 may be N or C(R21), Z22 may be N or C(R22), Z23 may be N or C(R23), Z24 may be N or C(R24), Z25 may be N or C(R25), and Z26 may be N or C(R26),
* indicates a binding site to neighboring M1, *′ and *″ each indicate a binding site to a neighboring carbon atom, L1, L2, or L4, and ** may be a binding site to neighboring L3 or R28, and
R21 to R28 are the same as described in connection with R1 to R8.
In Formula 1, L1 may be *—O—*′ or *—N(R7)—*′, and L2 to L4 may each independently be selected from a single bond, a double bond, *—N(R7)—*′, *—B(R7)—*′, *—P(R7)—*′, *—C(R7)(R8)—*′, *—Si(R7)(R8)—*′, *—Ge(R7)(R8)—*′, *—S—*′, *—Se—*′, *—O—*′, *—C(═O)—*′, *—S(═O)—*′, *—S(═O)2—*′, *—C(R7)=*′, *═C(R7)—*′, *—C(R7)═C(R8)—*′, *—C(═S)—*′, and *—C≡C—*′
a2 to a4 may each independently be an integer from 0 to 3, wherein, when a2 is 0, A2 and A3 may not be linked to each other, when a3 is 0, A3 and A4 may not be linked to each other, and when a4 is 0, A4 and A1 may not be linked to each other,
* and *′ each indicate a binding site to a neighboring atom.
In an embodiment, L2 to L4 may each independently be a single bond, *—N(R7)—*′, or *—C(R7)(R8)—*′. In an embodiment, a2 and a4 may each be 1, a3 may be 0 or 1, L2 may be a single bond or *—N(R7)—*′, L4 may be a single bond, and L3 may be *—C(R7)(R8)—*′.
The variables R1 to R8 in Formula 1 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group that is unsubstituted or substituted with at least one R10a, a C2-C60 alkenyl group that is unsubstituted or substituted with at least one R10a, a C2-C60 alkynyl group that is unsubstituted or substituted with at least one R10a, a C1-C60 alkoxy group that is unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group that is unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group that is unsubstituted or substituted with at least one R10a, a C6-C60 aryloxy group that is unsubstituted or substituted with at least one R10a, a C6-C60 arylthio group that is unsubstituted or substituted with at least one R10a, —Si(Q1)(Q2)(Q3), —N(Q1)(Q2), —B(Q1)(Q2), —C(═O)(Q1), —S(═O)2(Q1), or —P(═O)(Q1)(Q2),
b1 to b4 may each independently be an integer from 1 to 20,
neighboring two of R1 to R8 may optionally be linked to each other to form a C5-C60 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, and
R10a may be:
deuterium (-D), —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, or a nitro group;
a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, or a C1-C60 alkoxy group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C3-C60 carbocyclic group, a C1-C60 heterocyclic group, a C6-C60 aryloxy group, a C6-C60 arylthio 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-C60 carbocyclic group, a C1-C60 heterocyclic group, a C6-C60 aryloxy group, or a C6-C60 arylthio group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C60 carbocyclic group, a C1-C60 heterocyclic group, a C6-C60 aryloxy group, a C6-C60 arylthio 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),
wherein Q1 to Q3, Q11 to Q13, Q21 to Q23, and Q31 to Q33 may each independently be: hydrogen; deuterium; —F; —Cl; —Br; —I; a hydroxyl group; a cyano group; a nitro group; a C1-C60 alkyl group; a C2-C60 alkenyl group; a C2-C60 alkynyl group; a C1-C60 alkoxy group; a C3-C60 carbocyclic group; or a C1-C60 heterocyclic group, each unsubstituted or substituted with deuterium, —F, a cyano group, a C1-C60 alkyl group, a C1-C60 alkoxy group, a phenyl group, a biphenyl group, or any combination thereof.
In an embodiment, R1 to R8 may each independently be selected from hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C20 alkyl group, and a C1-C20 alkoxy group;
a C1-C20 alkyl group and a C1-C20 alkoxy group, each substituted with at least one selected from deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C20 alkyl group, and a C1-C20 alkoxy group;
a cyclopentyl group, a cyclohexyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a phenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a pyrrolyl group, an indolyl group, an isoindolyl group, an indazolyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, and a triazinyl group; and
a cyclopentyl group, a cyclohexyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a phenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, an indolyl group, an isoindolyl group, an indazolyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, and a triazinyl group;
a cyclopentyl group, a cyclohexyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a phenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, an indolyl group, an isoindolyl group, an indazolyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, and a triazinyl group, each substituted with at least one selected from a C1-C20 alkyl group and a C1-C20 alkoxy group, each substituted with at least one selected from deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a cyclopentyl group, a cyclohexyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a phenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, an indolyl group, an isoindolyl group, an indazolyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a triazinyl group, —Si(Q11)(Q12)(Q13), —N(Q11)(Q12), —B(Q11)(Q12), —C(═O)(Q11), —S(═O)2(Q11), and —P(═O)(Q11)(Q12); and
a cyclopentyl group, a cyclohexyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a phenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, an indolyl group, an isoindolyl group, an indazolyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, and a triazinyl group, each substituted with at least one selected from a cyclopentyl group, a cyclohexyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a phenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, an indolyl group, an isoindolyl group, an indazolyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, and a triazinyl group, each substituted with at least one selected from deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a cyclopentyl group, a cyclohexyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a phenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, an indolyl group, an isoindolyl group, an indazolyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a triazinyl group, —Si(Q21)(Q22)(Q23), —N(Q21)(Q22), —B(Q21)(Q22), —C(═O)(Q21), —S(═O)2(Q21), and —P(═O)(Q21)(Q22); and
—Si(Q1)(Q2)(Q3), —N(Q1)(Q2), —B(Q1)(Q2), —C(═O)(Q1), —S(═O)2(Q1), and —P(═O)(Q1)(Q2),
wherein Q1 to Q3, Q11 to Q13, Q21 to Q23, and Q31 to Q33 may each independently be selected from hydrogen, deuterium, —F, —Cl, —Br, —I, a cyano group, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C1-C20 alkoxy group, a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C20 aryl group, a C1-C20 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group.
In an embodiment, R7 may be a phenyl group, a phenyl group that is substituted with at least one C1-C20 alkyl group; or a phenyl group that is substituted with at least one a phenyl group substituted with at least one deuterium. In an embodiment, the organometallic compound represented by Formula 1 may be represented by Formula 1-1 or Formula 1-2:
wherein, in Formulae 1-1 and 1-2,
M1, Y10 to Y12, Y20 to Y22, Y30 to Y32, Y40 to Y42, A1 to A4, L1 to L4, R1 to R6, and b1 to b4 are the same as described above.
In an embodiment, the organometallic compound represented by Formula 1 may be represented by at least one selected from Formula 1(1) to Formula 1(12):
wherein, in Formulae 1(1) to 1(12),
M1, Y20 to Y40, and L1 to L4 are the same as described above,
X11 may be C(R11) or N, X12 may be C(R12) or N, X21 may be C(R21) or N, X22 may be C(R22) or N, X23 may be C(R23) or N, X24 may be C(R24) or N, X25 may be C(R25) or N, X26 may be C(R26) or N, X31 may be C(R31) or N, X32 may be C(R32) or N, X33 may be C(R33) or N, X34 may be C(R34) or N, X35 may be C(R35) or N, X36 may be C(R36) or N, X37 may be C(R37) or N, X41 may be C(R41) or N, X42 may be C(R42) or N, X43 may be C(R43) or N, and X44 may be C(R44) or N, X45 may be C(R45) or N, X46 may be C(R46) or N, and X47 may be C(R47) or N,
R11 to R12, R21 to R26, R31 to R37, and R41 to R44 are the same as described in connection with R1 to R8, and
two neighboring substituents of R1 to R12, R21 to R26, R31 to R37, and R41 to R44 may optionally be bonded to each other to form a C5-C60 carbocyclic group that is unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group that is unsubstituted or substituted with at least one R10a. The variable R10a is as described above.
In an embodiment, the organometallic compound represented by Formula 1 may be selected from Compounds BD1 to BD90, but embodiments are not limited thereto:
Although not wanting to be bound by theory, the organometallic compound represented by Formula 1 may have more flexible intramolecular structure due to the use of
—C(R5)(R6)O— or —C(R5)(R6)N(R7)— as a linker connecting A1 to A2, and as a result, the formation of exciplex or excimer between a dopant and a dopant, or between a dopant and a host in a light-emitting device may be inhibited and thus, a longer lifespan may be obtained.
In addition, the intramolecular conjugation may be broken by using carbon included in the linker connecting A1 to A2. Accordingly, when the linker is included in the organometallic compound represented by Formula 1 included in the light-emitting device, the high color purity, high efficiency, low driving voltage and lifespan of the light-emitting device may be derived.
The organometallic compound may emit blue light. In an embodiment, the organometallic compound may emit blue light (bottom emission CIEx,y color coordinates X=0.14, and Y=0.06 to 0.25) having a maximum emission wavelength of about 430 nanometer (nm) or more and about 485 nm or less, but embodiments are not limited thereto. Accordingly, the organometallic compound represented by Formula 1 may be useful for the manufacture of a light-emitting device that emits blue light. Synthesis methods of the organometallic compound represented by Formula 1 may be recognizable by one of ordinary skill in the art by referring to Examples provided below.
At least one of such organometallic compounds represented by Formula 1 may be used between a pair of electrodes of a light-emitting device. In an embodiment, the organometallic compound may be included in an emission layer. The organometallic compound included in the emission layer may act as a dopant. In one or more embodiments, the organometallic compound represented by Formula 1 may be used as a material for a capping layer located outside a pair of electrodes of a light-emitting device.
Accordingly, a light-emitting device constructed according to the principles and illustrative implementations of the invention may include: a first electrode; a second electrode facing the first electrode; an interlayer located between the first electrode and the second electrode and including an emission layer; and at least one organometallic compound represented by Formula 1.
In an embodiment, the light-emitting device may further include: a first capping layer located outside the first electrode and including the organometallic compound represented by Formula 1; a second capping layer located outside the second electrode and including the organometallic compound represented by Formula 1; or the first capping layer and the second capping layer. In an embodiment, the interlayer and/or the capping layer may include the organometallic compound.
For example, the interlayer and/or the capping layer may include Compound BD01 as the organometallic compound. In this regard, Compound BD1 may exist in the emission layer of the light-emitting device. In one or more embodiments, the interlayer and/or the capping layer may include, as the organometallic compound, Compound BD1 and Compound BD2. In this regard, Compound BD1 and Compound BD2 may exist in an identical layer (for example, both Compound BD1 and Compound BD2 may exist in an emission layer), or different layers (for example, Compound BD1 may exist in an emission layer and Compound BD2 may exist in an electron transport region).
In some embodiments, the first electrode of the light-emitting device may be an anode, the second electrode of the light-emitting device may be a cathode, the interlayer may further include a hole transport region between the first electrode and the emission layer and an electron transport region between the emission layer and the second electrode, 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, and the electron transport region may include a buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, or any combination thereof.
In an embodiment, the emission layer may include the organometallic compound. In an embodiment, the emission layer may include the organometallic compound represented by Formula 1, the emission layer may further include a host, and an amount of the host in the emission layer may be greater than an amount of the organometallic compound in the emission layer. In an embodiment, the host may include different hosts. In an embodiment, the host may include a hole transport host and an electron transport host. In an embodiment, the dopant may further include a fluorescence emitter or a thermally active delayed fluorescence (TADF) emitter. In this regard, the fluorescence emitter refers to any material that emits fluorescent light.
In an embodiment, the host may include an electron transport host compound represented by Formula 5 and a hole transport host compound including a group represented by Formula 7.
ring CY51 to ring CY53 and ring CY71 and ring CY72 in Formulae 5 and 7 may each independently be selected from a C5-C30 carbocyclic group and a C1-C30 heterocyclic group.
In an embodiment, in Formulae 5 and 7, ring CY51 to ring CY53 and ring CY71 and ring CY72 may each independently be i) a first ring, ii) a second ring, iii) a condensed cyclic group in which two or more first rings are condensed with each other, iv) a condensed cyclic group in which two or more second rings are condensed with each other, and v) a condensed cyclic group in which at least one first ring is condensed with at least one second ring,
the first ring may be 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, and
the second ring may be 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, or an azadibenzofuran group.
For example, ring CY51 to ring CY53 and ring CY71 and ring CY72 in Formulae 5 and 7 may each independently be selected from a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, cyclopentadiene group, a 1,2,3,4-tetrahydronaphthalene group, a thiophene group, a furan group, an indole group, a benzoborole group, a benzophosphole group, an indene group, a benzosilole group, a benzogermole group, a benzothiophene group, a benzoselenophene group, a benzofuran group, a carbazole group, a dibenzoborole group, a dibenzophosphole group, a fluorene group, a dibenzosilole group, a dibenzogermole group, a dibenzothiophene group, a dibenzoselenophene group, a dibenzofuran group, a dibenzothiophene 5-oxide group, 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isooxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, and a 5,6,7,8-tetrahydroquinoline group, but embodiments are not limited thereto.
