Patent Application
20250143168
This application claims priority to and benefits of Korean Patent Application No. 10-2023-0145425 under 35 U.S.C. § 119, filed on Oct. 27, 2023, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.
Embodiments relate to an organometallic compound, a light-emitting device including the same, and an electronic apparatus including the light-emitting device.
Among light-emitting devices, organic light-emitting devices are self-emissive devices that have wide viewing angles, high contrast ratios, short response times, and excellent characteristics in terms of luminance, driving voltage, and response speed, compared to devices in the art.
In an example, an organic light-emitting device may have a structure in which a first electrode is arranged 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. The excitons may transition from an excited state to a ground state, thereby generating light.
It is to be understood that this background of the technology section is, in part, intended to provide useful background for understanding the technology. However, this background of the technology section may also include ideas, concepts, or recognitions that were not part of what was known or appreciated by those skilled in the pertinent art prior to a corresponding effective filing date of the subject matter disclosed herein.
Embodiments provide a novel organometallic compound and a light-emitting device having low driving voltage and high efficiency by including the novel organometallic compound. Embodiments include an electronic apparatus and electronic equipment that include the light-emitting device.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the embodiments of the disclosure.
According to embodiments, an organometallic compound may be represented by Formula 1:
In Formulae 1 and 3A,
In an embodiment, two or more of R31 to R36 may each independently be a group represented by Formula 3A.
In an embodiment, R33 may be a group represented by Formula 3A; and one of R32, R34, R35, and R36 may be a group represented by Formula 3A.
In an embodiment, Z31 to Z37 may each independently be: hydrogen or deuterium; or a C1-C20 alkyl group unsubstituted or substituted with deuterium.
In an embodiment, M1 may be Pt, Pd, Cu, Ag, or Au.
In an embodiment, two of T1 to T4 may each be a coordinate bond; and the remainder of T1 to T4 may each be a covalent bond.
In an embodiment, L1 to L4 may each independently be a single bond, *—O—*′, *—S—*′, *—N(R5)—*′, *—C(R5)(R6)—*′, *—Si(R5)(R6)—*′, or *—B(R5)—*′; R5 and R6 may each be the same as defined in Formula 1; and * and *′ each indicate a binding site to a neighboring atom.
In an embodiment, a4 may be 0.
In an embodiment, a4 may be 0; and a moiety represented by
may be a moiety represented by Formula 1A or Formula 1B, which are explained below.
In an embodiment, R11 may be a group represented by one of Formulae 10A to 19A, which are explained below.
In an embodiment, the organometallic compound represented by Formula 1 may be represented by Formula 1-1 or Formula 1-2, which are explained below.
In an embodiment, the organometallic compound represented by Formula 1 may be one of Compounds 1 to 90, which are explained below.
According to embodiments, an organic light-emitting device may include: a first electrode; a second electrode facing the first electrode; an interlayer between the first electrode and the second electrode and including an emission layer; and an organometallic compound represented by Formula 1, which is explained herein.
In an embodiment, the emission layer may include the organometallic compound.
In an embodiment, the emission layer may include a host and a dopant; and the dopant may include the organometallic compound.
In an embodiment, the emission layer may emit blue light having a maximum emission wavelength in a range of about 410 nm to about 490 nm.
In an embodiment, the emission layer may further include a delayed fluorescence material.
According to embodiments, an electronic apparatus may include the organic light-emitting device.
In an embodiment, the electronic apparatus may further include a thin-film transistor, wherein
According to embodiments, an electronic equipment may include the electronic apparatus, wherein
It is to be understood that the embodiments above are described in a generic and explanatory sense only and not for the purposes of limitation, and the disclosure is not limited to the embodiments described above.
The accompanying drawings are included to provide a further understanding of the embodiments, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the disclosure and principles thereof. The above and other aspects and features, of the disclosure will be more apparent by describing in detail embodiments thereof with reference to the accompanying drawings, in which:
The disclosure will now be described more fully hereinafter with reference to the accompanying drawings, in which embodiments are shown. This disclosure may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
In the drawings, the sizes, thicknesses, ratios, and dimensions of the elements may be exaggerated for ease of description and for clarity. Like reference numbers and reference characters refer to like elements throughout.
In the specification, it will be understood that when an element (or region, layer, part, etc.) is referred to as being “on”, “connected to”, or “coupled to” another element, it can be directly on, connected to, or coupled to the other element, or one or more intervening elements may be present therebetween. In a similar sense, when an element (or region, layer, part, etc.) is described as “covering” another element, it can directly cover the other element, or one or more intervening elements may be present therebetween.
In the specification, when an element is “directly on,” “directly connected to,” or “directly coupled to” another element, there are no intervening elements present. For example, “directly on” may mean that two layers or two elements are disposed without an additional element such as an adhesion element therebetween.
In the specification, the expressions used in the singular such as “a,” “an,” and “the,” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
In the specification, the term “and/or” includes any and all combinations of one or more of the associated listed items. For example, “A and/or B” may be understood to mean “A, B, or A and B.” The terms “and” and “or” may be used in the conjunctive or disjunctive sense and may be understood to be equivalent to “and/or”.
In the specification and the claims, the term “at least one of” is intended to include the meaning of “at least one selected from the group consisting of” for the purpose of its meaning and interpretation. For example, “at least one of A, B, and C” may be understood to mean A only, B only, C only, or any combination of two or more of A, B, and C, such as ABC, ACC, BC, or CC. When preceding a list of elements, the term, “at least one of,” modifies the entire list of elements and does not modify the individual elements of the list.
It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element. Thus, a first element could be termed a second element without departing from the teachings of the disclosure. Similarly, a second element could be termed a first element, without departing from the scope of the disclosure.
The spatially relative terms “below”, “beneath”, “lower”, “above”, “upper”, or the like, may be used herein for ease of description to describe the relations between one element or component and another element or component as illustrated in the drawings. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation, in addition to the orientation depicted in the drawings. For example, in the case where a device illustrated in the drawing is turned over, the device positioned “below” or “beneath” another device may be placed “above” another device. Accordingly, the illustrative term “below” may include both the lower and upper positions. The device may also be oriented in other directions and thus the spatially relative terms may be interpreted differently depending on the orientations.
The terms “about” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the recited value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the recited quantity (i.e., the limitations of the measurement system). For example, “about” may mean within one or more standard deviations, or within ±20%, ±10%, or ±5% of the stated value.
It should be understood that the terms “comprises,” “comprising,” “includes,” “including,” “have,” “having,” “contains,” “containing,” and the like are intended to specify the presence of stated features, integers, steps, operations, elements, components, or combinations thereof in the disclosure, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.
Unless otherwise defined or implied herein, all terms (including technical and scientific terms) used have the same meaning as commonly understood by those skilled in the art to which this disclosure pertains. It will be further understood that 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 ideal or excessively formal sense unless clearly defined in the specification.
An embodiment provides an organic light-emitting device which may include: a first electrode; a second electrode facing the first electrode; an interlayer between the first electrode and the second electrode and including an emission layer; and an organometallic compound represented by Formula 1.
In an embodiment, the first electrode may be an anode. In an embodiment, the second electrode may be a cathode.
The term “interlayer” as used herein refers to a single layer and/or all layers arranged between the first electrode and the second electrode of the light-emitting device.
In an embodiment, 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 at least one of a hole injection layer, a hole transport layer, and an electron blocking layer. The electron transport region may include at least one of a hole blocking layer, an electron transport layer, and an electron injection layer.
In an embodiment, the interlayer may include the organometallic compound.
In an embodiment, the emission layer may include the organometallic compound.
In an embodiment, the emission layer may include a host and a dopant, and the dopant may include the organometallic compound.
In an embodiment, the emission layer may emit blue light. The emission layer may emit blue light having a maximum emission wavelength in a range of about 390 nm to about 500 nm. For example, the emission layer may emit blue light having a maximum emission wavelength in a range of about 410 nm to about 500 nm. As another example, the emission layer may emit blue light having a maximum emission wavelength in a range of about 390 nm to about 490 nm. For example, the emission layer may emit blue light having a maximum emission wavelength in a range of about 410 nm to about 490 nm. As yet another example, the emission layer may emit blue light having a maximum emission wavelength in a range of, or about 430 nm to about 480 nm. The emission layer may emit blue light having a maximum emission wavelength in a range of about 390 nm to about 500 nm. In an embodiment, the emission layer may emit blue light having a maximum emission wavelength in a range of about 410 nm to about 490 nm.
In an embodiment, the emission layer may further include a delayed fluorescence material.
Another embodiment provides an electronic apparatus which may include the organic light-emitting device.
In an embodiment, the electronic apparatus may further include a thin-film transistor, wherein the thin-film transistor may include a source electrode and a drain electrode, and the first electrode of the organic light-emitting device may be electrically connected to at least one of the source electrode and the drain electrode of the thin-film transistor.
Another embodiment provides an electronic equipment which may include the organic light-emitting device, wherein the electronic equipment may be a flat panel display, a curved display, a computer monitor, a medical monitor, a television, a billboard, an indoor light, an outdoor light, a signal light, a head-up display, a fully transparent display, a partially transparent display, a flexible display, a rollable display, a foldable display, a stretchable display, a laser printer, a telephone, a mobile phone, a tablet personal computer, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro display, a three-dimensional (3D) display, a virtual reality display, an augmented reality display, a vehicle, a video wall with multiple displays tiled together, a theater screen, a stadium screen, a phototherapy device, or a signboard.
Another embodiment provides an organometallic compound which may be represented by Formula 1:
Formulae 1 and 3A may be the same as described herein.
In Formula 1, M may be 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), or thulium (Tm).
In an embodiment, M may be Pt, Pd, Cu, Ag, or Au.
In Formula 1,
Examples of a chemical bond may include a covalent bond, a coordinate bond, and the like.
In an embodiment, two of T1 to T4 may each be a coordinate bond, and the remainder of T1 to T4 may each be a covalent bond.
In an embodiment, L1 to L4 may each independently be a single bond, *—O—*′, *—S—*′, *—N(R5)—*′, *—C(R5)(R6)—*′, *—Si(R5)(R6)—*′, or *—B(R5)—*′, wherein R5 and R6 may each be the same as described herein, * and *′ each indicate a binding site to a neighboring atom.
In an embodiment, a4 may be 0.