L51 to L53 in Formula 5 may each independently be a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In an embodiment, L51 to L53 in Formula 5 may each independently be selected from a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, cyclopentadiene group, a furan group, a thiophene group, a silole group, an indene group, a fluorene group, an indole group, a carbazole group, a benzofuran group, a dibenzofuran group, a benzothiophene group, a dibenzothiophene group, a benzosilole group, a dibenzosilole group, an azafluorene group, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isooxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, and a benzothiadiazole group;
a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, cyclopentadiene group, a furan group, a thiophene group, a silole group, an indene group, a fluorene group, an indole group, a carbazole group, a benzofuran group, a dibenzofuran group, a benzothiophene group, a dibenzothiophene group, a benzosilole group, a dibenzosilole group, an azafluorene group, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isooxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group and a benzothiadiazole group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a naphthalenyl group, an anthracenyl group, a phenanthrenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a cyclopentadienyl group, a furanyl group, a thiophenyl group, a silolyl group, an indenyl group, a fluorenyl group, an indolyl group, a carbazolyl group, a benzofuranyl group, a dibenzofuranyl group, a benzothiophenyl group, a dibenzothiophenyl group, a benzosilolyl group, a dibenzosilolyl group, an azafluorenyl group, an azacarbazolyl group, an azadibenzofuranyl group, an azadibenzothiophenyl group, an azadibenzosilolyl group, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a phenanthrolinyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a triazolyl 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, benzothiadiazolyl group, —Si(Q31)(Q32)(Q33), —N(Q31)(Q32), —B(Q31)(Q32), —C(═O)(Q31), —S(═O)2(Q31), —P(═O)(Q31)(Q32), and any combination thereof; and
*—C(Q1)(Q2)-*′, *—Si(Q1)(Q2)-*′, *—N(Q1)-*′, *—B(Q1)-*′, *—C(═O)—*′, *—S(═O)2—*′ and *—P(═O)(Q1)-*′,
wherein Q1 to Q2 and Q31 to Q33 may each independently be selected from hydrogen, deuterium, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a biphenyl group, a terphenyl group, a pyridinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, and a triazinyl group, but embodiments are not limited thereto.
* and *′ each indicate a binding site to a neighboring element.
In Formula 5, a bond between L51 and ring CY51, a bond between L52 and ring CY52, a bond between L53 and ring CY53, a bond between or among two or more of L51, a bond between or among two or more of L52, a bond between or among two or more of L53, a bond between L51 and carbon between X54 and X55 of Formula 5, a bond between L52 and carbon between X54 and X56 of Formula 5, and a bond between L53 and carbon between X55 and X56 of Formula 5 may each be a “carbon-carbon single bond”, a “carbon-silicon single bond”, or “carbon-nitrogen single bond.”
The variables b51 to b53 in Formula 5 may each independently be an integer from 0 to 5, wherein when b51 is 0, *-(L51)b51-*′ may be a single bond, when b52 is 0, *-(L52)b52-*′ may be a single bond, when b53 is 0, *-(L53)ab3-*′ may be a single bond. For example, b51 to b53 may each independently be 0, 1, or 2. In Formula 5, X54 may be N or C(R54), X55 may be N or C(R55), X56 may be N or C(R56), and at least one of X54 to X56 may be N. R54 to R56 are the same as described above. The variable X81 in Formula 7 may be a single bond, O, S, N(R81), B(R81), C(R81a)(R81b), or Si(R81a)(R81b). R81, R81a, and R81b are the same as described above.
The variables R51 to R56, R71, R72, R81, R81a and R81b in Formulae 5 and 7 may each independently be selected from hydrogen, deuterium, —F, —Cl, —Br, —I, —CH2D, —CHD2, —CD3, —CH2F, —CHF2, —CF3, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkenyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkynyl group unsubstituted or substituted with at least one R10a, a C1-C60 alkoxy group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, a C6-C60 aryloxy group unsubstituted or substituted with at least one R10a, a C6-C60 arylthio group unsubstituted or substituted with at least one R10a, —Si(Q1)(Q2)(Q3), —N(Q1)(Q2), —B(Q1)(Q2), —C(═O)(Q1), —S(═O)2(Q1), and —P(═O)(Q1)(Q2). Q1 to Q3 are the same as described herein.
In an embodiment, R51 to R56, R71, R72, R81, R81a, and R81b in Formulae 5 and 7 may each independently be selected from:
hydrogen, deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, and a nitro group;
a C1-C60 alkyl group and a C1-C60 alkoxy group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, or any combination thereof,
a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a phenyl group, a biphenyl group, a terphenyl group, a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, an indacenyl group, an acenaphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl 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 pentacenyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, a silolyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolyl group, an isoindolyl group, an indazolyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a benzoisoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a benzoquinoxalinyl group, a quinazolinyl group, a benzoquinazolinyl group, a cinnolinyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzosilolyl group, a benzothiazolyl group, a benzoisothiazolyl group, a benzoxazolyl group, a benzoisoxazolyl group, a triazolyl group, a tetrazolyl group, a thiadiazolyl group, an oxadiazolyl group, a triazinyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a dibenzosilolyl group, a benzocarbazolyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group, a naphthobenzosilolyl group, a dibenzocarbazolyl group, a dinaphthofuranyl group, a dinaphthothiophenyl group, a dinaphthosilolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an oxazolopyridinyl group, a thiazolopyridinyl group, a benzonaphthyridinyl group, an azafluorenyl group, an azaspiro-bifluorenyl group, an azacarbazolyl group, an azadibenzofuranyl group, an azadibenzothiophenyl group, an azadibenzosilolyl group, an indenopyrrolyl group, an indolopyrrolyl group, an indenocarbazolyl group, an indolocarbazolyl group, and a group represented by Formula 91, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group, and a C1-C60 alkoxy group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a phenyl group, a biphenyl group, a terphenyl group, a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, an indacenyl group, an acenaphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl 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 pentacenyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, a silolyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolyl group, an isoindolyl group, an indazolyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a benzoisoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a benzoquinoxalinyl group, a quinazolinyl group, a benzoquinazolinyl group, a cinnolinyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzosilolyl group, a benzothiazolyl group, a benzoisothiazolyl group, a benzoxazolyl group, a benzoisoxazolyl group, a triazolyl group, a tetrazolyl group, a thiadiazolyl group, an oxadiazolyl group, a triazinyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a dibenzosilolyl group, a benzocarbazolyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group, naphthobenzosilolyl group, a dibenzocarbazolyl group, a dinaphthofuranyl group, a dinaphthothiophenyl group, a dinaphthosilolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an oxazolopyridinyl group, a thiazolopyridinyl group, a benzonaphthyridinyl group, an azafluorenyl group, an azaspiro-bifluorenyl group, an azacarbazolyl group, an azadibenzofuranyl group, an azadibenzothiophenyl group, an azadibenzosilolyl group, an indenopyrrolyl group, an indolopyrrolyl group, an indenocarbazolyl group, an indolocarbazolyl group, —Si(Q31)(Q32)(Q33), —N(Q31)(Q32), —B(Q31)(Q32), —C(═O)(Q31), —S(═O)2(Q31), —P(═O)(Q31)(Q32), and any combination thereof; and
—Si(Q1)(Q2)(Q3), —N(Q1)(Q2), —B(Q1)(Q2), —C(═O)(Q1), —S(═O)2(Q1), and —P(═O)(Q1)(Q2), wherein
Q1 to Q3 and Q31 to Q33 may each independently be hydrogen; deuterium; —F; —Cl; —Br; —I; a hydroxyl group; a cyano group; a nitro group; a C1-C60 alkyl group; a C2-C60 alkenyl group; a C2-C60 alkynyl group; a C1-C60 alkoxy group; or a C3-C60 carbocyclic group or a C1-C60 heterocyclic group, each unsubstituted or substituted with deuterium, —F, a cyano group, a C1-C60 alkyl group, a C1-C60 alkoxy group, a phenyl group, a biphenyl group, or any combination thereof. However, embodiments are not limited thereto:
wherein, in Formula 91,
ring CY91 and ring CY92 may each independently be selected from a C5-C30 carbocyclic group and a C1-C30 heterocyclic group,
X91 may be a single bond, O, S, N(R91), B(R91), C(R91a)(R91b), or Si(R91a)(R91b),
R91, R91a, and R91b are the same as described in connection with R81, R81a, and R81b, and
* indicates a binding site to a neighboring atom.
For example, in Formula 91,
ring CY91 and ring CY92 may each independently be selected from a benzene group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, and a triazine group,
R91, R91a, and R91b may each independently be selected from:
hydrogen and a C1-C10 alkyl group;
a phenyl group, a biphenyl group, a pyridinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, and a triazinyl group; and
a phenyl group, a pyridinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, and a triazinyl group, each substituted with at least one selected from deuterium, a C1-C10 alkyl group, a phenyl group, a biphenyl group, a pyridinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, and a triazinyl group, but embodiments are not limited thereto.
The variables a51 to a53, a71 and a72 in Formulae 5 and 7 respectively indicate the numbers of R51 to R53 and R71 to R72, and may each independently be an integer from 0 to 10. When a51 is 2 or more, two or more of R51(s) may be identical to or different from each other, and this may be applied to a52, a53, a71, and a72 in the same manner.
In an embodiment, a group represented by
and a group represented by
in Formula 5 may not be a phenyl group.
In an embodiment, the group represented by
and the group represented by
in Formula 5 may be identical to each other.
In one or more embodiments, ring CY51 and ring CY52 in Formula 5 may each independently be a benzene group, a pyridine group, a pyrimidine group, a pyridazine group, a pyrazine group, or a triazine group,
The variables R51 and R52 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkenyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkynyl group unsubstituted or substituted with at least one R10a, a C1-C60 alkoxy group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, a C6-C60 aryloxy group unsubstituted or substituted with at least one R10a, a C6-C60 arylthio group unsubstituted or substituted with at least one R10a, or —Si(Q1)(Q2)(Q3),
Q1 to Q3 may each independently be selected from a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C1-C60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, and a C6-C60 aryl group that is substituted with at least one selected from deuterium, —F, a cyano group, a C1-C10 alkyl group, a phenyl group, and a biphenyl group,
a51 and a52 may each independently be 1, 2, or 3.
In one or more embodiments, a moiety represented by
in Formula 5 may be a group represented by one of Formulae CY51-1 to CY51-18, and/or
a moiety represented by
may be a group represented by one of Formulae CY52-1 to CY52-18, and/or
a moiety represented by
may be a group represented by one of Formulae CY53-1 to CY53-19:
wherein, in Formulae CY51-1 to CY51-18, CY52-1 to CY52-18, and CY53-1 to CY53-19,
T1 may be a single bond, O, S, N(T11), B(T11), C(T11)(T12), or Si(T11)(T12),
T2 may be a single bond, O, S, N(T21), B(T21), C(T21)(T22), or Si(T21)(T22),
T3 may be a single bond, O, S, N(T31), B(T31), C(T31)(T32), or Si(T31)(T32),
T4 may be a single bond, O, S, N(T41), B(T41), C(T41)(T42), or Si(T41)(T42),
each of T1 and T2 in Formulae CY51-16 and CY51-17 may not be a single bond,
each of T3 and T4 in Formula CY52-16 and CY52-17 may not be a single bond,
R51a to R51g, T11, T12, T21, and T22 are the same as described in connection with R51, and each of R51a to R51e is not hydrogen,
R52a to R52i, T31, T32, T41 and T42 are the same as described in connection with R52, and each of R52a to R52e is not hydrogen,
R53a to R53g are the same as described in connection with R53, and each of R53a to R53e is not hydrogen,
Z1 to Z9 in Formulae CY52-18 and CY53-19 may each independently be C or N, and
* indicates a binding site to a neighboring atom.
For example, R51a to R51e and R52a to R52e in Formulae CY51-1 to CY51-15 and Formulae CY52-1 to 52-15 may each independently be selected from:
a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a phenyl group, a biphenyl group, a C1-C10 alkylphenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an isoindolyl group, an indolyl group, an indazolyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a carbazolyl group, a phenanthrolinyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzoisothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, a triazinyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an azacarbazolyl group, an azadibenzofuranyl group, an azadibenzothiophenyl group, an azafluorenyl group, an azadibenzosilolyl group, and a group represented by Formula 91, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I,-CD3,-CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazine group, a hydrazone group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a phenyl group, a biphenyl group, a C1-C10 alkylphenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an isoindolyl group, an indolyl group, an indazolyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a carbazolyl group, a phenanthrolinyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzoisothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, a triazinyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, or any combination thereof, and
—C(Q1)(Q2)(Q3) and —Si(Q1)(Q2)(Q3),
Q1 to Q3 may each independently be:
a phenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, and a triazinyl group, each unsubstituted or substituted with deuterium, a C1-C10 alkyl group, a phenyl group, a biphenyl group, a pyridinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, a triazinyl group, or any combination thereof,
in Formulae CY51-16 and CY51-17, i) T1 is O or S and T2 is Si(T21)(T22), or ii) T1 is Si(T11)(T12) and T2 is O or S, and
in Formulae CY52-16 and CY52-17, i) T3 is O or S and T4 is Si(T41)(T42), or ii) T3 is Si(T31)(T32) and T4 is O or S, but embodiments are not limited thereto.