In an embodiment, a1, a2, and a3 may each be 1.
In an embodiment, in Formula 1, a4 may be 0, and a moiety represented by
may be a moiety represented by Formula 1A or Formula 1B:
In an embodiment, in Formulae 1A and 1B, R11 may be a group represented by one of Formulae 10A to 19A:
In Formulae 10A to 19A,
In an embodiment, Z11 to Z13 may each independently be:
In an embodiment, each Z11 may not be a carbazole group.
In an embodiment, in Formula 1, a moiety represented by
may be a moiety represented by Formula 2A:
In Formula 2A,
In an embodiment, in Formula 1, a4 may be 0, and a moiety represented by
may be a moiety represented by Formula 4A:
In Formula 4A,
In Formula 1, R31 to R36 may each independently be a group represented by Formula 3A, 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 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-C10 cycloalkyl group unsubstituted or substituted with at least one R10a, a C1-C10 heterocycloalkyl group unsubstituted or substituted with at least one R10a, a C3-C10 cycloalkenyl group unsubstituted or substituted with at least one R10a, a C1-C10 heterocycloalkenyl group unsubstituted or substituted with at least one R10a, a C6-C60 aryl 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, a C1-C60 heteroaryl group unsubstituted or substituted with at least one R10a, a C1-C60 heteroaryloxy group unsubstituted or substituted with at least one R10a, a C1-C60 heteroarylthio group unsubstituted or substituted with at least one R10a, a monovalent non-aromatic condensed polycyclic group unsubstituted or substituted with at least one R10a, a monovalent non-aromatic condensed heteropolycyclic group, —Si(Q1)(Q2)(Q3), —B(Q1)(Q2), —N(Q1)(Q2), —P(Q1)(Q2), —C(═O)(Q1), —S(═O)(Q1), —S(═O)2(Q1), —P(═O)(Q1)(Q2), or —P(═S)(Q1)(Q2), and
In an embodiment, at least two of R31 to R63 may each independently be a group represented by Formula 3A.
In an embodiment, R33 may be a group represented by Formula 3A, and one of R32, R34, R35, and R36 may be a group represented by Formula 3A.
In an embodiment, each of R31 to R36 may not form a ring by combining with neighboring groups among R31 to R36.
In Formula 1, R1, R2, R4, R5, and R6 may each independently be 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 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-C10 cycloalkyl group unsubstituted or substituted with at least one R10a, a C1-C10 heterocycloalkyl group unsubstituted or substituted with at least one R10a, a C3-C10 cycloalkenyl group unsubstituted or substituted with at least one R10a, a C1-C10 heterocycloalkenyl group unsubstituted or substituted with at least one R10a, a C6-C60 aryl 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, a C1-C60 heteroaryl group unsubstituted or substituted with at least one R10a, a C1-C60 heteroaryloxy group unsubstituted or substituted with at least one R10a, a C1-C60 heteroarylthio group unsubstituted or substituted with at least one R10a, a monovalent non-aromatic condensed polycyclic group unsubstituted or substituted with at least one R10a, a monovalent non-aromatic condensed heteropolycyclic group, —Si(Q1)(Q2)(Q3), —B(Q1)(Q2), —N(Q1)(Q2), —P(Q1)(Q2), —C(═O)(Q1), —S(═O)(Q1), —S(═O)2(Q1), —P(═O)(Q1)(Q2), or —P(═S)(Q1)(Q2),
In Formula 1, Z31 to Z37 may each independently be:
In an embodiment, Z31 to Z37 may each independently be:
hydrogen, deuterium, —F, —Cl, —Br, or —I; or
In an embodiment, Z31 to Z37 may each independently be: hydrogen; deuterium; or a C1-C20 alkyl group unsubstituted or substituted with deuterium.
In Formula 1, R10a may be:
In an embodiment, the organometallic compound represented by Formula 1 may be represented by Formula 1-1 or Formula 1-2:
In Formulae 1-1 or Formula 1-2,
In an embodiment, the organometallic compound may be electrically neutral.
In an embodiment, the organometallic compound represented by Formula 1 may be one of Compounds 1 to 90:
The organometallic compound represented by Formula 1 has a structure in which a long alkyl chain is introduced to a carbazole group, and thus may have a reduced sublimation temperature and improved heat resistance stability. The intensity of second emission may be reduced by the long alkyl chain, so that color purity may be improved, which can contribute to increased efficiency and improved lifespan.
Therefore, the organic light-emitting device including the organometallic compound may have low driving voltage and high efficiency. For example, in case that the organometallic compound represented by Formula 1 is included as a dopant in the emission layer, the organic light-emitting device including the organometallic compound may exhibit low driving voltage, high luminescence efficiency, high color conversion efficiency, and long lifespan.
Synthesis methods of the organometallic compound represented by Formula 1 may be recognizable by one of ordinary skill in the art by referring to the Examples provided below.
Hereinafter, the structure of the organic light-emitting device 10 according to an embodiment and a method of manufacturing the organic light-emitting device 10 will be described in connection with
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. In case that 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. In an embodiment, in case that the first electrode 110 is a transmissive electrode, a material for forming the first electrode 110 may include indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), or a combination thereof. In embodiments, in case that the first electrode 110 is a semi-transmissive electrode or a reflective electrode, a material for forming the first electrode 110 may include magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), or any combination thereof.
The first electrode 110 may have a structure consisting of a single layer, or a structure including multiple layers. For example, the first electrode 110 may have a three-layer structure of ITO/Ag/ITO.
The interlayer 130 is arranged on the first electrode 110. The interlayer 130 may include an emission layer.
The interlayer 130 may further include a hole transport region between the first electrode 110 and the emission layer and an electron transport region between the emission layer and the second electrode 150.
The interlayer 130 may further include a metal-containing compound, such as a heterocyclic compound, an inorganic material, such as a quantum dot, or the like, in addition to various organic materials.
In an embodiment, the interlayer 130 may include two or more emitting units sequentially stacked between the first electrode 110 and the second electrode 150, and at least one charge generation layer between adjacent units among the two or more emitting units. In case that the interlayer 130 includes the two or more emitting units and the at least one charge generation layer, the organic light-emitting device 10 may be a tandem organic light-emitting device.
The hole transport region may have a structure consisting of a layer consisting of a single material, a structure consisting of a layer including different materials, or a structure including multiple layers including different materials.
The hole transport region may include a hole injection layer, a hole transport layer, an emission auxiliary layer, an electron blocking layer, or any combination thereof.
In embodiments, the hole transport region may have a multi-layer structure including a hole injection layer/hole transport layer structure, a hole injection layer/hole transport layer/emission auxiliary layer structure, a hole injection layer/emission auxiliary layer structure, a hole transport layer/emission auxiliary layer structure, or a hole injection layer/hole transport layer/electron-blocking layer structure, wherein the layers of each structure may be stacked from the first electrode 110 in its respective stated order, but the structure of the hole transport region is not limited thereto.
In an embodiment, the hole transport region may include a compound represented by Formula 201, a compound represented by Formula 202, or any combination thereof:
In embodiments, the compound represented by Formula 201 and the compound represented by Formula 202 may each independently include at least one of groups represented by Formulae CY201 to CY217:
In Formulae CY201 to CY217, R10b and R10c may each independently be 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 an embodiment, in Formulae CY201 to CY217, ring CY201 to ring CY204 may each independently be a benzene group, a naphthalene group, a phenanthrene group, or an anthracene group.
In embodiments, the compound represented by Formula 201 and the compound represented by Formula 202 may each independently include at least one of the groups represented by Formulae CY201 to CY203.
In embodiments, the compound represented by Formula 201 may include at least one of the groups represented by Formulae CY201 to CY203 and at least one of the groups represented by Formulae CY204 to CY217.
In embodiments, in Formula 201, xa1 may be 1, R201 may be one of the groups represented by Formulae CY201 to CY203, xa2 may be 0, and R202 may be one of the groups represented by one of Formulae CY204 to CY207.
In embodiments, the compound represented by Formula 201 and the compound represented by Formula 202 may each not include the groups represented by Formulae CY201 to CY203.
In embodiments, the compound represented by Formula 201 and the compound represented by Formula 202 may each not include the groups represented by Formulae CY201 to CY203, and may each independently include at least one of the groups represented by Formulae CY204 to CY217.
In embodiments, the compound represented by Formula 201 and the compound represented by Formula 202 may each not include the groups represented by Formulae CY201 to CY217.
In embodiments, the hole transport region may include: one of Compounds HT1 to HT46; m-MTDATA; TDATA; 2-TNATA; NPB(NPD); β-NPB; TPD; spiro-TPD; spiro-NPB; methylated NPB; TAPC; HMTPD; 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA); polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA); poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS); polyaniline/camphor sulfonic acid (PANI/CSA); polyaniline/poly(4-styrenesulfonate) (PANI/PSS); or any combination thereof:
A thickness of the hole transport region may be in a range of about 50 Å to about 10,000 Å. For example, the thickness of the hole transport region may be in a range of about 100 Å to about 4,000 Å. In case that the hole transport region includes a hole injection layer, a hole transport layer, or any combination thereof, a thickness of the hole injection layer may be in a range of about 100 Å to about 9,000 Å, and a thickness of the hole transport layer may be in a range of about 50 Å to about 2,000 Å. For example, the thickness of the hole injection layer may be in a range of about 100 Å to about 1,000 Å. For example, the thickness of the hole transport layer may be in a range of about 100 Å to about 1,500 Å. In case that 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 a wavelength of light emitted by the emission layer, and the electron blocking layer may block the leakage of electrons from the emission layer to the hole transport region. Materials that may be included in the hole transport region may be included in the emission auxiliary layer and the electron blocking layer.
[p-Dopant]
The hole transport region may further include, in addition to the aforementioned 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 the charge-generation material).
The charge-generation material may be, for example, a p-dopant.
In embodiments, the p-dopant may have a lowest unoccupied molecular orbital (LUMO) energy level equal to or less than about −3.5 eV.
In an embodiment, the p-dopant may include a quinone derivative, a cyano group-containing compound, a compound including element EL1 and element EL2, or a combination thereof.
Examples of a quinone derivative may include TCNQ, F4-TCNQ, and the like.