In an embodiment, the hole transport host compound may be represented by one of Formulae 7-1 to 7-5:
wherein, in Formulae 7-1 to 7-5,
ring CY71, ring CY72, X81, R71, R72, a71, and a72 are the same as described herein,
ring CY73, ring CY74, R73, R74, a73, and a74 are the same as described in connection with ring CY71, ring CY72, R71, R72, a71, and a72,
L81 and L82 may each independently be selected from *—C(Q4)(Q5)—*′, *—Si(Q4)(Q5)—*′, a substituted or unsubstituted C5-C30 carbocyclic group, and a substituted or unsubstituted C1-C30 heterocyclic group, and Q4 and Q5 are the same as described in connection with Q1,
b81 and b82 may each be an integer from 0 to 5, wherein, when b81 is 0, *-(L81)b81-*′ may be a single bond, when b81 is 2 or more, two or more of L81(s) may be identical to or different from each other, when b82 is 0, *-(L82)b82-*′ may be a single bond, and when b82 is 2 or more, two or more of L82(s) may be identical to or different from each other,
X82 may be a single bond, O, S, N(R82), B(R82), C(R82a)(R82b), or Si(R82a)(R82b),
X83 may be a single bond, O, S, N(R83), B(R83), C(R83a)(R83b), or Si(R83a)(R83b),
each of X82 and X83 in Formulae 7-2 and 7-4 may not be a single bond,
X84 may be C or Si,
R80, R82, R83, R82a, R82b, R83a, R83b, and R84 are the same as described in connection with R81, and
* and *′ each indicate a binding site to a neighboring atom.
For example, L81 and L82 may each independently be selected from:
*—C(Q4)(QS)—*′ and *—Si(Q4)(QS)—*′; and
a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, cyclopentadiene group, a furan group, a thiophene group, a silole group, an indene group, a fluorene group, an indole group, a carbazole group, a benzofuran group, a dibenzofuran group, a benzothiophene group, a dibenzothiophene group, a benzosilole group, a dibenzosilole group, an azafluorene group, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isooxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, and a benzothiadiazole group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazine group, a hydrazone group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a naphthalenyl group, an anthracenyl group, a phenanthrenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a cyclopentadienyl group, a furanyl group, a thiophenyl group, a silolyl group, an indenyl group, a fluorenyl group, an indolyl group, a carbazolyl group, a benzofuranyl group, a dibenzofuranyl group, a benzothiophenyl group, a dibenzothiophenyl group, a benzosilolyl group, a dibenzosilolyl group, an azafluorenyl group, an azacarbazolyl group, an azadibenzofuranyl group, an azadibenzothiophenyl group, an azadibenzosilolyl group, a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a phenanthrolinyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a triazolyl 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, benzothiadiazolyl group, —Si(Q31)(Q32)(Q33), —N(Q31)(Q32), —B(Q31)(Q32), —C(═O)(Q31), —S(═O)2(Q31), —P(═O)(Q31)(Q32), —P(═O)(Q31)(Q32), or any combination thereof,
wherein Q4, Qs, and Q31 to Q33 may each independently be selected from hydrogen, deuterium, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a biphenyl group, a terphenyl group, a pyridinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, and a triazinyl group, but embodiments are not limited thereto.
For example, a moiety represented by
in Formulae 7-1 and 7-2 may be a group represented by one of Formulae CY71-1(1) to CY71-1(8),
a moiety represented by
in Formulae 7-1 and 7-3 may be a group represented by one of Formulae CY71-2(1) to CY71-2(8),
a moiety represented by
in Formulae 7-2 and 7-4 may be a group represented by one of Formulae CY71-3(1) to CY71-3(32),
a moiety represented by
in Formulae 7-3 to 7-5 may be a group represented by one of Formulae CY71-4(1) to CY71-4(32), and
a moiety represented by
in Formulae 7-5 may be a group represented by one of Formulae CY71-5(1) to CY71-5(8), but embodiments are not limited thereto:
In Formulae CY71-1(1) to CY71-1(8), CY71-2(1) to CY71-2(8), CY71-3(1) to CY71-3(32), CY71-4(1) to CY71-4(32), and CY71-5(1) to CY71-5(8),
X81 to X84, R80 and R84 are the same as described herein,
X85 may be a single bond, O, S, N(R85), B(R85), C(R85a)(R85b), or Si(R85a)(R85b),
X86 may be a single bond, O, S, N(R86), B(R86), C(R86a)(R86b), or Si(R86a)(R86b),
each of X85 and X86 in Formulae CY71-1(1) to CY71-1(8) and CY71-4(1) to CY71-4(32) is not a single bond,
X87 may be a single bond, O, S, N(R87), B(R87), C(R87a)(R87b), or Si(R87a)(R87b),
X88 may be a single bond, O, S, N(R88), B(R88), C(R88a)(R88b), or Si(R88a)(R88b),
each of X87 and X88 in Formulae CY71-2(1) to CY71-2(8), CY71-3(1) to CY71-3(32) and CY71-5(1) to CY71-5(8) may not be a single bond, and
R85 to R88, R85a, R85b, R86a, R86b, R87a, R87b, R88a and R88b are the same as described in connection with R81.
In an embodiment, the electron transport host compound may be selected from compounds ETH1 to ETH84:
In an embodiment, the hole transport host compound may be selected from compounds HTH1 to HTH52:
In this regard, Ph is phenyl, Ph3 is three phenyl groups, and D4 is four deuterium atoms. The emission layer of the light-emitting device may include:
1) the organometallic compound represented by Formula 1,
2) an electron transport host compound represented by Formula 5 (a bond between L51 and ring CY51, a bond between L52 and ring CY52, a bond between L53 and ring CY53, a bond between or among two or more of L51, a bond between or among two or more of L52, a bond between or among two or more of L53, a bond between L51 and carbon between X54 and X55 of Formula 5, a bond between L52 and carbon between X54 and X56 of Formula 5, and a bond between L53 and carbon between X55 and X56 of Formula 5 may each be a “carbon-carbon single bond”, a “carbon-silicon single bond”, or “carbon-nitrogen single bond,” and
3) an electron transport host compound which includes a group represented by Formula 7, which is different from Formula 1.
Accordingly, the formation of exciplexes between a first compound and either a second compound or a third compound is effectively suppressed, and thus, a light-emitting device with high emission efficiency, high color purity and long lifespan can be achieved.
Although not wanting to be bound by theory, the organometallic compound is a 4-coordination organometallic compound, and has a rigid structure by the introduction of the bulky group of A1, thereby inhibiting the formation of exciplex between the organometallic compound and the host compound, and as a result, the manufactured light-emitting device may have high efficiency and high color purity.
In an embodiment, the fluorescence emitter or the TADF emitter may include a compound represented by Formula 9-1, a compound represented by Formula 9-2, or any combination thereof:
wherein, in Formulae 9-1 and 9-2,
ring A91 to ring A94 may each independently be a C5-C60 carbocyclic group or a C1-C60 heterocyclic group,
Y91 and Y92 may each independently be B, N, P, or P(═O),
X91 to X94 may each independently be O, S, N(R97), B(R97), C(R97)(R98), or Si(R97)(R98),
R91 to R98 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkenyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkynyl group unsubstituted or substituted with at least one R10a, a C1-C60 alkoxy group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, a C6-C60 aryloxy group unsubstituted or substituted with at least one R10a, a C6-C60 arylthio group unsubstituted or substituted with at least one R10a, —C(Q1)(Q2)(Q3), —Si(Q1)(Q2)(Q3), —N(Q1)(Q2), —B(Q1)(Q2), —C(═O)(Q1), —S(═O)2(Q1), or —P(═O)(Q1)(Q2),
b91 to b94 may each independently be an integer from 0 to 20, and
R10a and Q1 to Q3 are each the same as described herein.
The difference between the excitation triplet energy level of the organometallic compound represented by Formula 1 and the excitation triplet energy level of the compound represented by one of Formula 9-1 or 9-2 is sufficiently small that Dexter energy transfer may occur.
Regarding Formula 9-1 or Formula 9-2, the difference between the excitation triplet energy level and the excitation singlet energy level is small (for example, within about 0.3 eV), so that the excitons of the excitation triplet energy can be converted into excitons of the excitation singlet energy by the reverse inter system crossing (RISC) mechanism.
Therefore, in the case of a light-emitting device further including a compound represented by Formula 9-1 or Formula 9-2 according to an embodiment, excitation triplet excitons delivered from an organometallic compound do not extinct, but are transferred to excitation singlet excitons and then to a ground state, thereby enabling the manufacture of an (organic) light-emitting device having high efficiency and a long lifespan.
In an embodiment, the compound represented by Formula 9-1 or Formula 9-2 may be a fluorescence emitter. For example, the compound represented by Formula 9-1 or Formula 9-2 may be a delayed fluorescence dopant.
The variables Y91 and Y92 in Formula 9-1 and Formula 9-2 may each independently be B or N. For example, Y91 and Y92 may be B. In an embodiment, X91 to X94 may be N(R97). In an embodiment, R91 to R98 may each independently be:
hydrogen, deuterium, —F, —Cl, —Br, —I, —CH2D, —CHD2,-CD3, —CH2F, —CHF2, —CF3, a hydroxyl group, a cyano group, and a nitro group;
a C1-C60 alkyl group and a C1-C60 alkoxy group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I,-CD3,-CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, or any combination thereof,
a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a phenyl group, a biphenyl group, a terphenyl group, a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, an indacenyl group, an acenaphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl 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 pentacenyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, a silolyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolyl group, an isoindolyl group, an indazolyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a benzoisoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a benzoquinoxalinyl group, a quinazolinyl group, a benzoquinazolinyl group, a cinnolinyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzosilolyl group, a benzothiazolyl group, a benzoisothiazolyl group, a benzoxazolyl group, a benzoisoxazolyl group, a triazolyl group, a tetrazolyl group, a thiadiazolyl group, an oxadiazolyl group, a triazinyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a dibenzosilolyl group, a benzocarbazolyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group, a naphthobenzosilolyl group, a dibenzocarbazolyl group, a dinaphthofuranyl group, a dinaphthothiophenyl group, a dinaphthosilolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an oxazolopyridinyl group, a thiazolopyridinyl group, a benzonaphthyridinyl group, an azafluorenyl group, an azaspiro-bifluorenyl group, an azacarbazolyl group, an azadibenzofuranyl group, an azadibenzothiophenyl group, an azadibenzosilolyl group, an indenopyrrolyl group, an indolopyrrolyl group, an indenocarbazolyl group, and an indolocarbazolyl group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I,-CD3,-CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C60 alkyl group, a C1-C60 alkoxy group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a phenyl group, a biphenyl group, a terphenyl group, a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, an indacenyl group, an acenaphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl 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 pentacenyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, a silolyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolyl group, an isoindolyl group, an indazolyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a benzoisoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a benzoquinoxalinyl group, a quinazolinyl group, a benzoquinazolinyl group, a cinnolinyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzosilolyl group, a benzothiazolyl group, a benzoisothiazolyl group, a benzoxazolyl group, a benzoisoxazolyl group, a triazolyl group, a tetrazolyl group, a thiadiazolyl group, an oxadiazolyl group, a triazinyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a dibenzosilolyl group, a benzocarbazolyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group, naphthobenzosilolyl group, a dibenzocarbazolyl group, a dinaphthofuranyl group, a dinaphthothiophenyl group, a dinaphthosilolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an oxazolopyridinyl group, a thiazolopyridinyl group, a benzonaphthyridinyl group, an azafluorenyl group, an azaspiro-bifluorenyl group, an azacarbazolyl group, an azadibenzofuranyl group, an azadibenzothiophenyl group, an azadibenzosilolyl group, an indenopyrrolyl group, an indolopyrrolyl group, an indenocarbazolyl group, an indolocarbazolyl group, —Si(Q31)(Q32)(Q33), —N(Q31)(Q32), —B(Q31)(Q32), —C(═O)(Q31), —S(═O)2(Q31), —P(═O)(Q31)(Q32), or any combination thereof, and
—Si(Q1)(Q2)(Q3), —N(Q1)(Q2), —B(Q1)(Q2), —C(═O)(Q1), —S(═O)2(Q1), and —P(═O)(Q1)(Q2), wherein
Q1 to Q3 and Q31 to Q33 may each independently be: hydrogen; deuterium; —F; —Cl; —Br; —I; a hydroxyl group; a cyano group; a nitro group; a C1-C60 alkyl group; a C2-C60 alkenyl group; a C2-C60 alkynyl group; a C1-C60 alkoxy group; a C3-C60 carbocyclic group; or a C1-C60 heterocyclic group, each unsubstituted or substituted with deuterium, —F, a cyano group, a C1-C60 alkyl group, a C1-C60 alkoxy group, a phenyl group, a biphenyl group, or any combination thereof. However, embodiments are not limited thereto.