Examples of a cyano group-containing compound may include HAT-CN, a compound represented by Formula 221, and the like:
In Formula 221,
In the compound including element EL1 and element EL2, element EL1 may be a metal, a metalloid, or a combination thereof, and element EL2 may be a non-metal, a metalloid, or a combination thereof.
Examples of a metal may include: an alkali metal (e.g., lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.); an alkaline earth metal (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.); a transition metal (e.g., 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 (e.g., zinc (Zn), indium (In), tin (Sn), etc.); a lanthanide metal (e.g., 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.); and the like.
Examples of a metalloid may include silicon (Si), antimony (Sb), tellurium (Te), and the like.
Examples of a non-metal may include oxygen (O), a halogen (for example, F, Cl, Br, I, etc.), and the like.
Examples of a compound including element EL1 and element EL2 may include a metal oxide, a metal halide (e.g., a metal fluoride, a metal chloride, a metal bromide, a metal iodide, etc.), a metalloid halide (e.g., a metalloid fluoride, a metalloid chloride, a metalloid bromide, a metalloid iodide, etc.), a metal telluride, or any combination thereof.
Examples of a metal oxide may include a tungsten oxide (e.g., WO, W2O3, WO2, WO3, W2O5, etc.), a vanadium oxide (e.g., VO, V2O3, VO2, V2O5, etc.), a molybdenum oxide (e.g., MoO, Mo2O3, MoO2, MoO3, Mo2O5, etc.), a rhenium oxide (e.g., ReO3, etc.), and the like.
Examples of a metal halide may include an alkali metal halide, an alkaline earth metal halide, a transition metal halide, a post-transition metal halide, a lanthanide metal halide, and the like.
Examples of an alkali metal halide may include LiF, NaF, KF, RbF, CsF, LiCl, NaCl, KCl, RbCl, CsCl, LiBr, NaBr, KBr, RbBr, CsBr, LiI, NaI, KI, RbI, CsI, and the like.
Examples of an alkaline earth metal halide may include BeF2, MgF2, CaF2, SrF2, BaF2, BeCl2, MgCl2, CaCl2), SrCl2, BaCl2, BeBr2, MgBr2, CaBr2, SrBr2, BaBr2, Bel2, MgI2, CaI2, SrI2, BaI2, and the like.
Examples of a transition metal halide may include a titanium halide (e.g., TiF4, TiCl4, TiBr4, TiI4, etc.), a zirconium halide (e.g., ZrF4, ZrCl4, ZrBr4, ZrI4, etc.), a hafnium halide (e.g., HfF4, HfCl4, HfBr4, HfI4, etc.), a vanadium halide (e.g., VF3, VCl3, VBrs, VI3, etc.), a niobium halide (e.g., NbF3, NbCl3, NbBr3, NbI3, etc.), a tantalum halide (e.g., TaF3, TaCl3, TaBr3, TaI3, etc.), a chromium halide (e.g., CrF3, CrO3, CrBr3, CrI3, etc.), a molybdenum halide (e.g., MoF3, MoCl3, MoBr3, MoI3, etc.), a tungsten halide (e.g., WF3, WCl3, WBrs, WI3, etc.), a manganese halide (e.g., MnF2, MnCl2, MnBr2, Mn12, etc.), a technetium halide (e.g., TcF2, TcCl2, TcBr2, TcI2, etc.), a rhenium halide (e.g., ReF2, ReCl2, ReBr2, ReI2, etc.), an iron halide (e.g., FeF2, FeCl2, FeBr2, FeI2, etc.), a ruthenium halide (e.g., RuF2, RuCl2, RuBr2, RuI2, etc.), an osmium halide (e.g., OsF2, OsC12, OsBr2, OsI2, etc.), a cobalt halide (e.g., CoF2, COCl2, CoBr2, CoI2, etc.), a rhodium halide (e.g., RhF2, RhCl2, RhBr2, RhI2, etc.), an iridium halide (e.g., IrF2, IrCl2, IrBr2, IrI2, etc.), a nickel halide (e.g., NiF2, NiCl2, NiBr2, NiI2, etc.), a palladium halide (e.g., PdF2, PdCl2, PdBr2, PdI2, etc.), a platinum halide (e.g., PtF2, PtCl2, PtBr2, PtI2, etc.), a copper halide (e.g., CuF, CuCl, CuBr, CuI, etc.), a silver halide (e.g., AgF, AgCl, AgBr, AgI, etc.), a gold halide (e.g., AuF, AuCl, AuBr, AuI, etc.), and the like.
Examples of a post-transition metal halide may include a zinc halide (e.g., ZnF2, ZnCl2, ZnBr2, ZnI2, etc.), an indium halide (e.g., InI3, etc.), a tin halide (e.g., SnI2, etc.), and the like.
Examples of a lanthanide metal halide may include YbF, YbF2, YbF3, SmF3, YbCl, YbCl2, YbCl3 SmCl3, YbBr, YbBr2, YbBr3 SmBrs, YbI, YbI2, YbI3, SmI3, and the like.
Examples of a metalloid halide may include an antimony halide (e.g., SbCl5, etc.) and the like.
Examples of a metal telluride may include an alkali metal telluride (e.g., Li2Te, Na2Te, K2Te, Rb2Te, Cs2Te, etc.), an alkaline earth metal telluride (e.g., BeTe, MgTe, CaTe, SrTe, BaTe, etc.), a transition metal telluride (e.g., 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 (e.g., ZnTe, etc.), a lanthanide metal telluride (e.g., LaTe, CeTe, PrTe, NdTe, PmTe, EuTe, GdTe, TbTe, DyTe, HoTe, ErTe, TmTe, YbTe, LuTe, etc.), and the like.
In case that the organic light-emitting device 10 is a full-color organic light-emitting device, the emission layer may be patterned into a red emission layer, a green emission layer, and/or a blue emission layer, according to a subpixel. In an embodiment, the emission layer may have a stacked structure of two or more layers of a red emission layer, a green emission layer, and a blue emission layer, in which the two or more layers may contact each other or may be separated from each other, to emit white light. In embodiments, the emission layer may include two or more materials among a red light-emitting material, a green light-emitting material, and a blue light-emitting material, in which the two or more materials may be mixed with each other in a single layer, to emit white light.
In an embodiment, the emission layer may include a host and a dopant. The dopant may include a phosphorescent dopant, a fluorescent dopant, or any combination thereof.
An amount of the dopant in the emission layer may be in a range of about 0.01 parts by weight to about 15 parts by weight, based on 100 parts by weight of the host.
In embodiments, the emission layer may include quantum dots.
In embodiments, the emission layer may include a delayed fluorescence material. The delayed fluorescence material may serve as a host or as a dopant in the emission layer.
The emission layer may further include a host, an auxiliary dopant, a sensitizer, a delayed fluorescence material, or any combination thereof, in addition to the aforementioned heterocyclic compound. Each of the host, the auxiliary dopant, the sensitizer, the delayed fluorescence material, or any combination thereof may include at least one deuterium atom.
In embodiments, the emission layer may include the organometallic compound and the host. The host may be different from the organometallic compound, and the host may include an electron-transporting compound, a hole-transporting compound, a bipolar compound, or any combination thereof. The host may not include metal. The electron-transporting compound, the hole-transporting compound, and the bipolar compound may be different from each other.
In an embodiment, the emission layer may include the organometallic compound and the host, and the host may include an electron-transporting compound and a hole-transporting compound.
In an embodiment, the electron-transporting compound and the hole-transporting compound may form an exciplex.
A thickness of the emission layer may be in a range of about 100 Å to about 1,000 Å. For example, the thickness of the emission layer may be in a range of about 200 Å to about 600 Å. In case that the thickness of the emission layer is within these ranges, excellent luminescence characteristics may be obtained without a substantial increase in driving voltage.
In an embodiment, the host may include a compound represented by Formula 301:
[Ar301]xb11-[(L301)xb1-R301]xb21 [Formula 301]
In Formula 301,
In an embodiment, in Formula 301, when xb11 is 2 or more, two or more of Ar301 may be linked to each other via a single bond.
In embodiments, the host may include a compound represented by Formula 301-1, a compound represented by Formula 301-2, or any combination thereof:
In Formulae 301-1 and 301-2,
In embodiments, the host may include an alkali earth metal complex, a post-transition metal complex, or any combination thereof. In embodiments, the host may include a Be complex (e.g., Compound H55), an Mg complex, a Zn complex, or any combination thereof.
In embodiments, 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-9-carbazolylbenzene (mCP), 1,3,5-tri(carbazol-9-yl)benzene (TCP), or a combination thereof:
In an embodiment, the host may include a first host compound and a second host compound.
In an embodiment, the first host compound may be a hole-transporting host.
In an embodiment, the second host compound may be an electron-transporting host.
In an embodiment, the term “hole-transporting host” as used herein may be a compound including a hole-transporting moiety.
In an embodiment, the term “electron-transporting host” as used herein may be a compound not only including an electron-transporting moiety but also having bipolar properties.
The terms “hole-transporting host” and “electron-transporting host” as used herein may be understood according to the relative difference in hole mobility and electron mobility therebetween. For example, even when the electron-transporting host does not include an electron-transporting moiety, a bipolar compound exhibiting relatively higher electron mobility than the hole-transporting host may be also understood as the electron-transporting host.
In an embodiment, the hole-transporting host may be represented by one of Formulae 311-1 to 311-6, and the electron-transporting host may be represented by one of Formulae 312-1 to 312-4 and 313:
In Formulae 311-1 to 311-6, 312-1 to 312-4, 313, and 313 Å,
In an embodiment, the first host compound and the second host compound may form an exciplex.
In an embodiment, the emission layer may further include a phosphorescent dopant.
For example, the emission layer may further include a phosphorescent dopant, and the phosphorescent dopant may serve as a sensitizer.
The phosphorescent dopant may include at least one transition metal as a central metal.
The phosphorescent dopant may include a monodentate ligand, a bidentate ligand, a tridentate ligand, a tetradentate ligand, a pentadentate ligand, a hexadentate ligand, or any combination thereof.
The phosphorescent dopant may be electrically neutral.
In an embodiment, the phosphorescent dopant may be the organometallic compound.
In embodiments, the phosphorescent dopant may include an organometallic compound represented by Formula 401:
M(L401)xc1(L402)xc2 [Formula 401]
In Formulae 401 and 402,
In embodiments, in Formula 402, X401 may be nitrogen and X402 may be carbon, or X401 and X402 may each be nitrogen.