According to an embodiment, the compound represented by Formula 9-1 or Formula 9-2 may be selected from Compounds DFD1 to DFD12.
wherein Ph represents a phenyl group and D5 is five deuterium atoms.
According to another aspect of the invention, an electronic apparatus includes an embodiment of a light-emitting device constructed according to the principles of the invention. The electronic apparatus may further include a thin-film transistor. In one or more embodiments, the electronic apparatus may further include a thin-film transistor including a source electrode and a drain electrode, and the first electrode of the light-emitting device may be electrically connected to the source electrode or the drain electrode. In an embodiment, the electronic apparatus may further include a color filter, a color conversion layer, a touch screen layer, a polarizing layer, or any combination thereof. More details on the electronic apparatus are the same as described herein.
Particularly,
In
The first electrode 110 may be formed by, for example, depositing or sputtering a material for forming the first electrode 110 on the substrate. When the first electrode 110 is an anode, a material for forming the first electrode 110 may be a high work function material that facilitates 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 an indium tin oxide (ITO), an indium zinc oxide (IZO), a tin oxide (SnO2), a zinc oxide (ZnO), or any combinations thereof. In one or more embodiments, when the first electrode 110 is a semi-transmissive electrode or a reflective electrode, magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), or any combinations thereof may be used as a material for forming a first electrode.
The first electrode 110 may have a single-layered structure consisting of a single layer or a multi-layered structure including a plurality of layers. For example, the first electrode 110 may have a three-layered structure of an ITO/Ag/ITO.
The interlayer 130 may be located on the first electrode 110. The interlayer 130 may include an emission layer. The interlayer 130 may further include a hole transport region placed between the first electrode 110 and the emission layer and an electron transport region placed between the emission layer and the second electrode 150. The interlayer 130 may further include, in addition to various organic materials, metal-containing compounds such as organometallic compounds, inorganic materials such as quantum dots, and the like.
In one or more embodiments, the interlayer 130 may include, i) two or more emitting units sequentially stacked between the first electrode 110 and the second electrode 150 and ii) a charge generation layer located between the two emitting units. When the interlayer 130 includes the emitting unit and the charge generation layer as described above, the light-emitting device 10 may be a tandem light-emitting device.
The hole transport region may have: i) a single-layered structure consisting of a single layer consisting of a single material, ii) a single-layered structure consisting of a single layer consisting of a plurality of different materials, or iii) a multi-layered structure including a plurality of layers including different materials. The hole transport region may include at least one layer selected from a hole injection layer, a hole transport layer, an emission auxiliary layer, and an electron blocking layer.
In an embodiment, the hole transport region may have a single-layered structure including a single layer including a plurality of different materials, or a multi-layered structure having 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 for each structure, constituting layers are sequentially stacked from the first electrode 110 in this 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.
wherein, in Formulae 201 and 202,
L201 to L204 may each independently be a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a,
L205 may be *—O—*′, *—S—*′, *—N(Q201)-*′, a C1-C20 alkylene group unsubstituted or substituted with at least one R10a, a C2-C20 alkenylene group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a,
xa1 to xa4 may each independently be an integer from 0 to 5,
xa5 may be an integer from 1 to 10,
R201 to R204 and Q201 may each independently be a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a,
R201 and R202 may optionally be linked to each other, via a single bond, a C1-C5 alkylene group unsubstituted or substituted with at least one R10a, or a C2-C5 alkenylene group unsubstituted or substituted with at least one R10a, to form a C8-C60 polycyclic group (for example, a carbazole group or the like) unsubstituted or substituted with at least one R10a (for example, Compound HT16),
R203 and R204 may optionally be linked to each other, via a single bond, a C1-C5 alkylene group unsubstituted or substituted with at least one R10a, or a C2-C5 alkenylene group unsubstituted or substituted with at least one R10a, to form a C8-C60 polycyclic group unsubstituted or substituted with at least one R10a, and
na1 may be an integer from 1 to 4.
In one or more embodiments, each of Formulae 201 and 202 may include at least one of groups represented by Formulae CY201 to CY217.
The variables R10b and R10c in Formulae CY201 to CY217 are the same as described in connection with R10a, ring CY201 to ring CY204 may each independently be a C3-C20 carbocyclic group or a C1-C20 heterocyclic group, and at least one hydrogen in Formulae CY201 to CY217 may be unsubstituted or substituted with R10a.
In one or more embodiments, ring CY201 to ring CY204 in Formulae CY201 to CY217 may each independently be a benzene group, a naphthalene group, a phenanthrene group, or an anthracene group. In one or more embodiments, each of Formulae 201 and 202 may include at least one of groups represented by Formulae CY201 to CY203.
In one or more embodiments, Formula 201 may include at least one of groups represented by Formulae CY201 to CY203 and at least one of groups represented by Formulae CY204 to CY217. In one or more embodiments, xa1 in Formula 201 may be 1, R201 may be a group represented by one of Formulae CY201 to CY203, xa2 may be 0, and R202 may be a group represented by one of Formulae CY204 to CY207. In one or more embodiments, each of Formulae 201 and 202 may not include a group represented by one of Formulae CY201 to CY203.
In one or more embodiments, each of Formulae 201 and 202 may not include a group represented by one of Formulae CY201 to CY203, and may include at least one of groups represented by Formulae CY204 to CY217. In one or more embodiments, each of Formulae 201 and 202 may not include a group represented by one of Formulae CY201 to CY217.
In some embodiments, the hole transport region may include one of Compounds HT1 to HT46 and 4,4′,4″-tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), 1-N,1-N-bis[4-(diphenylamino)phenyl]-4-N,4-N-diphenylbenzene-1,4-diamine (TDATA), 4,4′,4″-tris[2-naphthyl(phenyl)amino]triphenylamine (2-TNATA), bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidine (NPB or NPD), N4,N4′-di(naphthalen-2-yl)-N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (P-NPB), N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-9,9-spirobifluorene-2,7-diamine (spiro-TPD), N2,N7-di-1-naphthalenyl-N2,N7-diphenyl-9,9′-spirobi[9H-fluorene]-2,7-diamine (spiro-NPB), N,N′-di(1-naphthyl)-N,N′-diphenyl-2,2′-dimethyl-(1,1′-biphenyl)-4,4′-diamine (methylated-NPB), 4,4′-cyclohexylidenebis[N,N-bis(4-methylphenyl)benzenamine] (TAPC), N,N,N′,N′-tetrakis(3-methylphenyl)-3,3′-dimethylbenzidine (HMTPD), 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (PANI/CSA), polyaniline/poly(4-styrenesulfonate (PANI/PSS), Compounds HTH1 to HTH52, or any combination thereof:
The thickness of the hole transport region may be in a range of about 50 angstrom (Å) to about 10,000 Å, for example, 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, the thickness of the hole injection layer may be in a range of about 100 Å to about 9,000 Å, for example, about 100 Å to about 1,000 Å, and the thickness of the hole transport layer may be in a range of about 50 Å to about 2,000 Å, for example, 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 increase light-emission efficiency by compensating for an optical resonance distance according to the wavelength of light emitted by an emission layer, and the electron-blocking layer may block the injection of leaked electrons from an emission layer to a 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. In an embodiment, the lowest unoccupied molecular orbital (LUMO) energy level of the p-dopant may be about −3.5 eV or less.
In an embodiment, the p-dopant may include a quinone derivative, a cyano group-containing compound, a compound containing element EL1 and element EL2, or any combination thereof.
Examples of the quinone derivative are tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), etc.
Examples of the cyano group-containing compound are 1,4,5,8,9,12-hexaazatriphenylene-hexacarbonitrile (HAT-CN), and a compound represented by Formula 221 below.
In Formula 221,
R221 to R223 may each independently be a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, and
at least one of R221 to R223 may each independently be a C3-C60 carbocyclic group or a C1-C60 heterocyclic group, each substituted with a cyano group; —F; —Cl; —Br; —I; a C1-C20 alkyl group substituted with a cyano group, —F, —Cl, —Br, —I, or any combination thereof, or any combination thereof.
In the compound including element EL1 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 (Rb), 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.).
In an embodiment, examples of the compound containing 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 a tungsten oxide (for example, WO, W2O3, WO2, WO3, W2O5, etc.), a vanadium oxide (for example, VO, V2O3, VO2, V2O5, etc.), a molybdenum oxide (MoO, Mo2O3, MoO2, MoO3, Mo2O5, etc.), and a 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, YbCl3, SmCl3, YbBr, YbBr2, YbBr3, SmBr3, YbI, YbI2, YbI3, and SmI3. 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.).
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 sub-pixel. In one or more 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 contact each other or are separated from each other. In one or more 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 are 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 at least one selected from a phosphorescent dopant and a fluorescent dopant. The phosphorescent dopant may include the organometallic compound represented by Formula 1. The amount of the dopant in the emission layer may be from about 0.01 to about 15 parts by weight based on 100 parts by weight of the host. In one or more embodiments, the emission layer may include a quantum dot. The emission layer may include a delayed fluorescence material. The delayed fluorescence material may act as a host or a dopant in the emission layer.
The thickness of the emission layer may be in a range of about 100 Å to about 1,000 Å, for example, about 200 Å to about 600 Å. When the thickness of the emission layer is within these ranges, excellent light-emission characteristics may be obtained without a substantial increase in driving voltage.
In one or more embodiments, the host may include a compound represented by Formula 301 below:
[Ar301]xb11-[(L301)xb1-R301]xb21 Formula 301
wherein, in Formula 301,
Ar301 and L301 may each independently be a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a,
xb11 may be 1, 2, or 3,
xb1 may be an integer from 0 to 5,
R301 may be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkenyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkynyl group unsubstituted or substituted with at least one R10a, a C1-C60 alkoxy group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, —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
Q301 to Q303 are the same as described in connection with Q1.
For example, when xb11 in Formula 301 is 2 or more, two or more of Ar301(s) may be linked to each other via a single bond. In one or more embodiments, the host may include a compound represented by Formula 301-1, a compound represented by Formula 301-2, or any combination thereof.
wherein, in Formulae 301-1 and 301-2,
ring A301 to ring A304 may each independently be a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a,
X301 may 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 R301 are each the same as described herein,
L302 to L304 are each independently the same as described in connection with L301,
xb2 to xb4 may each independently be the same as described in connection with xb1, and
R302 to R305 and R311 to R314 are each the same as described in connection with R301.
In one or more embodiments, the host may include an alkali earth metal complex, a post-transition metal complex, or any combination thereof. In one or more embodiments, the host may include a Be complex (for example, Compound H55), an Mg complex, a Zn complex, or any combination thereof.
In an embodiment, the host may include one of Compounds H1 to H124, 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(carbazol-9-yl)benzene (mCP), 1,3,5-tri(carbazol-9-yl)benzene (TCP), or any combination thereof:
The phosphorescent dopant may include an organometallic compound represented by Formula 1. In an embodiment, 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. For example, the phosphorescent dopant may include an organometallic compound represented by Formula 401:
wherein, in Formulae 401 and 402,
M may be 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)),
L401 may be a ligand represented by Formula 402, and xc1 may be 1, 2, or 3, wherein when xc1 is 2 or more, two or more of L401(s) may be identical to or different from each other,
L402 may be an organic ligand, xc2 may be 0, 1, 2, 3, or 4, and when xc2 is 2 or more, two or more of L402(s) may be identical to or different from each other,
X401 and X402 may each independently be nitrogen or carbon,
ring A401 and ring A402 may each independently be a C3-C60 carbocyclic group or a C1-C60 heterocyclic group,
T401 may be a single bond, *—O—*′, *—S—*′, *—C(═O)—*′, *—N(Q411)-*′, *—C(Q411)(Q412)-*′, *—C(Q411)=C(Q412)-*′, *—C(Q411)=*′, or *═C═*′,
X403 and X404 may 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),
Q411 to Q414 are the same as described in connection with Q1,
R401 and R402 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C20 alkyl group unsubstituted or substituted with at least one R10a, a C1-C20 alkoxy group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, —Si(Q401)(Q402)(Q403), —N(Q401)(Q402), —B(Q401)(Q402), —C(═O)(Q401), —S(═O)2(Q401), or —P(═O)(Q401)(Q402),
Q401 to Q403 are the same as described in connection with 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.
For example, in Formula 402, i) X401 may be nitrogen, and X402 may be carbon, or ii) each of X401 and X402 may be nitrogen. In one or more embodiments, when xc1 in Formula 402 is 2 or more, two ring A401(s) in two or more of L401(s) may be optionally linked to each other via T402, which is a linking group, and two ring A402(s) may be optionally linked to each other via T403, which is a linking group (see Compounds PD1 to PD4 and PD7). The variables T402 and T403 are the same as described in connection with T401.
The group L402 in Formula 401 may be an organic ligand. For example, L402 may include a halogen group, a diketone group (for example, an acetylacetonate group), a carboxylic acid group (for example, a picolinate group), a —C(═O) group, 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, one of compounds PD1 to PD25, or any combination thereof:
The fluorescent dopant may include an amine group-containing compound, a styryl group-containing compound, or any combination thereof. In one or more embodiments, the fluorescent dopant may include a compound represented by Formula 501:
wherein, in Formula 501,
Ar501, L501 to L503, R501, and R502 may each independently be a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a,
xd1 to xd3 may each independently be 0, 1, 2, or 3, and
xd4 may be 1, 2, 3, 4, 5, or 6.
In one or more embodiments, Ar501 in Formula 501 may 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 one or more embodiments, xd4 in Formula 501 may be 2.
In one or more embodiments, the fluorescent dopant may include: one of Compounds FD1 to FD36; DPVBi; DPAVBi; or any combination thereof:
The emission layer may include a delayed fluorescence material. 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 act as a host or a dopant depending on the type of other materials included in the emission layer. In one or more embodiments, the difference between the triplet energy level in electron volt (eV) of the delayed fluorescence material and the singlet energy level (eV) of the delayed fluorescence material may be greater than or equal to about 0 eV and less than or equal 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 emission efficiency of the light-emitting device 10 may be improved.
In one or more embodiments, the delayed fluorescence material may include i) a material including at least one electron donor (for example, a π electron-rich C3-C60 cyclic group, such as a carbazole group) and at least one electron acceptor (for example, a sulfoxide group, a cyano group, or a π electron-deficient nitrogen-containing C1-C60 cyclic group), and ii) a material including a C8-C60 polycyclic group in which two or more cyclic groups are condensed while sharing boron (B).
In one or more embodiments, the delayed fluorescence material may include at least one of Compounds DF1 to DF9:
The emission layer may include a quantum dot. The 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.
According to the wet chemical process, a precursor material is mixed with an organic solvent to grow 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 through a process which is more easily performed than vapor deposition methods, such as metal organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE), and which requires low costs.
The quantum dot may include a semiconductor compound of Groups II-VI, a semiconductor compound of Groups III-V, a semiconductor compound of Groups III-VI, a semiconductor compound of Groups I, III, and VI, a semiconductor compound of Groups IV-VI, an element or a compound of Group IV; or any combination thereof.
Examples of the semiconductor compound of Groups II-VI may include a binary compound, such as 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 semiconductor compound of Groups III-V may include a binary compound, such as GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, or the like; a ternary compound, such as GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InGaP, InNP, InAlP, InNAs, InNSb, InPAs, InPSb, or the like; a quaternary compound, such as GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, or the like; or any combination thereof. The semiconductor compound of Groups III-V may further include Group II elements. Examples of the semiconductor compound of Groups III-V further including the Group II element may include InZnP, InGaZnP, InAlZnP, etc.
Examples of the semiconductor compound of Groups II-VI 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 semiconductor compound of Groups I, III, and VI may include: a ternary compound, such as AgInS, AgInS2, CuInS, CuInS2, CuGaO2, AgGaO2, or AgAlO2; or any combination thereof.
Examples of the semiconductor compound of Groups IV-VI 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. The element or compound of Group IV may include: a single element compound, 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 the binary compound, the ternary compound, and the quaternary compound, may exist at a uniform concentration or non-uniform concentration in a particle. The quantum dot may have a single structure or a dual core-shell structure. In the case of the quantum dot having a single structure, the concentration of each element included in the corresponding quantum dot may be uniform. In one or more embodiments, the material contained in the core and the material contained in the shell may be different from each other.
The shell of the quantum dot may act as a protective layer to prevent chemical degeneration of the core to maintain semiconductor characteristics and/or as a charging layer to impart electrophoretic characteristics to the quantum dot. The shell may be a single layer or a multi-layer. The interface between the core and the shell may have a concentration gradient in which the concentration of an element existing in the shell is decreased as the element is located closer to the center of the core.
Examples of the shell of the quantum dot may be include oxide of a metal, a metalloid, or a non-metal, a semiconductor compound, and any combination thereof. Examples of the oxide of a metal, a metalloid, or a non-metal 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; and any combination thereof. Examples of the semiconductor compound may include, as described herein, the semiconductor compound of Groups II-VI; the semiconductor compound of Groups III-V; the semiconductor compound of Groups III-VI; the semiconductor compound of Groups I, III, and VI; the semiconductor compound of Groups IV-VI; and any combination thereof. In addition, 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.
The full width at half maximum (FWHM) of an emission wavelength spectrum of the quantum dot may be about 45 nm or less, for example, about 40 nm or less, for example, about 30 nm or less, and within these ranges, color purity or color gamut may be increased. In addition, since the light emitted through the quantum dot is emitted in all directions, the wide viewing angle may be improved. In addition, the quantum dot may be in the form of a generally spherical particle, a generally pyramidal particle, a generally multi-armed particle, a generally cubic nanoparticle, a generally nanotube-shaped particle, a generally nanowire-shaped particle, a generally nanofiber-shaped particle, or a generally nanoplate-shaped particle.
Because the energy band gap may be adjusted by controlling the size of the quantum dot, light having various wavelength bands may be obtained from the quantum dot emission layer. Accordingly, by using quantum dots of different sizes, a light-emitting device that emits light of various wavelengths may be implemented. In one or more embodiments, the size of the quantum dot may be selected to emit red, green and/or blue light. In addition, the size of the quantum dot may be configured to emit white light by combining light of various colors.
The electron transport region may have: i) a single-layered structure consisting of a single layer consisting of a single material, ii) a single-layered structure consisting of a single layer consisting of a plurality of different materials, or iii) a multi-layered structure including a plurality of 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 an embodiment, 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, for each structure, constituting layers are sequentially stacked from an emission layer.
The electron transport region (for example, the buffer layer, the hole blocking layer, the electron control layer, or the electron transport layer in the electron transport region) may include a metal-free compound including at least one π electron-deficient nitrogen-containing C1-C60 cyclic group.
In an embodiment, the electron transport region may include a compound represented by Formula 601 below:
[Ar601]xe11-[(L601)xe1-R601]xe21 Formula 601
wherein, in Formula 601,
Ar601 and L601 may each independently be a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic 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,
R601 may be a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, —Si(Q601)(Q602)(Q603), —C(═O)(Q601), —S(═O)2(Q601), or —P(═O)(Q601)(Q602),
Q601 to Q603 are the same as described in connection with Q1,
xe21 may be 1, 2, 3, 4, or 5, and
at least one of Ar601, L601, and R601 may each independently be a π electron-deficient nitrogen-containing C1-C60 cyclic group unsubstituted or substituted with at least one R10a.
For example, when xe11 in Formula 601 is 2 or more, two or more of Ar601(s) may be linked to each other via a single bond. In one or more embodiments, Ar601 in Formula 601 may be a substituted or unsubstituted anthracene group.
In an embodiment, the electron transport region may include a compound represented by Formula 601-1:
wherein, in Formula 601-1,
X614 may be N or C(R614), X615 may be N or C(R615), X616 may be N or C(R616), and at least one of X614 to X616 may be N,
L611 to L613 are each the same as described in connection with L601,
xe611 to xe613 are each the same as described in connection with xe1,
R611 to R613 are each the same as described in connection with R601, and
R614 to R616 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a. For example, xe1 and xe611 to xe613 in Formulae 601 and 601-1 may each independently be 0, 1, or 2.
The electron transport region may include one of Compounds ET1 to ET45, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), tris-(8-hydroxyquinoline)aluminum (Alq3), bis(2-methyl-8-quinolinolato-N1,08)—(1,1′-biphenyl-4-olato)aluminum (BAlq), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole (NTAZ), Compounds ETH1 to ETH84, or any combination thereof:
The thickness of the electron transport region may be from about 160 Å to about 5,000 Å, for example, from about 100 Å to about 4,000 Å. When the electron transport region includes the buffer layer, the hole blocking layer, the electron control layer, the electron transport layer, or any combination thereof, the thickness of the buffer layer, the hole blocking layer, or the electron control layer may each independently be from about 20 Å to about 1,000 Å, for example, about 30 Å to about 300 Å, and the thickness of the electron transport layer may be from about 100 Å to about 1,000 Å, for example, about 150 Å to about 500 Å. When the thicknesses of the buffer layer, the hole blocking layer, the electron control layer, the electron transport layer and/or the electron transport layer are within these ranges, satisfactory electron transporting characteristics may be obtained without a substantial increase in driving voltage.
The electron transport region (for example, the 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. The 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 the metal ion of the 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 the alkaline earth-metal complex may 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 Li complex. The Li complex may include, for example, Compound ET-D1 (lithium quinolate, LiQ) or ET-D2:
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: i) a single-layered structure consisting of a single layer consisting of a single material, ii) a single-layered structure consisting of a single layer consisting of a plurality of different materials, or iii) a multi-layered structure including a plurality of 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, and alkali metal halides such as LiF, NaF, CsF, KF, LiI, NaI, CsI, KI, or any combination thereof. The alkaline earth metal-containing compound may include an alkaline earth metal compound, such as BaO, SrO, CaO, BaxSr1-xO (x is a real number satisfying the condition of 0<x<1), BaxCa1-xO (x is a real number satisfying the condition of 0<x<1), and 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 one or more embodiments, the rare earth metal-containing compound may include a lanthanide metal telluride. Examples of the lanthanide metal telluride may be 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 i) one of ions of the alkali metal, the alkaline earth metal, and the rare earth metal and ii), as 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 hydroxyphenylbenzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or any combination thereof.
The electron injection layer may 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 one or more embodiments, the electron injection layer may further include an organic material (for example, a compound represented by Formula 601).
In one or more embodiments, the electron injection layer may consist of i) an alkali metal-containing compound (for example, an alkali metal halide), ii) a) an alkali metal-containing compound (for example, an alkali metal halide); and b) an alkali metal, an alkaline earth metal, a rare earth metal, or any combination thereof. In one or more embodiments, the electron injection layer may be a KI:Yb co-deposited layer, an RbI:Yb co-deposited layer, 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 homogeneously or non-homogeneously dispersed in a matrix including the organic material.
The thickness of the electron injection layer may be in a range of about 1 Å to about 100 Å, and, for example, about 3 Å to about 90 Å. When the thickness of the electron injection layer is within the range described above, the electron injection layer may have satisfactory electron injection characteristics without a substantial increase in driving voltage.
The second electrode 150 may be located on the interlayer 130 as described above. The second electrode 150 may be a cathode, which is an electron injection electrode, and as the material for the second electrode 150, a metal, an alloy, an electrically conductive compound, or any combination thereof, each having a low work function, may be used.
In one or more embodiments, 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), an ITO, an 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 including two or more layers.
A first capping layer may be located outside the first electrode 110, and/or a second capping layer may be located outside the second electrode 150. In detail, 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 sequentially 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 sequentially 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 sequentially stacked in this stated order.
Light generated in an emission layer of the interlayer 130 of the light-emitting device 10 may be extracted toward the outside through the first electrode 110, which is a semi-transmissive electrode or a transmissive electrode, and the first capping layer. In one or more embodiments, light generated in an emission layer of the interlayer 130 of the light-emitting device 10 may be extracted toward the outside through the second electrode 150, which is a semi-transmissive electrode or a transmissive electrode, and the second capping layer.
Although not wanting to be bound by theory, the first capping layer and the second capping layer may 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.
Each of the first capping layer and second capping layer may include a material having a refractive index (at 589 nm) of about 1.6 or more. 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 a composite capping layer including an organic material and an inorganic material.
At least one of the first capping layer and the second capping layer may each independently include carbocyclic compounds, heterocyclic compounds, amine group-containing compounds, porphyrin derivatives, phthalocyanine derivatives, naphthalocyanine derivatives, alkali metal complexes, alkaline earth metal complexes, or any combination thereof. 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 one or more embodiments, at least one of the first capping layer and the second capping layer may each independently include an amine group-containing compound.