In an embodiment, in Formula 401, when xc1 is 2 or more, two ring A401(s) among two or more L401(s) may optionally be linked to each other via T402, which is a linking group, and two ring A402(s) among two or more L401(s) may optionally be linked to each other via T403, which is a linking group (see Compounds PD1 to PD4 and PD7). T402 and T403 may each independently be the same as described in connection with T401.
In Formula 401, L402 may be an organic ligand. For example, L402 may include a halogen group, a diketone group (e.g., an acetylacetonate group), a carboxylic acid group (e.g., a picolinate group), —C(═O), an isonitrile group, —CN group, a phosphorus group (e.g., a phosphine group, a phosphite group, etc.), or any combination thereof.
The phosphorescent dopant may be, for example, one of Compounds PD1 to PD41 or any combination thereof:
In an embodiment, the emission layer may further include a phosphorescent dopant.
The fluorescent dopant may include an amine group-containing compound, a styryl group-containing compound, or any combination thereof.
In embodiments, the fluorescent dopant may include a compound represented by Formula 501:
In Formula 501,
In an embodiment, in Formula 501, Ar501 may be a condensed cyclic group (e.g., an anthracene group, a chrysene group, a pyrene group, etc.) in which three or more monocyclic groups are condensed together.
In an embodiment, in Formula 501, xd4 may be 2.
In an embodiment, the fluorescent dopant may include: one of Compounds FD1 to FD36; DPVBi; DPAVBi; or any combination thereof:
In an embodiment, the emission layer may further include a delayed fluorescence material.
In the specification, the delayed fluorescence material may be selected from compounds capable of emitting delayed fluorescence based on a delayed fluorescence emission mechanism.
The delayed fluorescence material included in the emission layer may serve as a host or as a dopant, depending on the types of other materials included in the emission layer.
In an embodiment, a difference between a triplet energy level (eV) of the delayed fluorescence material and the singlet energy level (eV) of the delayed fluorescence material may be in a range of about 0 eV to about 0.5 eV. When the difference between the triplet energy level (eV) of the delayed fluorescence material and the singlet energy level (eV) of the delayed fluorescence material is satisfied within the range above, up-conversion from the triplet state to the singlet state of the delayed fluorescence materials may effectively occur, and thus, the light-emitting device 10 may have improved luminescence efficiency.
In embodiments, the delayed fluorescence material may include a material including at least one electron donor (e.g., a π electron-rich C3-C60 cyclic group, such as a carbazole group, etc.) and at least one electron acceptor (e.g., a sulfoxide group, a cyano group, a π electron-deficient nitrogen-containing C1-C60 cyclic group, etc.), or the delayed fluorescence material may include a material including a C8-C60 polycyclic group in which two or more cyclic groups are condensed while sharing boron (B).
In an embodiment, the delayed fluorescence material may include at least one of Compounds DF1 to DF9:
In an embodiment, the emission layer may include quantum dots.
In the specification, a quantum dot may be a crystal of a semiconductor compound, and may include any material capable of emitting light of various emission wavelengths according to a size of the crystals.
A diameter of a quantum dot may be, for example, in a range of about 1 nm to about 10 nm.
The quantum dots may be synthesized by a wet chemical process, a metal organic chemical vapor deposition process, a molecular beam epitaxy process, or any process similar thereto.
The wet chemical process is a method including mixing a precursor material with an organic solvent and growing quantum dot particle crystals. When the crystals grow, the organic solvent naturally acts as a dispersant coordinated on the surface of the quantum dot crystals and controls the growth of the crystals so that the growth of quantum dot particles may be controlled through a process which costs less and may be more readily performed than vapor deposition methods, such as metal organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE).
The quantum dots may include: a Group II-VI semiconductor compound; a Group III-V semiconductor compound; a Group III-VI semiconductor compound; a Group I-III-VI semiconductor compound; a Group IV-VI semiconductor compound; a Group IV element or compound; or any combination thereof.
Examples of a Group II-VI semiconductor compound may include: a binary compound, such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, and the like; a ternary compound, such as CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS, and the like; a quaternary compound, such as CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and the like; or any combination thereof.
Examples of a Group III-V semiconductor compound may include: a binary compound, such as GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, etc. a ternary compound, such as GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InGaP, InNP, InAlP, InNAs, InNSb, InPAs, InPSb, etc.; a quaternary compound, such as GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, etc.; or any combination thereof. In an embodiment, a Group III-V semiconductor compound may further include a Group II element. Examples of a Group III-V semiconductor compound further including a Group II element may include InZnP, InGaZnP, InAlZnP, etc.
Examples of a Group Ill-VI semiconductor compound may include: a binary compound, such as GaS, GaSe, Ga2Se3, GaTe, InS, InSe, In2S3, In2Se3, InTe, etc.; a ternary compound, such as InGaS3, InGaSes, etc.; or any combination thereof.
Examples of a Group I-III-VI semiconductor compound may include: a ternary compound, such as AgInS, AgInS2, CuInS, CuInS2, CuGaO2, AgGaO2, AgAlO2, etc.; or any combination thereof.
Examples of a Group IV-VI semiconductor compound may include: a binary compound, such as SnS, SnSe, SnTe, PbS, PbSe, or PbTe; a ternary compound, such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, etc.; a quaternary compound, such as SnPbSSe, SnPbSeTe, SnPbSTe, etc.; or any combination thereof.
Examples of a Group IV element or compound may include: a single element material, such as Si, Ge, etc.; a binary compound, such as SiC, SiGe, etc.; or any combination thereof.
Each element included in a multi-element compound, such as a binary compound, a ternary compound, or a quaternary compound, may be present in a particle at a uniform concentration or at a non-uniform concentration.
In embodiments, the quantum dots may have a single structure in which the concentration of each element in the quantum dots is uniform, or the quantum dots may have a core-shell structure. For example, materials included in the core and materials included in the shell may be different from each other.
The shell of the quantum dots may serve as a protective layer that prevents chemical degeneration of the core to maintain semiconductor characteristics, and/or may serve as a charging layer that imparts electrophoretic characteristics to the quantum dots. The shell may be single-layered or multi-layered. An interface between the core and the shell may have a concentration gradient in which the concentration of a material that is present in the shell decreases toward the core.
Examples of a quantum dot shell may include: a metal oxide, a metalloid oxide, a non-metal oxide, a semiconductor compound, or any combination thereof. Examples of a metal oxide, a metalloid, or a non-metal oxide may include: a binary compound, such as SiO2, Al2O3, TiO2, ZnO, MnO, Mn2O3, Mn3O4, CuO, FeO, Fe2O3, Fe3O4, CoO, Co3O4, NiO, and the like; a ternary compound, such as MgAl2O4, CoFe2O4, NiFe2O4, CoMn2O4, and the like; or any combination thereof. Examples of the semiconductor compound may include: a Group II-VI semiconductor compound; a Group Ill-V semiconductor compound; a Group Ill-VI semiconductor compound; a Group 1-Ill-VI semiconductor compound; a Group IV-VI semiconductor compound; or any combination thereof. Examples of a semiconductor compound may include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnSeS, ZnTeS, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InGaP, InSb, AlAs, AlP, AlSb, or any combination thereof.
A full width at half maximum (FWHM) of an emission wavelength spectrum of the quantum dots may be equal to or less than about 45 nm. For example, the FWHM of an emission wavelength spectrum of the quantum dots may be equal to or less than about 40 nm. For example, the FWHM of an emission wavelength spectrum of the quantum dots may be equal to or less than about 30 nm. Within any of these ranges, color purity or color reproducibility of the quantum dots may be improved. Light emitted through the quantum dots may be emitted in all directions, so that a wide viewing angle may be improved.
In an embodiment, the quantum dots may be in the form of a spherical particle, a pyramidal particle, a multi-arm particle, a cubic nanoparticle, a nanotube particle, a nanowire particle, a nanofiber particle, a nanoplate particle, or the like.
By controlling the size of the quantum dot, an energy band gap may be adjustable so that light having various wavelength bands may be obtained from the emission layer including the quantum dot. Accordingly, by using quantum dots of different sizes, the organic light-emitting device that emits light of various wavelengths may be implemented. In an embodiment, the size of quantum dots may be selected to emit red light, green light, and/or blue light. In an embodiment, the size of quantum dots may be configured to emit white light by combining light of various colors.
The electron transport region may have a structure consisting of a layer consisting of a single material, a structure consisting of a layer consisting of different materials, or a structure including multiple layers including different materials.
The electron transport region may include a buffer layer, a hole blocking layer, an electron control layer, an electron transport layer, an electron injection layer, or any combination thereof.
In embodiments, the electron transport region may have an electron transport layer/electron injection layer structure, a hole blocking layer/electron transport layer/electron injection layer structure, an electron control layer/electron transport layer/electron injection layer structure, or a buffer layer/electron transport layer/electron injection layer structure, wherein the layers of each structure may be stacked from the emission layer in its respective stated order, but the structure of the electron transport region is not limited thereto.
In an embodiment, the electron transport region (for example, a buffer layer, a hole blocking layer, an electron control layer, or an electron transport layer in the electron transport region) may include a metal-free compound including at least one π electron-deficient nitrogen-containing C1-C60 cyclic group.
In embodiments, the electron transport region may include a compound represented by Formula 601:
[Ar601]xe11-[(L601)xe1-R601]xe21. [Formula 601]
In Formula 601,
In an embodiment, in Formula 601, when xe11 is 2 or more, two or more of Ar601 may be linked to each other via a single bond.
In an embodiment, in Formula 601, Ar601 may be a substituted or unsubstituted anthracene group.
In embodiments, the electron transport region may include a compound represented by Formula 601-1:
In Formula 601-1,
In embodiments, in Formulae 601 and 601-1, xe1 and xe611 to xe613 may each independently be 0, 1, or 2.