In one or more embodiments, at least one of 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 one or more embodiments, at least one of the first capping layer and the second capping layer may each independently include one of Compounds HT28 to HT33, one of Compounds CP1 to CP6, N4,N4′-di(naphthalen-2-yl)-N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (p-NPB), or any combination thereof:
The light-emitting device 10 may be included in various electronic apparatuses. In one or more embodiments, the electronic apparatus including the light-emitting device may be a light-emitting apparatus, an authentication apparatus, and the like.
The electronic apparatus (for example, light-emitting apparatus) may further include, in addition to the light-emitting device 10, i) a color filter, ii) a color conversion layer, or iii) a color filter and a color conversion layer. The color filter and/or the color conversion layer may be located in at least one traveling direction of light emitted from the light-emitting device 10. In one or more embodiments, the light emitted from the light-emitting device 10 may be blue light or white light. The light-emitting device 10 may be the same as described above. In one or more embodiments, the color conversion layer may include one or more quantum dots. 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 a plurality of subpixel areas, the color filter may include a plurality of color filter areas respectively corresponding to the subpixel areas, and the color conversion layer may include a plurality of color conversion areas respectively corresponding to the subpixel areas.
A pixel-defining film may be located among the subpixel areas to define each of the subpixel areas. The color filter may further include a plurality of color filter areas and light-shielding patterns located among the color filter areas, and the color conversion layer may include a plurality of color conversion areas and light-shielding patterns located among 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/or a third area emitting third color light, and the first color light, the second color light, and/or the third color light may have different maximum emission wavelengths from one another. In one or more embodiments, 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 one or more embodiments, the color filter areas (or the color conversion areas) may include quantum dots. In detail, 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 a quantum dot. The quantum dot is the same as described herein. The first area, the second area, and/or the third area may each include a scatterer.
In one or more embodiments, the light-emitting device 10 may emit a first light, the first area may absorb the first light to emit first first-color light, the second area may absorb the first light to emit second first-color light, and the third area may absorb the first light to emit third first-color light. In this regard, the first first-color light, the second first-color light, and the third first-color light may have different maximum emission wavelengths. In detail, 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 10 as described above. The thin-film transistor may include a source electrode, a drain electrode, and an activation layer, wherein any one of the source electrode and the drain electrode may be electrically connected to any one of the first electrode and the second electrode of the light-emitting device 10.
The thin-film transistor may further include a gate electrode, a gate insulating film, and the like. The activation layer may include a crystalline silicon, an amorphous silicon, an organic semiconductor, an oxide semiconductor, and the like.
The electronic apparatus may further include a sealing portion for sealing the light-emitting device 10. The sealing portion and/or the color conversion layer may be placed between the color filter and the light-emitting device 10. The sealing portion allows light from the light-emitting device 10 to be extracted to the outside, while simultaneously preventing ambient air and moisture from penetrating into the light-emitting device 10. 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 at least one layer of 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 additionally located on the sealing portion, in addition to the color filter and/or the color conversion layer, according to the use of the electronic apparatus. The functional layers may include a touch screen layer, a polarizing layer, and 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 using biometric information of a living body (for example, fingertips, pupils, etc.). The authentication apparatus may further include, in addition to the light-emitting device 10, a biometric information collector.
The electronic apparatus may take the form of or be applied to various 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, various measuring instruments, meters (for example, meters for a vehicle, an aircraft, and a vessel), projectors, and the like.
The light-emitting apparatus 180 of
The TFT 200 may be located on the buffer layer 210. The TFT 200 may include an activation layer 220, a gate electrode 240, a source electrode 260, and a drain electrode 270. The activation layer 220 may include an inorganic semiconductor such as silicon or a polysilicon, an organic semiconductor, or an oxide semiconductor, and may include a source region, a drain region and a channel region.
A gate insulating film 230 for insulating the activation layer 220 from the gate electrode 240 may be located on the activation 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 placed 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 activation layer 220, and the source electrode 260 and the drain electrode 270 may be in contact with the exposed portions of the source region and the drain region of the activation layer 220.
The TFT 200 is electrically connected to a light-emitting device 10 to drive the light-emitting device 10, and is covered by a passivation layer 280. The passivation layer 280 may include an inorganic insulating film, an organic insulating film, or any combination thereof. The light-emitting device 10 is provided on the passivation layer 280. The light-emitting device 10 may include a first electrode 110, an interlayer 130, and a second electrode 150.
The first electrode 110 may be formed on the passivation layer 280. The passivation layer 280 may not completely cover the drain electrode 270 and expose a portion of the drain electrode 270, and the first electrode 110 may be 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 region of the first electrode 110, and an interlayer 130 may be formed in the exposed region of the first electrode 110. The pixel defining layer 290 may be a polyimide or polyacrylic organic film. At least some layers of the interlayer 130 may extend beyond the upper portion of the pixel defining layer 290 to be located 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 additionally formed 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 10 to protect the light-emitting device 10 from moisture or oxygen. The encapsulation portion 300 may include: an inorganic film including a silicon nitride (SiNx), a silicon oxide (SiOx), an indium tin oxide, an indium zinc oxide, or any combination thereof, an organic film including a polyethylene terephthalate, a polyethylene naphthalate, a polycarbonate, a polyimide, a polyethylene sulfonate, a polyoxymethylene, a polyarylate, a hexamethyldisiloxane, an acrylic resin (for example, a polymethyl methacrylate, a polyacrylic acid, or the like), an epoxy-based resin (for example, an aliphatic glycidyl ether (AGE), or the like), or any combination thereof; or any combination of the inorganic film and the organic film.
The light-emitting apparatus 190 of
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 using 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 10−8 torr to about 10−3 torr, and a deposition speed of about 0.01 angstrom per second (A/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.
As used herein, the “(interlayer and/or capping layer) includes at least one organometallic compound” as used herein may be understood as “(interlayer and/or capping layer) may include one kind of organometallic compound represented by Formula 1 or two different kinds of organometallic compounds, each represented by Formula 1.”
The term “interlayer” as used herein refers to a single layer and/or all of a plurality of layers located between a first electrode and a second electrode of a light-emitting device. A material included in the “interlayer” is not limited to an organic material.
As used herein, the term “quantum dot” refers to a crystal of a semiconductor compound, and may include any material capable of emitting light of various emission wavelengths according to the size of the crystal.
As used herein, the term “energy level” may be expressed in “electron volts” and “energy level” and “electron volt” may be abbreviated, independently, as “eV”.
As used herein, the term “atom” may mean an element or its corresponding radical bonded to one or more other atoms.
The terms “hydrogen” and “deuterium” refer to their respective atoms and corresponding radicals with the deuterium radical abbreviated “-D”, and the terms “—F, —Cl, —Br, and —I” are radicals of, respectively, fluorine, chlorine, bromine, and iodine.
As used herein, a substituent for a monovalent group, e.g., alkyl, may also be, independently, a substituent for a corresponding divalent group, e.g., alkylene.
As used herein, the term “fused” may refer to a ring having one or more sides in common with another ring, and includes a condensed ring.
The term “C3-C60 carbocyclic group” as used herein refers to a cyclic group consisting of carbon only and having three to sixty carbon atoms, and the term “C1-C60 heterocyclic group” as used herein refers to a cyclic group that has one to sixty carbon atoms and further has, in addition to carbon, a heteroatom. The C3-C60 carbocyclic group and the C1-C60 heterocyclic group may each be a monocyclic group consisting of one ring or a polycyclic group in which two or more rings are fused with each other. For example, the number of ring-forming atoms of the C1-C60 heterocyclic group may be from 3 to 61.
The “cyclic group” as used herein may include the C3-C60 carbocyclic group and the C1-C60 heterocyclic group.
The term “n electron-rich C3-C60 cyclic group” as used herein refers to a cyclic group that has three to sixty carbon atoms and does not include *—N=*′ as a ring-forming moiety, and the term “n electron-deficient nitrogen-containing C1-C60 cyclic group” as used herein refers to a heterocyclic group that has one to sixty carbon atoms and includes *—N=*′ as a ring-forming moiety.
For example, the C3-C60 carbocyclic group may be i) a group T1G or ii) a fused cyclic group in which at least two groups T1G are fused 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-C60 heterocyclic group may be i) a group T2G, ii) a fused cyclic group in which at least two groups T2G are fused with each other, or iii) a fused cyclic group in which at least one group T2G and at least one group T1G are fused 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, etc.
The π electron-rich C3-C60 cyclic group may be i) a group T1G, ii) a fused cyclic group in which two or more groups T1G are fused with each other, iii) a group T3G, iv) a fused cyclic group in which two or more groups T3G are fused with each other, or v) a fused cyclic group in which at least one group T3G and at least one group T1G are fused with each other for example, the C3-C60 carbocyclic group, 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, etc.
The π electron-deficient nitrogen-containing C1-C60 cyclic group may be i) a group T4G, ii) a fused cyclic group in which at least two groups T4G are fused with each other, iii) a fused cyclic group in which at least one group T4G and at least one group T1G are fused with each other, iv) a fused cyclic group in which at least one group T4G and at least one group T3G are fused with each other, or v) a fused cyclic group in which at least one group T4G, at least one group T1G, and at least one group T3G are fused 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, etc.
The group T1G 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 group T2G 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, or a tetrazine group.
The group T3G may be a furan group, a thiophene group, a 1H-pyrrole group, a silole group, or a borole group.
The group T4G 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 “the cyclic group, the C3-C60 carbocyclic group, the C1-C60 heterocyclic group, the π electron-rich C3-C60 cyclic group, or the π electron-deficient nitrogen-containing C1-C60 cyclic group” as used herein refer to a group fused with any cyclic group, a monovalent group, or a polyvalent group (for example, a divalent group, a trivalent group, a tetravalent group, etc.), depending on the structure of a formula in connection with which the terms are used. In one or more embodiments, “a benzene group” may be a benzo group, a phenyl group, a phenylene group, or the like, which may be easily understood by one of ordinary skill in the art according to the structure of a formula including the “benzene group.”
Examples of the monovalent C3-C60 carbocyclic group and the monovalent C1-C60 heterocyclic group are a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C1-C60 heteroaryl group, a monovalent non-aromatic fused polycyclic group, and a monovalent non-aromatic fused heteropolycyclic group, and examples of the divalent C3-C60 carbocyclic group and the monovalent C1-C60 heterocyclic group are a C3-C10 cycloalkylene group, a C1-C10 heterocycloalkylene group, a C3-C10 cycloalkenylene group, a C1-C10 heterocycloalkenylene group, a C6-C60 arylene group, a C1-C60 heteroarylene group, a divalent non-aromatic fused polycyclic group, and a substituted or unsubstituted divalent non-aromatic fused heteropolycyclic group.
The term “C1-C60 alkyl group” as used herein refers to a linear or branched aliphatic hydrocarbon monovalent group that has one to sixty carbon atoms, and examples thereof are 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 iso-nonyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, and a tert-decyl group. The term “C1-C60 alkylene group” as used herein refers to a divalent group having a structure corresponding to the C1-C60 alkyl group.
The term “C2-C60 alkenyl group” as used herein refers to a monovalent hydrocarbon group having at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof are an ethenyl group, a propenyl group, and a butenyl group. The term “C2-C60 alkenylene group” as used herein refers to a divalent group having a structure corresponding to the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethynyl group and a propynyl group. The term “C2-C60 alkynylene group” as used herein refers to a divalent group having a structure corresponding to the C2-C60 alkynyl group.
The term “C1-C60 alkoxy group” as used herein refers to a monovalent group represented by —OA101 (wherein A101 is the C1-C60 alkyl group), and examples thereof include a methoxy group, an ethoxy group, and an isopropyloxy group.
The term “C3-C10 cycloalkyl group” as used herein refers to a monovalent saturated hydrocarbon cyclic group having three to ten carbon atoms, and examples thereof are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group (or 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-C10 cycloalkylene group” as used herein refers to a divalent group having a structure corresponding to the C3-C10 cycloalkyl group.
The term “C1-C10 heterocycloalkyl group” as used herein refers to a monovalent cyclic group that further includes, in addition to a carbon atom, at least one heteroatom as a ring-forming atom and has one to ten carbon atoms, and examples thereof are a 1,2,3,4-oxatriazolidinyl group, a tetrahydrofuranyl group, and a tetrahydrothiophenyl group. The term “C1-C10 heterocycloalkylene group” as used herein refers to a divalent group having a structure corresponding to the C1-C10 heterocycloalkyl group.
The term C3-C10 cycloalkenyl group used herein refers to a monovalent cyclic group that has three to ten carbon atoms and at least one carbon-carbon double bond in the ring thereof and no aromaticity, and examples thereof are a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group. The term “C3-C10 cycloalkenylene group” as used herein refers to a divalent group having a structure corresponding to the C3-C10 cycloalkenyl group.