In embodiments, the electron transport region may include: one of Compounds ET1 to ET45; 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP); 4,7-diphenyl-1,10-phenanthroline (Bphen); Alq3; BAlq; TAZ; NTAZ; or any combination thereof:
A thickness of the electron transport region may be in a range of about 100 Å to about 5,000 Å. For example, the thickness of the electron transport region may be in a range of about 160 Å to about 4,000 Å. When the electron transport region includes a buffer layer, a hole blocking layer, an electron control layer, an electron transport layer, or any combination thereof, a thickness of the buffer layer, the hole blocking layer, or the electron control layer may each independently be in a range of about 20 Å to about 1,000 Å, and a thickness of the electron transport layer may be in a range of about 100 Å to about 1,000 Å. For example, the thickness of the buffer layer, the hole blocking layer, or the electron control layer may each independently be in a range of about 30 Å to about 300 Å. For example, the thickness of the electron transport layer may be in a range of about 150 Å to about 500 Å. When the thicknesses of the buffer layer, the hole blocking layer, the electron control layer, the electron transport layer, and/or the electron transport region are within these ranges, satisfactory electron transporting characteristics may be obtained without a substantial increase in driving voltage.
The electron transport region (e.g., an electron transport layer in the electron transport region) may further include, in addition to the aforementioned materials, a metal-containing material.
The metal-containing material may include an alkali metal complex, an alkaline earth metal complex, or any combination thereof. A metal ion of the alkali metal complex may be a Li ion, a Na ion, a K ion, a Rb ion, or a Cs ion, and a metal ion of 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 a metal ion of an alkali metal complex or a metal ion of an alkaline earth-metal complex may each independently include a hydroxyquinoline, a hydroxyisoquinoline, a hydroxybenzoquinoline, a hydroxyacridine, a hydroxyphenanthridine, a hydroxyphenyloxazole, a hydroxyphenylthiazole, a hydroxyphenyloxadiazole, a hydroxyphenylthiadiazole, a hydroxyphenylpyridine, a hydroxyphenylbenzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or any combination thereof.
For example, the metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 (LiQ) or Compound 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 contact (e.g., directly contact) the second electrode 150.
The electron injection layer may have a structure consisting of a layer consisting of a single material, a structure consisting of a layer including different materials, or a structure including multiple layers including different materials.
In an embodiment, 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 (e.g., 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: an alkali metal oxide, such as Li2O, Cs2O, K2O, and the like; an alkali metal halide, such as LiF, NaF, CsF, KF, LiI, NaI, CsI, KI, and the like; or any combination thereof. The alkaline earth metal-containing compound may include an alkaline earth metal compound, such as BaO, SrO, CaO, BaxSr1-xO (wherein x is a real number satisfying 0<x<1), BaxCa1-xO (wherein x is a real number satisfying 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 an embodiment, the rare earth metal-containing compound may include a lanthanide metal telluride. Examples of a lanthanide metal telluride may include LaTe, CeTe, PrTe, NdTe, PmTe, SmTe, EuTe, GdTe, TbTe, DyTe, HoTe, ErTe, TmTe, YbTe, LuTe, La2Te3, Ce2Te3, Pr2Te3, Nd2Te3, Pm2Te3, Sm2Te3, Eu2Te3, Gd2Te3, Tb2Te3, Dy2Te3, Ho2Te3, Er2Te3, Tm2Te3, Yb2Te3, Lu2Te3, and the like.
The alkali metal complex, the alkaline earth-metal complex, and the rare earth metal complex may include: an alkali metal ion, an alkaline earth metal ion, or a rare earth metal ion; and a ligand bonded to the metal ion (for example, hydroxyquinoline, hydroxyisoquinoline, hydroxybenzoquinoline, hydroxyacridine, hydroxyphenanthridine, hydroxyphenyloxazole, hydroxyphenylthiazole, hydroxyphenyloxadiazole, hydroxyphenylthiadiazole, hydroxyphenylpyridine, hydroxyphenyl benzimidazole, hydroxyphenylbenzothiazole, bipyridine, phenanthroline, cyclopentadiene, or any combination thereof).
In an embodiment, 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 embodiments, the electron injection layer may further include an organic material (e.g., the compound represented by Formula 601).
In embodiments, the electron injection layer may consist of an alkali metal-containing compound (e.g., an alkali metal halide); or the electron injection layer may consist of an alkali metal-containing compound (e.g., an alkali metal halide), and an alkali metal, an alkaline earth metal, a rare earth metal, or any combination thereof. For example, the electron injection layer may be a KI:Yb co-deposited layer, an RbI:Yb co-deposited layer, a LiF:Yb co-deposited layer, and the like.
In case that the electron injection layer further includes an organic material, an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal-containing compound, an alkaline earth metal-containing compound, a rare earth metal-containing compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or any combination thereof may be uniformly or non-uniformly dispersed in a matrix including the organic material.
A thickness of the electron injection layer may be in a range of about 1 Å to about 100 Å. For example, the thickness of the electron injection layer may be in a range of about 3 Å to about 90 Å. When the thickness of the electron injection layer is within any of these ranges, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.
The second electrode 150 is arranged on the interlayer 130 having the aforementioned structure. The second electrode 150 may be a cathode, which is an electron injection electrode. When the second electrode 150 is a cathode, a material for forming the second electrode 150 may include a material having a low-work function, such as a metal, an alloy, an electrically conductive compound, or any combination thereof.
The second electrode 150 may include Li, Ag, Mg, Al, Al—Li, Ca, Mg—In, Mg—Ag, Yb, Ag—Yb, ITO, IZO, or any combination thereof. The second electrode 150 may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode.
The second electrode 150 may have a single-layer structure or a multi-layer structure.
The organic light-emitting device 10 may include a first capping layer arranged outside the first electrode 110, and/or a second capping layer arranged outside the second electrode 150. In embodiments, the organic light-emitting device 10 may have a structure in which the first capping layer, the first electrode 110, the interlayer 130, and the second electrode 150 are stacked in the stated order, a structure in which the first electrode 110, the interlayer 130, the second electrode 150, and the second capping layer are stacked in the stated order, or a structure in which the first capping layer, the first electrode 110, the interlayer 130, the second electrode 150, and the second capping layer are stacked in the stated order.
Light generated in an emission layer of the interlayer 130 of the organic light-emitting device 10 may be extracted through the first electrode 110, which may be a semi-transmissive electrode or a transmissive electrode, and through the first capping layer to the outside. Light generated in an emission layer of the interlayer 130 of the organic light-emitting device 10 may be extracted through the second electrode 150, which may be a semi-transmissive electrode or a transmissive electrode, and through the second capping layer to the outside.
The first capping layer and the second capping layer may each increase external emission efficiency according to the principle of constructive interference. Accordingly, light extraction efficiency of the organic light-emitting device 10 is increased, so that the luminescence efficiency of the organic light-emitting device 10 may be improved.
The first capping layer and the second capping layer may each include a material having a refractive index equal to or greater than about 1.6 (with respect to a wavelength of about 589 nm).
The first capping layer and the second capping layer may each independently be an organic capping layer including an organic material, an inorganic capping layer including an inorganic material, or an organic-inorganic composite capping layer including an organic material and an inorganic material.
At least one of the first capping layer and the second capping layer may each independently include a carbocyclic compound, a heterocyclic compound, an amine group-containing compound, a porphine derivative, a phthalocyanine derivative, a naphthalocyanine derivative, an alkali metal complex, an alkaline earth metal complex, or any combination thereof. The carbocyclic compound, the heterocyclic compound, and the amine group-containing compound may optionally be substituted with a substituent including O, N, S, Se, Si, F, Cl, Br, I, or any combination thereof.
In an embodiment, at least one of the first capping layer and the second capping layer may each independently include an amine group-containing compound.
In 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 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; β-NPB; or any combination thereof:
The organometallic compound represented by Formula 1 may be included in various films. Thus, another embodiment provides a film including the organometallic compound represented by Formula 1. The film may be, for example, an optical member (or a light control means) (for example, a color filter, a color conversion member, a capping layer, a light extraction efficiency enhancement layer, a selective light absorbing layer, a polarizing layer, a quantum dot-containing layer, or like), a light blocking member (for example, a light reflective layer, a light absorbing layer, or the like), a protective member (for example, an insulating layer, a dielectric layer, or the like), or the like.
The organic light-emitting device may be included in various electronic apparatuses. For example, an electronic apparatus including the organic light-emitting device may be a light-emitting apparatus, an authentication apparatus, and the like.
The electronic apparatus (for example, a light-emitting apparatus) may further include, in addition to the organic light-emitting device, a color filter, a color conversion layer, or a color filter and a color conversion layer. The color filter and/or the color conversion layer may be arranged in at least one traveling direction of light emitted from the organic light-emitting device. For example, the light emitted from the organic light-emitting device may be blue light or white light. The organic light-emitting device may be the same as described above. In an embodiment, the color conversion layer may include quantum dots. The quantum dots may be, for example, the quantum dots as described above.
The electronic apparatus may include a first substrate. The first substrate may include subpixels, the color filter may include color filter areas respectively corresponding to the subpixels, and the color conversion layer may include color conversion areas respectively corresponding to the subpixels.
A pixel-defining film may be arranged between the subpixels to define each subpixel.
The color filter may further include color filter areas and light-shielding patterns arranged between the color filter areas, and the color conversion layer may further include color conversion areas and light-shielding patterns arranged between the color conversion areas.
The color filter areas (or the color conversion areas) may include a first area emitting first color light, a second area emitting second color light, and/or a third area emitting third color light, wherein the first color light, the second color light, and/or the third color light may have different maximum emission wavelengths from one another. For example, the first color light may be red light, the second color light may be green light, and the third color light may be blue light. In an embodiment, the color filter areas (or the color conversion areas) may include quantum dots. For example, the first area may include red quantum dots, the second area may include green quantum dots, and the third area may not include quantum dots. Further details on the quantum dots may be the same as described herein. Each of the first area, the second area, and/or the third area may further include a scatterer.
In embodiments, the organic light-emitting device may emit 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. The first-first color light, the second-first color light, and the third-first color light may have different maximum emission wavelengths from one another. For example, the first light may be blue light, the first-first color light may be red light, the second-first color light may be green light, and the third-first color light may be blue light.
The electronic apparatus may further include a thin-film transistor in addition to the aforementioned organic light-emitting device. The thin-film transistor may include a source electrode, a drain electrode, and an active 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 organic light-emitting device.
The thin-film transistor may further include a gate electrode, a gate insulating film, and the like.
The active layer may include crystalline silicon, amorphous silicon, an organic semiconductor, an oxide semiconductor, and the like.
The electronic apparatus may further include a sealing portion for sealing the organic light-emitting device. The sealing portion may be arranged between the color filter and/or the color conversion layer and the organic light-emitting device. The sealing portion allows light from the organic light-emitting device to be extracted to the outside, and simultaneously prevents ambient air and moisture from penetrating into the light-emitting device. The sealing portion may be a sealing substrate that includes a transparent glass substrate or a plastic substrate. The sealing portion may be a thin-film encapsulation layer that includes at least one 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 further included on the sealing portion, in addition to the color filter and/or the color conversion layer, according to the use of the electronic apparatus. Examples of a functional layer 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 further include, in addition to the light-emitting device as described above, a biometric information collector. The authentication apparatus may be, for example, a biometric authentication apparatus that authenticates an individual by using biometric information of a living body (e.g., fingertips, pupils, etc.).
The electronic apparatus may be applied to various displays, light sources, lighting, personal computers (e.g., mobile personal computers), mobile phones, digital cameras, electronic organizers, electronic dictionaries, electronic game machines, medical instruments (e.g., 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 (e.g., meters for a vehicle, an aircraft, and a vessel), projectors, and the like.
The organic light-emitting device may be included in various types of electronic equipment.
In an embodiment, an electronic equipment including the organic light-emitting device may be a flat panel display, a curved display, a computer monitor, a medical monitor, a television, a billboard, an indoor light, an outdoor light, a signal light, a head-up display, a fully transparent display, a partially transparent display, a flexible display, a rollable display, a foldable display, a stretchable display, a laser printer, a telephone, a mobile phone, a tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro display, a (three-dimensional (3D) display, a virtual reality display, an augmented reality display, a vehicle, a video wall including multiple displays tiled together, a theater screen, a stadium screen, a phototherapy device, a signboard, an automotive sensor, a home sensor, or a solar cell.
Since the organic light-emitting device has excellent photoelectric properties or the like, the electronic equipment including the organic light-emitting device may have an optical sensor function such as a fingerprint recognition sensor or the like.
The electronic apparatus (for example, a light-emitting apparatus) of
The substrate 100 may be a flexible substrate, a glass substrate, or a metal substrate. A buffer layer 210 may be arranged on the substrate 100. The buffer layer 210 may prevent penetration of impurities through the substrate 100, and provide a flat surface on the substrate 100.
A TFT may be arranged on the buffer layer 210. The TFT may include an active layer 220, a gate electrode 240, a source electrode 260, and a drain electrode 270.
The active layer 220 may include an inorganic semiconductor, such as silicon or polysilicon, an organic semiconductor, or an oxide semiconductor, and may include a source region, a drain region, and a channel region.
A gate insulating film 230 for insulating the active layer 220 from the gate electrode 240 may be arranged on the active layer 220, and the gate electrode 240 may be arranged on the gate insulating film 230.
An interlayer insulating film 250 may be arranged on the gate electrode 240. The interlayer insulating film 250 may be arranged between the gate electrode 240 and the source electrode 260 and between the gate electrode 240 and the drain electrode 270 to insulate these electrodes from one another.
The source electrode 260 and the drain electrode 270 may be arranged on the interlayer insulating film 250. The interlayer insulating film 250 and the gate insulating film 230 may be formed to expose a source region and a drain region of the active layer 220, and the source electrode 260 and the drain electrode 270 may respectively contact the exposed portions of the source region and the drain region of the active layer 220.
The TFT may be electrically connected to the organic light-emitting device to drive the organic light-emitting device, and may be covered and protected by a passivation layer 280. The passivation layer 280 may include an inorganic insulating film, an organic insulating film, or a combination thereof. The passivation layer 280 may include an inorganic insulating film, an organic insulating film, or any combination thereof. An organic light-emitting device may be provided on the passivation layer 280. The organic light-emitting device may include the first electrode 110, the interlayer 130, and the second electrode 150.
The first electrode 110 may be arranged on the passivation layer 280. The passivation layer 280 may not completely cover the drain electrode 270 and may expose a portion of the drain electrode 270. The first electrode 110 may be connected (for example, electrically connected) to the exposed portion of the drain electrode 270.
A pixel defining layer 290 including an insulating material may be arranged on the first electrode 110. The pixel defining layer 290 may expose a region of the first electrode 110, and the interlayer 130 may be formed on the exposed region of the first electrode 110. The pixel defining layer 290 may be a polyimide-based organic film or a polyacrylic-based organic film. Although not shown in
The second electrode 150 may be arranged on the interlayer 130, and a capping layer 170 may be further included on the second electrode 150. The capping layer 170 may be formed to cover the second electrode 150.
The encapsulation portion 300 may be arranged on the capping layer 170. The encapsulation portion 300 may be arranged on the organic light-emitting device to protect the organic light-emitting device from moisture and/or oxygen. The encapsulation portion 300 may include: an inorganic film including silicon nitride (SiNx), silicon oxide (SiOx), indium tin oxide, indium zinc oxide, or any combination thereof; an organic film including polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyethylene sulfonate, polyoxymethylene, polyarylate, hexamethyldisiloxane, an acrylic resin (e.g., polymethyl methacrylate, polyacrylic acid, etc.), an epoxy-based resin (e.g., aliphatic glycidyl ether (AGE), etc.), or any combination thereof; or any combination of the inorganic films and the organic films.
The electronic apparatus (for example a light-emitting apparatus) of
The electronic equipment 1, which may be an apparatus that displays a moving image or a still image, may be not only a portable electronic equipment, such as a mobile phone, a smartphone, a tablet personal computer (PC), a mobile communication terminal, an electronic notebook, an electronic book, a portable multimedia player (PMP), a navigation device, or an ultra-mobile PC (UMPC), but may also be various products, such as a television, a laptop computer, a monitor, a billboard, or an Internet of things (IOT). The electronic equipment 1 may be any product as described above or a part thereof.
In an embodiment, the electronic apparatus 1 may be a wearable device, such as a smart watch, a watch phone, a glasses-type display, or a head mounted display (HMD), or a part of such a wearable device. However, embodiments of the disclosure are not limited thereto.
Examples of the electronic equipment 1 may include a dashboard of a vehicle, a center fascia of a vehicle, a center information display (CID)_arranged on a dashboard of a vehicle, a room mirror display that replaces a side mirror of a vehicle, an entertainment display for the rear seat of a vehicle or a display arranged on the back of the front seat, or a head up display (HUD) installed at the front of a vehicle or projected on a front window glass, a computer generated hologram augmented reality head up display (CGH AR HUD).
The electronic equipment 1 may include a display area DA and a non-display area NDA outside the display area DA. A display device may implement an image through a two-dimensional array of pixels that are arranged in the display area DA.
The non-display area NDA is an area that does not display an image, and may surround (for example, entirely surround) the display area DA. A driver for providing electrical signals or power to display devices arranged in the display area DA may be arranged in the non-display area NDA. A pad, which is an area to which an electronic element or a printed circuit board may be electrically connected, may be arranged in the non-display area NDA.
In the electronic equipment 1, a length in the x-axis direction and a length in the y-axis direction may be different from each other. In an embodiment as shown in
Referring to
The vehicle 1000 may travel on a road or a track. The vehicle 1000 may move in a selected or given direction according to rotation of at least one wheel. Examples of a vehicle 1000 may include a three-wheeled or four-wheeled vehicle, a construction machine, a two-wheeled vehicle, a prime mover device, a bicycle, and a train running on a track.
The vehicle 1000 may include a body having an interior and an exterior, and a chassis that is a portion excluding the body in which mechanical apparatuses necessary for driving are installed. The exterior of the body of the vehicle 1000 may include a front panel, a bonnet, a roof panel, a rear panel, a trunk, a pillar provided at a boundary between doors, and the like. The chassis of the vehicle 1000 may include a power generating device, a power transmitting device, a driving device, a steering device, a braking device, a suspension device, a transmission device, a fuel device, front, rear, left, and right wheels, and the like.
The vehicle 1000 may include a side window glass 1100, a front window glass 1200, a side mirror 1300, a cluster 1400, a center fascia 1500, a passenger seat dashboard 1600, and a display device 2.
The side window glass 1100 and the front window glass 1200 may be partitioned by a pillar arranged between the side window glass 1100 and the front window glass 1200.
The side window glass 1100 may be installed on a side of the vehicle 1000. In an embodiment, the side window glass 1100 may be installed on a door of the vehicle 1000. Multiple side window glasses 1100 may be provided and may face each other. In an embodiment, the side window glass 1100 may include a first side window glass 1110 and a second side window glass 1120. In an embodiment, the first side window glass 1110 may be arranged adjacent to the cluster 1400, and the second side window glass 1120 may be arranged adjacent to the passenger seat dashboard 1600.
In an embodiment, the side window glasses 1100 may be spaced apart from each other in the x-direction or the −x-direction. For example, the first side window glass 1110 and the second side window glass 1120 may be spaced apart from each other in the x direction or the −x direction. For example, a virtual straight line L connecting the side window glasses 1100 may extend in the x-direction or the −x-direction. For example, a virtual straight line L connecting the first side window glass 1110 and the second side window glass 1120 to each other may extend in the x direction or the −x direction.
The front window glass 1200 may be installed in front of the vehicle 1000. The front window glass 1200 may be arranged between the side window glasses 1100 facing each other.
The side mirror 1300 may provide a rear view of the vehicle 1000. The side mirror 1300 may be installed on the exterior of the body of the vehicle 1000. In an embodiment, multiple side mirrors 1300 may be provided. For example, one of the side mirrors 1300 may be arranged outside the first side window glass 1110, and another of the side mirrors 1300 may be arranged outside the second side window glass 1120.
The cluster 1400 may be arranged in front of the steering wheel. The cluster 1400 may include a tachometer, a speedometer, a coolant thermometer, a fuel gauge, a turn signal indicator, a high beam indicator, a warning light, a seat belt warning light, an odometer, a tachograph, an automatic shift selector indicator light, a door open warning light, an engine oil warning light, and/or a low fuel warning light.
The center fascia 1500 may include a control panel on which buttons for adjusting an audio device, an air conditioning device, and a seat heater are disposed. The center fascia 1500 may be arranged on a side of the cluster 1400.