The term “C1-C10 heterocycloalkenyl group” as used herein refers to a monovalent cyclic group that has, in addition to a carbon atom, at least one heteroatom as a ring-forming atom, one to ten carbon atoms, and at least one carbon-carbon double bond in the cyclic structure thereof. Examples of the C1-C10 heterocycloalkenyl group include a 4,5-dihydro-1,2,3,4-oxatriazolyl group, a 2,3-dihydrofuranyl group, and a 2,3-dihydrothiophenyl group. The term “C1-C10 heterocycloalkenylene group” as used herein refers to a divalent group having a structure corresponding to the C1-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as used herein refers to a monovalent group having a carbocyclic aromatic system having six to sixty carbon atoms, and the term “C6-C60 arylene group” as used herein refers to a divalent group having a carbocyclic aromatic system having six to sixty carbon atoms. Examples of the C6-C60 aryl group are 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. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the rings may be fused with each other.
The term “C1-C60 heteroaryl group” as used herein refers to a monovalent group having a heterocyclic aromatic system that has, in addition to a carbon atom, at least one heteroatom as a ring-forming atom, and 1 to 60 carbon atoms. The term “C1-C60 heteroarylene group” as used herein refers to a divalent group having a heterocyclic aromatic system that has, in addition to a carbon atom, at least one heteroatom as a ring-forming atom, and one to sixty carbon atoms. Examples of the C1-C60 heteroaryl group are 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. When the C1-C60 heteroaryl group and the C1-C60 heteroarylene group each include two or more rings, the rings may be fused with each other.
The term “monovalent non-aromatic fused polycyclic group” as used herein refers to a monovalent group (for example, having eight to sixty carbon atoms) having two or more rings fused with each other, only carbon atoms as ring-forming atoms, and no aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic fused polycyclic group are 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 fused polycyclic group” as used herein refers to a divalent group having a structure corresponding to a monovalent non-aromatic fused polycyclic group.
The term “monovalent non-aromatic fused heteropolycyclic group” as used herein refers to a monovalent group (for example, having one to sixty carbon atoms) having two or more rings fused with each other, at least one heteroatom other than carbon atoms, as a ring-forming atom, and no aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic fused heteropolycyclic group are 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 benzonaphtho silolyl group, a benzofurodibenzofuranyl group, a benzofurodibenzothiophenyl group, and a benzothienodibenzothiophenyl group. The term “divalent non-aromatic fused heteropolycyclic group” as used herein refers to a divalent group having a structure corresponding to a monovalent non-aromatic fused heteropolycyclic group.
The term “C6-C60 aryloxy group” as used herein indicates —OA102 (wherein A102 is the C6-C60 aryl group), and the term “C6-C60 arylthio group” as used herein indicates —SA103 (wherein A103 is the C6-C60 aryl group).
The term “R10a” as used herein refers to:
deuterium (-D), —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, or a nitro group;
a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, or a C1-C60 alkoxy group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C3-C60 carbocyclic group, a C1-C60 heterocyclic group, a C6-C60 aryloxy group, a C6-C60 arylthio 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-C60 carbocyclic group, a C1-C60 heterocyclic group, a C6-C60 aryloxy group, or a C6-C60 arylthio group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C60 carbocyclic group, a C1-C60 heterocyclic group, a C6-C60 aryloxy group, a C6-C60 arylthio 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).
The term “C2-C60 heterocyclic group” as used herein refers to a group having a structure corresponding to the C4-C60 carbocyclic group, except that as a ring-forming atom, at least one heteroatom selected from N, O, Si, P, and S is used in addition to carbon (the number of carbon atoms may be in a range of 2 to 60).
At least one substituent of the substituted C4-C60 carbocyclic group, the substituted C2-C60 heterocyclic group, the substituted C3-C10 cycloalkylene group, the substituted C1-C10 heterocycloalkylene group, the substituted C3-C10 cycloalkenylene group, the substituted C1-C10 heterocycloalkenylene group, the substituted C6-C60 arylene group, the substituted C1-C60 heteroarylene group, the substituted divalent non-aromatic fused polycyclic group, the substituted divalent non-aromatic fused heteropolycyclic group, the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C1-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl group, the substituted monovalent non-aromatic fused polycyclic group, and the substituted monovalent non-aromatic fused heteropolycyclic group may be selected from:
deuterium (-D), —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, and a C1-C60 alkoxy group;
a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, and a C1-C60 alkoxy group, each substituted with at least one selected from deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C1-C60 heteroaryl group, a monovalent non-aromatic fused polycyclic group, a monovalent non-aromatic fused heteropolycyclic group, —Si(Q11)(Q12)(Q13), —N(Q11)(Q12), —B(Q11)(Q12), —C(═O)(Q12), —S(═O)2(Q11), and —P(═O)(Q11)(Q12);
a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C0-C60 arylthio group, a C1-C60 heteroaryl group, a monovalent non-aromatic fused polycyclic group, and a monovalent non-aromatic fused heteropolycyclic group, each optionally substituted with at least one selected from deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a is C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C1-C60 heteroaryl group, a monovalent non-aromatic fused polycyclic group, a monovalent non-aromatic fused heteropolycyclic group, —Si(Q21)(Q22)(Q23), —N(Q21)(Q22), —B(Q21)(Q22), —C(═O)(Q21), —S(═O)2(Q21), and —P(═O)(Q21)(Q22); and
—Si(Q31)(Q32)(Q33), —N(Q31)(Q32), —B(Q31)(Q32), —C(═O)(Q31), —S(═O)2(Q31), and —P(═O)(Q31)(Q32).
The variables Q11 to Q13, Q21 to Q23, and Q31 to Q33 may each independently be selected from hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C1-C60 heteroaryl group, a monovalent non-aromatic fused polycyclic group, a monovalent non-aromatic fused heteropolycyclic group, a C1-C60 alkyl group substituted with at least one selected from deuterium, —F, and a cyano group, a C6-C60 aryl group substituted with at least one selected from deuterium, —F, and a cyano group, a biphenyl group, and a terphenyl group.
The variables Q1 to Q3, Q11 to Q13, Q21 to Q23 and Q31 to Q33 used herein may also each independently be: hydrogen; deuterium; —F; —Cl; —Br; —I; a hydroxyl group; a cyano group; a nitro group; a C1-C60 alkyl group; a C2-C60 alkenyl group; a C2-C60 alkynyl group; a C1-C60 alkoxy group; a C3-C60 carbocyclic group; or a C1-C60 heterocyclic group, each unsubstituted or substituted with deuterium, —F, a cyano group, a CI-Coo alkyl group, a CI-Coo alkoxy group, a phenyl group, a biphenyl group, or any combination thereof.
The term “heteroatom” as used herein refers to any atom other than a carbon atom. Examples of the heteroatom are O, S, N, P, Si, B, Ge, Se, and any combination thereof.
The term “the third-row transition metal” used herein includes hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and the like.
As used herein, the term “Ph” refers to a phenyl group, the term “Me” refers to a methyl group, the term “Et” refers to an ethyl group, the term “ter-Bu” or “But” refers to a tert-butyl group, and the term “OMe” refers to a methoxy group.
The term “biphenyl group” as used herein refers to “a phenyl group substituted with a phenyl group.” In other words, the “biphenyl group” is a substituted phenyl group having a C6-C60 aryl group as a substituent.
The term “terphenyl group” as used herein refers to “a phenyl group substituted with a biphenyl group”. In other words, the “terphenyl group” is a substituted phenyl group having, as a substituent, a C6-C60 aryl group substituted with a C6-C60 aryl group.
As used herein, the abbreviation “eq” means mole equivalent.
The symbols *, *′, and *″, as used herein, unless defined otherwise, each refer to a binding site to a neighboring atom in a corresponding formula.
Hereinafter, a compound made according to the principles and embodiments of the invention and a light-emitting device including the same will be described in detail with reference to Synthesis Examples and Examples. The wording “B was used instead of A” used in describing Synthesis Examples refers to that an identical molar equivalent of B was used in place of A.
Synthesis of Intermediate [BD2-A]
The compounds 2-nitroaniline (2.4 eq), bromomethyl hypobromite (cas No. 1301178-48-2) (1.0 eq), tris(dibenzylideneacetone)dipalladium (0) (Pd2(dba)3) (0.1 eq), dicyclohexyl-[2-(2,6-dimethoxyphenyl)phenyl]phosphane (Sphos) in an amount of 0.15 eq, and sodium tert-butoxide (4.0 eq) were placed in a reaction vessel and then suspended in toluene (0.1 molar (M)). The reaction mixture was heated to a temperature of 110° C. and stirred for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated sodium chloride (NaCl) aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD2-A] (yield of 81 percent (%)).
Synthesis of Intermediate [BD2-B]
The compounds [BD2-A] (1.0 eq), tin (Sn) in an amount of 5.0 eq, and hydrogen chloride (HCl) in an amount of 10.0 eq were placed in a reaction vessel and suspended in ethanol (0.1 M). The reaction mixture was heated and stirred at 80° C. for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and excess distilled water was added thereto, which was then neutralized with an aqueous sodium hydroxide solution and ammonium chloride. The neutralized solution was extracted three times with dichloromethane to obtain an organic layer. After drying the obtained organic layer by using magnesium sulfate, the solvent was removed to obtain Intermediate [BD2-B] (yield of 89%).
Synthesis of Intermediate [BD2-C]
The compounds [BD2-B] (1.0 eq), bromobenzene (2.4 eq), Pd2(dba)3 (0.1 eq), Sphos (0.15 eq), and sodium tert-butoxide (4.0 eq) were placed in a reaction vessel and then suspended in toluene (0.1M). The reaction mixture was heated to a temperature of 110° C. and stirred for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD2-C] (yield of 83%).
Synthesis of Intermediate [BD2-D]
The compounds [BD2-C] (1.0 eq), HCl (2.4 eq), and triethyl orthoformate (100.0 eq) were placed in a reaction vessel and then suspended therein. The reaction mixture was heated and stirred at 80° C. for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD2-D](yield of 87%).
Synthesis of Intermediate [BD2-E]
The compound [BD2-D] (1.0 eq) was added to a reaction vessel, followed by suspension onto a mixed solution of methanol and distilled water at a ratio of 2:1. The reaction mixture was sufficiently dissolved, and then, ammonium hexafluorophosphate (2.2 eq) was slowly added thereto, followed by stirring the reaction solution at room temperature for 12 hours. After completion of the reaction, the obtained solid was filtered and dried to obtain Intermediate [BD2-E] (yield of 98%).
Synthesis of Compound BD2
The compounds [BD2-E] (1.0 eq), dichloro(1,5-cyclooctadiene)platinum (1.1 eq), and sodium acetate (3.0 eq) were suspended in 1,4-dioxane (0.1 M). The reaction mixture was heated to a temperature of 120° C. and stirred for 72 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Compound BD2 (yield of 37%).
Synthesis of Intermediate [BD5-A]
The same synthesis method was performed as used to obtain Intermediate [BD2-A].
Synthesis of Intermediate [BD5-B]
The same synthesis method was performed as used to obtain Intermediate [BD2-B].
Synthesis of Intermediate [BD5-C]
Intermediate [BD5-C](yield of 78%) was obtained in the same manner as used to Intermediate [BD2-C], except that 1-bromo-3-tert-butylbenzene was used instead of bromobenzene.
Synthesis of Intermediate [BD5-D]
Intermediate [BD5-D](yield of 72%) was obtained in the same manner as used to synthesize Intermediate [BD2-D], except that [BD5-C] was used instead of [BD2-C].
Synthesis of Intermediate [BD5-E]
Intermediate [BD5-E] (yield of 90%) was obtained in the same manner as used to synthesize Intermediate [BD2-E], except that [BD5-D] was used instead of [BD2-D].
Synthesis of Compound BD5
Compound BD5 (yield of 39%) was obtained in the same manner as used to synthesize Compound BD2, except that [BD5-E] was used instead of [BD2-E].
Synthesis of Intermediate [BD7-A]
The compounds 1-amino-2-nitroethene (1.0 eq), bromomethyl hypobromite (cas No. 1301178-48-2) (1.5 eq), Pd2(dba)3 (0.05 eq), Sphos (0.075 eq), and sodium tert-butoxide (2.0 eq) were placed in a reaction vessel and then suspended in toluene (0.1M). The reaction mixture was heated to a temperature of 110° C. and stirred for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD7-A] (yield of 85%).
Synthesis of Intermediate [BD7-B]
The compounds 2-nitroaniline (1.2 eq), [BD7-A] (1.0 eq), Pd2(dba)3 (0.05 eq), Sphos (0.075 eq), and sodium tert-butoxide (2.0 eq) were placed in a reaction vessel and then, suspended in toluene (0.1M). The reaction mixture was heated to a temperature of 110° C. and stirred for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD7-B] (yield of 78%).
Synthesis of Intermediate [BD7-C]
Intermediate [BD7-C] (yield of 76%) was obtained in the same manner as used to synthesize Intermediate [BD2-B], except that [BD7-B] was used instead of [BD2-A].