A passenger seat dashboard 1600 may be spaced apart from the cluster 1400, and the center fascia 1500 may be arranged between the cluster 1400 and the passenger seat dashboard 1600. In an embodiment, the cluster 1400 may be arranged to correspond to a driver seat (not shown), and the passenger seat dashboard 1600 may be disposed to correspond to a passenger seat (not shown). In an embodiment, the cluster 1400 may be adjacent to the first side window glass 1110, and the passenger seat dashboard 1600 may be adjacent to the second side window glass 1120.
In an embodiment, the display device 2 may include a display panel 3, and the display panel 3 may display an image. The display device 2 may be arranged inside the vehicle 1000. In an embodiment, the display device 2 may be arranged between the side window glasses 1100 facing each other. The display device 2 may be arranged on at least one of the cluster 1400, the center fascia 1500, and the passenger seat dashboard 1600.
The display device 2 may include an organic light-emitting display device, an inorganic electroluminescent display device, a quantum dot display device, and the like. Hereinafter, an organic light-emitting display apparatus including the aforementioned organic light-emitting device will be described as an example of the display device 2. However, various types of the aforementioned display apparatus may be used in embodiments.
Referring to
Referring to
Referring to
Layers constituting the hole transport region, the emission layer, and the layers constituting the electron transport region may be formed in a selected region by using various methods such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) deposition, ink-jet printing, laser-printing, laser-induced thermal imaging, and the like.
When respective layers included in the hole transport region, the emission layer, and respective layers included in 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 in a range of about 10−8 torr to about 10−3 torr, and a deposition speed of about 0.01 Å/sec to about 100 Å/sec, depending on a material to be included in a layer to be formed and the structure of a layer to be formed.
The term “C3-C60 carbocyclic group” as used herein may be a cyclic group consisting of carbon atoms as the only ring-forming atoms and having three to sixty carbon atoms. The term “C1-C60 heterocyclic group” as used herein may be a cyclic group that has 1 to 60 carbon atoms and further has, in addition to a carbon atom, at least one heteroatom as a ring-forming atom. 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 condensed with each other. For example, the number of ring-forming atoms in a C1-C60 heterocyclic group may be from 3 to 61.
The term “cyclic group” as used herein may be a C3-C60 carbocyclic group or a C1-C60 heterocyclic group.
The term “π electron-rich C3-C60 cyclic group” as used herein may be a cyclic group that has three to sixty carbon atoms and may not include *—N═*′ as a ring-forming moiety. The term “π electron-deficient nitrogen-containing C1-C60 cyclic group” as used herein may be a heterocyclic group that has one to sixty carbon atoms and may include *—N═*′ as a ring-forming moiety.
In embodiments,
The terms “cyclic group”, “C3-C60 carbocyclic group”, “C1-C60 heterocyclic group”, “π electron-rich C3-C60 cyclic group”, and “π electron-deficient nitrogen-containing C1-C60 cyclic group” as used herein may each be a group condensed to any cyclic group, a monovalent group, or a polyvalent group (for example, a divalent group, a trivalent group, a tetravalent group, etc.) according to the structure of a formula for which the corresponding term is used. In an embodiment, a “benzene group” may be a benzo group, a phenyl group, a phenylene group, or the like, which may be readily understood by one of ordinary skill in the art according to the structure of a formula including the “benzene group.”
Examples of a monovalent C3-C60 carbocyclic group or a monovalent C1-C60 heterocyclic group may include 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 condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group. Examples of a divalent C3-C60 carbocyclic group or a divalent C1-C60 heterocyclic group may include a C3-C10 cycloalkylene group, a C1-C10 heterocycloalkylene group, a C3-C10 cycloalkenylene group, a C1-C1 heterocycloalkenylene group, a C6-C60 arylene group, a C1-C60 heteroarylene group, a divalent non-aromatic condensed polycyclic group, and a divalent non-aromatic condensed heteropolycyclic group.
The term “C1-C60 alkyl group” as used herein may be a linear or branched monovalent aliphatic hydrocarbon group that has 1 to 60 carbon atoms, and examples thereof may include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, and a tert-decyl group. The term “C1-C60 alkylene group” as used herein may be a divalent group having a same structure as the C1-C60 alkyl group.
The term “C2-C60 alkenyl group” as used herein may be a monovalent hydrocarbon group having at least one carbon-carbon double bond in the middle or at a terminus of a C2-C60 alkyl group, and examples thereof may include an ethenyl group, a propenyl group, a butenyl group, and the like. The term “C2-C60 alkenylene group” as used herein may be a divalent group having a same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein may be a monovalent hydrocarbon group having at least one carbon-carbon triple bond in the middle or at a terminus of a C2-C60 alkyl group, and examples thereof may include an ethynyl group, a propynyl group, and the like. The term “C2-C60 alkynylene group” as used herein may be a divalent group having a same structure as the C2-C60 alkynyl group.
The term “C1-C60 alkoxy group” as used herein may be a monovalent group represented by —O(A101) (wherein A101 may be a C1-C60 alkyl group), and examples thereof may include a methoxy group, an ethoxy group, an isopropyloxy group, and the like.
The term “C3-C10 cycloalkyl group” as used herein may be a monovalent saturated hydrocarbon cyclic group having 3 to 10 carbon atoms, and examples thereof may include 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, a bicyclo[2.2.2]octyl group, and the like. The term “C3-C10 cycloalkylene group” as used herein may be a divalent group having a same structure as the C3-C10 cycloalkyl group.
The term “C1-C1 heterocycloalkyl group” as used herein may be a monovalent cyclic group having 1 to 10 carbon atoms, further including, in addition to carbon atoms, at least one heteroatom as ring-forming atoms, and examples thereof may include a 1,2,3,4-oxatriazolidinyl group, a tetrahydrofuranyl group, a tetrahydrothiophenyl group, and the like. The term “C1-C1 heterocycloalkylene group” as used herein may be a divalent group having a same structure as the C1-C1 heterocycloalkyl group.
The term “C3-C10 cycloalkenyl group” as used herein may be a monovalent cyclic group having 3 to 10 carbon atoms, at least one carbon-carbon double bond in the cyclic structure thereof, and no aromaticity, and examples thereof may include a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and the like. The term “C3-C10 cycloalkenylene group” as used herein may be a divalent group having a same structure as the C3-C10 cycloalkenyl group.
The term “C1-C1a heterocycloalkenyl group” as used herein may be a monovalent cyclic group having 1 to 10 carbon atoms, further including, in addition to carbon atoms, at least one heteroatom as ring-forming atoms and at least one carbon-carbon double bond in the cyclic structure thereof. Examples of a C1-C1a heterocycloalkenyl group may include a 4,5-dihydro-1,2,3,4-oxatriazolyl group, a 2,3-dihydrofuranyl group, a 2,3-dihydrothiophenyl group, and the like. The term “C1-C1a heterocycloalkylene group” as used herein may be a divalent group having a same structure as the C1-C1a heterocycloalkyl group.
The term “C6-C60 aryl group” as used herein may be a monovalent group having a carbocyclic aromatic system of 6 to 60 carbon atoms, and the term “C6-C6a arylene group” as used herein may be a divalent group having a carbocyclic aromatic system of 6 to 60 carbon atoms. Examples of a C6-C60 aryl group may include a phenyl group, a pentalenyl group, a naphthyl group, an azulenyl group, an indacenyl group, an acenaphthyl group, a phenalenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a pentaphenyl group, a heptalenyl group, a naphthacenyl group, a picenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group, an ovalenyl group, and the like. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the respective two or more rings may be condensed with each other.
The term “C1-C60 heteroaryl group” as used herein may be a monovalent group having a heterocyclic aromatic system of 1 to 60 carbon atoms, further including, in addition to carbon atoms, at least one heteroatom as ring-forming atoms. The term “C1-C60 heteroarylene group” as used herein may be a divalent group having a heterocyclic aromatic system of 1 to 60 carbon atoms, further including, in addition to carbon atoms, at least one heteroatom as ring-forming atoms. Examples of a C1-C60 heteroaryl group may include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, a benzoquinolinyl group, an isoquinolinyl group, a benzoisoquinolinyl group, a quinoxalinyl group, a benzoquinoxalinyl group, a quinazolinyl group, a benzoquinazolinyl group, a cinnolinyl group, a phenanthrolinyl group, a phthalazinyl group, a naphthyridinyl group, and the like. When the C1-C60 heteroaryl group and the C1-C60 heteroarylene group each include two or more rings, the respective two or more rings may be condensed with each other.
The term “monovalent non-aromatic condensed polycyclic group” as used herein may be a monovalent group (for example, having 8 to 60 carbon atoms) having two or more rings condensed to each other, only carbon atoms as ring-forming atoms, and no aromaticity in the molecular structure as a whole. Examples of a monovalent non-aromatic condensed polycyclic group may include an indenyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, an indenophenanthrenyl group, an indeno anthracenyl group, and the like. The term “divalent non-aromatic condensed polycyclic group” as used herein may be a divalent group having a same structure as the monovalent non-aromatic condensed polycyclic group described above.
The term “monovalent non-aromatic condensed heteropolycyclic group” as used herein may be a monovalent group (for example, having 1 to 60 carbon atoms) having two or more rings condensed to each other, further including, in addition to carbon atoms, at least one heteroatom as ring-forming atoms, and having no aromaticity in its molecular structure as a whole. Examples of a monovalent non-aromatic condensed heteropolycyclic group may include a pyrrolyl group, a thiophenyl group, a furanyl group, an indolyl group, a benzoindolyl group, a naphthoindolyl group, an isoindolyl group, a benzoisoindolyl group, a naphthoisoindolyl group, a benzosilolyl group, a benzothiophenyl group, a benzofuranyl group, a carbazolyl group, a dibenzosilolyl group, a dibenzothiophenyl group, a dibenzofuranyl group, an azacarbazolyl group, an azafluorenyl group, an azadibenzosilolyl group, an azadibenzothiophenyl group, an azadibenzofuranyl group, a pyrazolyl group, an imidazolyl group, a triazolyl group, a tetrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzopyrazolyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a benzoxadiazolyl group, a benzothiadiazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an imidazotriazinyl group, an imidazopyrazinyl group, an imidazopyridazinyl group, an indeno carbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzosilolocarbazolyl group, a benzoindolocarbazolyl group, a benzocarbazolyl group, a benzonaphthofuranyl group, a benzonaphthothiophenyl group, a benzonaphthosilolyl group, a benzofurodibenzofuranyl group, a benzofurodibenzothiophenyl group, and a benzothienodibenzothiophenyl group. The term “divalent non-aromatic condensed heteropolycyclic group” as used herein may be a divalent group having a same structure as the monovalent non-aromatic condensed heteropolycyclic group.