Synthesis of Intermediate [BD7-D]
Intermediate [BD7-D] (yield of 72%) was obtained in the same manner as used to Intermediate [BD2-C], except that 1-bromo-3-methylbenzene was used instead of bromobenzene, and [BD7-C] was used instead of [BD2-B].
Synthesis of Intermediate [BD7-E]
Intermediate [BD7-E] (yield of 80%) was obtained in the same manner as used to synthesize Intermediate [BD2-D], except that [BD7-D] was used instead of [BD2-C].
Synthesis of Intermediate [BD7-F]
Intermediate [BD7-F] (yield of 92%) was obtained in the same manner as used to synthesize Intermediate [BD2-E], except that [BD7-E] was used instead of [BD2-D].
Synthesis of Compound BD7
Compound BD7(yield of 35%) was obtained in the same manner as used to synthesize Compound BD2, except that [BD7-F] was used instead of [BD2-E].
Synthesis of Intermediate [BD46-A]
The compounds 2-bromo-4-(bromomethyl)-1-methyl-1H-imidazole (cas No. 1999344-51-2)(1.5 eq), carbazole (1.0 eq), Pd2(dba)3 (0.05 eq), Sphos (0.075 eq), and sodium tert-butoxide (2.0 eq) were placed in a reaction vessel and then suspended in toluene (0.1M). The reaction mixture was heated to a temperature of 110° C. and stirred for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD46-A] (yield of 78%).
Synthesis of Intermediate [BD46-B]
The compounds [BD46-A] (1.0 eq), (Z)—N-(2-nitrovinyl)hydroxylamine (cas No. 860439-13-0)(1.2 eq), copper iodide (CuI) in an amount of 0.1 eq, 1,10-phenanthroline (0.1 eq), and potassium carbonate (K2CO3) in an amount of 2.0 eq were placed in a reaction vessel and then suspended in dimethylformamide (DMF) in an amount of 0.25M. The reaction mixture was heated, and stirred at 160° C. for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD46-B](yield of 71%).
Synthesis of Intermediate [BD46-C]
The compounds [BD46-B] (1.0 eq), Sn (5.0 eq), and HCl (10.0 eq) were placed in a reaction vessel and then, suspended in ethanol (0.1 M). The reaction mixture was heated and stirred at 80° C. for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and excess distilled water was added thereto, which was then neutralized with an aqueous sodium hydroxide solution and ammonium chloride. The neutralized solution was extracted three times with dichloromethane to obtain an organic layer. After drying the obtained organic layer by using magnesium sulfate, the solvent was removed to obtain Intermediate[BD46-C](yield of 92%).
Synthesis of Intermediate [BD46-D]
The compounds [BD46-B] (1.0 eq), bromobenzene (1.2 eq), Pd2(dba)3 (0.05 eq), Sphos (0.075 eq), and sodium tert-butoxide (2.0 eq) were placed in a reaction vessel and then, suspended in toluene (0.1 M). The reaction mixture was heated to a temperature of 110° C. and stirred for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD46-D](yield of 80%).
Synthesis of Intermediate [BD46-E]
The compounds [BD46-D] (1.0 eq), HCl (1.2 eq), and triethyl orthoformate (50.0 eq) were placed in a reaction vessel and then suspended therein. The reaction mixture was heated and stirred at 80° C. for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD46-E](yield of 87%).
Synthesis of Intermediate [BD46-F]
The compound [BD46-E] (1.0 eq) was added to a reaction vessel, followed by suspension onto a mixed solution of methanol and distilled water at a ratio of 2:1. The reaction mixture was sufficiently dissolved, and then, ammonium hexafluorophosphate (1.1 eq) was slowly added thereto, followed by stirring the reaction solution at room temperature for 12 hours. After completion of the reaction, the obtained solid was filtered and dried to obtain Intermediate [BD46-F] (yield of 97%).
Synthesis of Compound BD46
The compound BD46 (yield of 32%) was obtained in the same manner as used to synthesize Compound BD2, except that [BD46-F] was used instead of [BD2-E].
Synthesis of Intermediate [BD86-A]
The compounds 3-bromo-1-nitro-1H-pyrazole (cas No. 2457296-45-4) (1.0 eq), phenyl boronic acid (1.5 eq), tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) in an amount of 0.02 eq, and K2CO3 (2.0 eq) were placed in a reaction vessel and then, suspended in toluene (0.1M). The reaction mixture was heated to a temperature of 110° C. and stirred for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and dichloromethane. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD86-A] (yield of 85%).
Synthesis of Intermediate [BD86-B]
The compounds [BD86-A] (1.0 eq), Sn (3.0 eq), and HCl (5.0 eq) were placed in a reaction vessel and then suspended in ethanol (0.1 M). The reaction mixture was heated and stirred at 80° C. for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and excess distilled water was added thereto, which was then neutralized with an aqueous sodium hydroxide solution and ammonium chloride. The neutralized solution was extracted three times with dichloromethane to obtain an organic layer. After drying the obtained organic layer by using magnesium sulfate, the solvent was removed to obtain Intermediate [BD2-B] (yield of 89%).
Synthesis of Intermediate [BD86-C]
The compounds [BD86-B] (1.0 eq), 2,6-diphenyl(d5)-1-iodobenzene (1.2 eq), CuI (0.1 eq), 1,10-phenanthroline (0.1 eq), potassium hydroxide (KOH) in an amount of 2.0 eq were placed in a reaction vessel and then suspended in DMF (0.25 M). The reaction mixture was heated, and stirred at 160° C. for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD86-C](yield of 65%).
Synthesis of Intermediate [BD86-D]
The compounds fluoromethanamine (1.2 eq), 1-bromo-2-nitroethene (1.0 eq), Pd2(dba)3 (0.05 eq), Sphos (0.075 eq), and sodium tert-butoxide (2.0 eq) were placed in a reaction vessel and then, suspended in toluene (0.1M). The reaction mixture was heated to a temperature of 110° C. and stirred for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD86-D](yield of 65%).
Synthesis of Intermediate [BD86-E]
The compounds Intermediate [BD86-C] (1.5 eq), Intermediate [BD86-D] (1.0 eq), and K3PO4 (2.0 eq) were placed in a reaction vessel and then suspended in DMF (0.1M). The reaction mixture was heated to a temperature of 160° C. and stirred for 12 hours. Once the reaction was complete, the mixture was cooled to room temperature, and an extraction process was performed thereon by using distilled water and ethyl acetate. The extracted organic layer was washed using a saturated NaCl aqueous solution and dried using magnesium sulfate. The residue from which the solvent had been removed was separated by using column chromatography to thereby obtain Intermediate [BD86-E](yield of 75%).
Synthesis of Intermediate [BD86-F]
The compound Intermediate [BD86-F] (yield of 86%) was obtained in the same manner as used to synthesize Intermediate [BD46-C], except that [BD86-E] was used instead of [BD46-B].
Synthesis of Intermediate [BD86-G]
Intermediate [BD86-G](yield of 74%) was obtained in the same manner as used to synthesize Intermediate [BD46-D], except that [BD86-F] was used instead of [BD46-C].
Synthesis of Intermediate [BD86-H]
Intermediate [BD86-H](yield of 84%) was obtained in the same manner as used to synthesize Intermediate [BD46-E], except that [BD86-G] was used instead of [BD46-D].
Synthesis of Intermediate [BD86-I]
Intermediate [BD86-I](yield of 97%) was obtained in the same manner as used to synthesize Intermediate [BD46-F], except that [BD86-H] was used instead of [BD46-E].
Synthesis of Compound BD86
The compound BD86 (yield of 30%) was obtained in the same manner as used to synthesize Compound BD2, except that [BD86-H] was used instead of [BD2-E].
The 1H nuclear magnetic resonance (NMR) and mass spectroscopy/fast atom bombardment (MS/FAB) results are shown in Table 1.
1H NMR (CDCl3, 400 MHz)
As a substrate and an anode, a glass substrate with 15 ohms per centimeter squared (Ω/cm2) and 1,200 Å ITO thereon, which was manufactured by Corning Inc., of Corning, N.Y. was cut to a size of 50 millimeter (mm)×50 mm×0.7 mm, and the glass substrate was sonicated by using isopropyl alcohol and pure water for 5 minutes each, and then ultraviolet (UV) light was irradiated for 30 minutes thereto and ozone was exposed thereto for cleaning. Next, the resultant glass substrate was loaded onto a vacuum deposition apparatus.
The compound 2-TNATA was vacuum-deposited on the ITO anode formed on the ITO glass substrate to form a hole injection layer having a thickness of 600 Å, and the compound NPB was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 300 Å.
An amount of 10 weight percent (wt %) Compound BD2, which was used as a dopant, and ETH66 and HTH29, which were used as a mixed host, were co-deposited on the hole transport layer at a weight ratio of 3:7 to form an emission layer having a thickness of 400 Å.
The compound ETH2 was deposited on the emission layer to form a hole-blocking layer having a thickness of 50 Å, Alq3 was deposited on the hole-blocking layer to form an electron transport layer having a thickness of 300 Å, lithium fluoride (LiF) was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and then, aluminum (Al) was deposited on the electron injection layer to form a cathode having a thickness of 3,000 Å, thereby completing the manufacture of a light-emitting device.
Light-emitting devices were manufactured in the same manner as in Example 1, except that in forming an emission layer, for use as a dopant, corresponding compounds shown in Table 2 were used instead of Compound BD2.
The driving voltage in volt (V), luminance candela per meter squared (cd/m2 or cd/A), luminescence efficiency (cd/A), emission wavelength in nanometer (nm), and lifespan of the light-emitting devices manufactured according to Examples 1 to 4, and Comparative Example 1 were measured by using a source meter unit sold under the trade designation Keithley SMU 236, by Tektronix, Inc., of Beaverton, Oreg. (Keithley 236) and a luminance photometer sold under the trade designation PR650 by Photo Research Inc. of Los Angeles, Calif. (PR650). The lifespan (T95) is a period of time that was taken until the luminance (@1000 nit) was reduced to 9500 of initial luminance (100%) after the organic light-emitting device was driven. Results thereof are shown in Table 2.
The results summarized in Table 2 show that the light-emitting devices of Examples 1 to 4 had significantly and unexpectedly superior characteristics in terms of a lower driving voltage, a higher level of luminescence efficiency, and a longer lifespan than the light-emitting devices of Comparative Examples 1 to 3.
As a substrate and an anode, a glass substrate with 15 Ωcm2 (1,200 Å) ITO thereon, which was manufactured by Corning Inc., was cut to a size of 50 mm×50 mm×0.7 mm, and the glass substrate was sonicated by using isopropyl alcohol and pure water for 5 minutes each, and then ultraviolet (UV) light was irradiated for 30 minutes thereto and ozone was exposed thereto for cleaning. Next, the resultant glass substrate was loaded onto a vacuum deposition apparatus.
The compound 2-TNATA was vacuum-deposited on the ITO anode formed on the ITO glass substrate to form a hole injection layer having a thickness of 600 Å, and NPB was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 300 Å.
The compound BD2 in an amount of 10 wt %, which was used as an auxiliary dopant, and 0.5 wt % DFD2, which was used as a dopant, and ETH66 and HTH29, which were used as a mixed host, were co-deposited on the hole transport layer at a weight ratio of 3:7 to form an emission layer having a thickness of 400 Å.
The compound ETH2 was deposited on the emission layer to form a hole-blocking layer having a thickness of 50 Å, Alq3 was deposited on the hole-blocking layer to form an electron transport layer having a thickness of 300 Å, LiF was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and then, Al was deposited on the electron injection layer to form a cathode having a thickness of 3,000 Å, thereby completing the manufacture of a light-emitting device.
Light-emitting devices were manufactured in the same manner as in Example 5, except that in forming an emission layer, for use as a dopant, corresponding compounds shown in Table 3 were used instead of Compound BD2.
The driving voltage, luminance, luminescence efficiency, emission wavelength, and lifespan of the light-emitting devices manufactured according to Examples 5 to 7, and Comparative Examples 4 to 6 were measured by using source meter unit Keithley 236 and a luminance photometer PR650, and results thereof are shown in Table 3.
The results summarized in Table 3 show that the light-emitting devices of Examples 5 to 7 had significantly and unexpectedly superior characteristics in terms of a lower driving voltage, a higher level of luminescence efficiency, and a longer lifespan than the light-emitting devices of Comparative Examples 4 to 6. Light-emitting devices including an organometallic compound made according to the principles and embodiments of the invention have a low driving voltage, a high efficiency, and a long lifespan.
Although certain embodiments and implementations have been described herein, other embodiments and modifications will be apparent from this description. Accordingly, the inventive concepts are not limited to such embodiments, but rather to the broader scope of the appended claims and various obvious modifications and equivalent arrangements as would be apparent to a person of ordinary skill in the art.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0070962 | Jun 2021 | KR | national |