The term “C6-C60 aryloxy group” as used herein may be a group represented by —O(A102) (wherein A102 may be a C6-C60 aryl group), and the term “C6-C60 arylthio group” as used herein may be a group represented by —S(A103) (wherein A103 may be a C6-C60 aryl group).
The term “C7-C60 arylalkyl group” as used herein may be a group represented by -(A104)(A105) (wherein A104 may be a C1-C54 alkylene group, and A105 may be a C6-C59 aryl group), and the term “C2-C60 heteroarylalkyl group” as used herein may be a group represented by -(A106)(A107) (wherein A106 may be a C1-C59 alkylene group, and A107 may be a C1-C59 heteroaryl group).
In the specification, the group “R10a” may be:
In the specification, 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; or a C3-C60 carbocyclic group, a C1-C60 heterocyclic group, a C7-C60 arylalkyl group, or a C2-C60 heteroarylalkyl 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.
The term “heteroatom” as used herein may be any atom other than a carbon atom or a hydrogen atom. Examples of a heteroatom may include O, S, N, P, Si, B, Ge, Se, and any combination thereof.
The term “Ph” as used herein refers to a phenyl group, the term “Me” as used herein refers to a methyl group, the term “Et” as used herein refers to an ethyl group, the terms “tert-Bu” or “But” as used herein each refer to a tert-butyl group, and the term “OMe” as used herein refers to a methoxy group.
The term “biphenyl group” as used herein may be a “phenyl group substituted with a phenyl group.” For example, a “biphenyl group” may be a substituted phenyl group having a C6-C60 aryl group as a substituent.
The term “terphenyl group” as used herein may be a “phenyl group substituted with a biphenyl group”. For example, a “terphenyl group” may be a substituted phenyl group having, as a substituent, a C6-C60 aryl group substituted with a C6-C60 aryl group.
In the specification, the terms “x-axis”, “y-axis”, and “z-axis” are not limited to three axes in an orthogonal coordinate system (for example, a Cartesian coordinate system), and may be interpreted in a broader sense that the aforementioned three axes in an orthogonal coordinate system. For example, the x-axis, y-axis, and z-axis may describe axes that are orthogonal to each other, or may describe axes that are in different directions that are not orthogonal to each other.
In the specification, the symbols * and *′ as used herein, unless defined otherwise, each refer to a binding site to a neighboring atom in a corresponding formula or moiety.
Hereinafter, a compound according to embodiments and an organic light-emitting device according to embodiments will be described in detail with reference to the Synthesis Examples and the 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.
5.6 g (18 mmol) of 5,6-diisobutyl-2-methoxy-9H-carbazole, 5.8 g (27 mmol) of 2-bromo-4(tert-butyl)pyridine, 8.3 g (36 mmol) of potassium phosphate tribasic, 0.66 g (3.6 mmol) of CuI, and 0.4 g (3.6 mmol) of picolinic acid were added to a reaction container, and suspended in 100 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C. and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 6.3 g (14.2 mmol) of the target compound.
6.3 g (14.2 mmol) of Intermediate [9-1] was suspended in an excess of bromic acid solution. The reaction mixture was heated to 110° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, and an appropriate amount of sodium bicarbonate was added thereto for neutralization. 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 4.8 g (11.3 mmol) of the target compound.
4.8 g (11.3 mmol) of Intermediate [9-2], 3.0 g (17.0 mmol) of 1-bromo-3-fluorobenzene, and 5.3 g (22.6 mmol) of potassium phosphate tribasic were added to a reaction container, and suspended in 110 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 12 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.1 g (8.7 mmol) of the target compound.
5.1 g (8.7 mmol) of Intermediate [9-3], 2.9 g (8.7 mmol) of N1-([1,1′: 3′,1″-terphenyl]-2′-nyl)benzene-1,2-diamine, SPhos (0.66 mmol), Pd2(dba)3 (0.44 mmol), and sodium t-butoxide (17.4 mmol) were suspended in 90 ml of toluene solvent, and stirred for 4 hours after raising the temperature to 110° C. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 6.4 g (7.6 mmol) of the target compound.
6.4 g (7.6 mmol) of Intermediate [9-4] was dissolved in 63 mmol of triethyl orthoformate, and 9.1 mmol of HCl was added dropwise thereto. The reaction mixture was heated to a temperature of 80° C., and stirred for 20 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 6.1 g (6.8 mmol) of the target compound.
6.1 g (6.8 mmol) of Intermediate [9-5], 3.1 g (7.5 mmol) of potassium tetrachloroplatinate, and 2.9 g (27.5 mmol) of 2,6-lutidine were suspended in 130 mL of 1,2-dichlorobenzene. The reaction mixture was heated to 120° C., and stirred for 18 hours. After completion of the reaction, the resulting product was cooled to room temperature, the solvent was removed therefrom, and the residue was separated by column chromatography to obtain 3.0 g (2.9 mmol) of the target compound.
6.6 g (18 mmol) of Intermediate [20-1], 5.8 g (27 mmol) of 2-bromo-4(tert-butyl)pyridine, 8.3 g (36 mmol) of potassium phosphate tribasic, 0.66 g (3.6 mmol) of CuI, and 0.4 g (3.6 mmol) of picolinic acid were added to a reaction container, and suspended in 100 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 6.9 g (13.7 mmol) of the target compound.
6.9 g (13.7 mmol) of Intermediate [20-2] was added to a reaction container, and suspended in 130 mL of dichloromethane. After stirring the reaction mixture at 0° C., boron tribromide was slowly added dropwise thereto. After raising the temperature to room temperature, the resulting mixture was stirred for 2 hours, 200 mL of distilled water was added thereto, and an extraction process was performed thereon by using dichloromethane. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 4.4 g (9.0 mmol) of the target compound.
4.4 g (9.0 mmol) of Intermediate [20-3], 3.7 g (13.5 mmol) of Intermediate [A-1], 4.2 g (18 mmol) of potassium phosphate tribasic, 0.33 g (0.18 mmol) of CuI, and 0.02 g (0.18 mmol) of picolinic acid were added to a reaction container, and suspended in 90 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 20 hours. After completion of the reaction, the reaction result was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 4.4 g (6.5 mmol) of the target compound.
4.4 g (6.5 mmol) of Intermediate [20-4], 5.7 g (9.8 mmol) of Intermediate [A-2], and 0.12 g (0.65 mmol) of Cu(OAc)2 were added to dimethyl sulfoxide, and the reaction mixture was stirred for 12 hours after raising the temperature to 150° C. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 4.6 g (4.5 mmol) of the target compound.
4.6 g (4.5 mmol) of Intermediate [20-5], 2.1 g (5.0 mmol) of potassium tetrachloroplatinate, and 1.9 g (18.2 mmol) of 2,6-lutidine were suspended in 90 mL of 1,2-dichlorobenzene. The reaction mixture was heated to 120° C., and stirred for 18 hours. After completion of the reaction, the resulting product was cooled to room temperature, the solvent was removed therefrom, and the residue was separated by column chromatography to obtain 1.9 g (1.8 mmol) of the target compound.
5.8 g (18 mmol) of Intermediate [31-1], 5.8 g (27 mmol) of 2-bromo-4(tert-butyl)pyridine, 8.3 g (36 mmol) of potassium phosphate tribasic, 0.66 g (3.6 mmol) of CuI, and 0.4 g (3.6 mmol) of picolinic acid were added to a reaction container, and suspended in 100 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 7.0 g (15.3 mmol) of the target compound.
7.0 g (15.3 mmol) of Intermediate [31-2] was suspended in an excess of bromic acid solution. The reaction mixture was heated to 110° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, and an appropriate amount of sodium bicarbonate was added thereto for neutralization. 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.2 g (11.8 mmol) of the target compound.
5.2 g (11.8 mmol) of Intermediate [31-3], 3.1 g (17.7 mmol) of 1-bromo-3-fluorobenzene, and 5.5 g (23.6 mmol) of potassium phosphate tribasic were added to a reaction container, and suspended in 120 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 12 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.3 g (8.9 mmol) of the target compound.
5.3 g (8.9 mmol) of Intermediate [31-4], 4.6 g (8.9 mmol) of Intermediate [A-3], SPhos (0.68 mmol), Pd2(dba)3 (0.45 mmol), and sodium t-butoxide (17.8 mmol) were suspended in 90 mL of toluene solvent, and stirred for 4 hours after raising the temperature to 110° C. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 8.2 g (8.0 mmol) of the target compound.
8.2 g (8.0 mmol) of Intermediate [31-5] was dissolved in 66 mmol of triethyl orthoformate, and 9.6 mmol of HCl was added dropwise thereto. The reaction mixture was heated to a temperature of 80° C., and stirred for 20 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 6.7 g (6.2 mmol) of the target compound.
6.7 g (6.2 mmol) of Intermediate [31-6], 2.8 g (6.8 mmol) of potassium tetrachloroplatinate, and 2.6 g (25.1 mmol) of 2,6-lutidine were suspended in 120 mL of 1,2-dichlorobenzene. The reaction mixture was heated to a temperature of 120° C. and stirred for 18 hours. After completion of the reaction, the resulting product was cooled to room temperature, the solvent was removed therefrom, and the residue was separated by column chromatography to obtain 3.2 g (2.6 mmol) of the target compound.
5.6 g (18 mmol) of 1,3-diisobutyl-7-methoxy-9H-carbazole, 5.8 g (27 mmol) of 2-bromo-4(tert-butyl)pyridine, 8.3 g (36 mmol) of potassium phosphate tribasic, 0.66 g (3.6 mmol) of CuI, and 0.4 g (3.6 mmol) of picolinic acid were added to a reaction container, and suspended in 100 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.4 g (12.3 mmol) of the target compound.
5.4 g (12.3 mmol) of Intermediate [43-1] was suspended in an excess of bromic acid solution. The reaction mixture was heated to 110° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, and an appropriate amount of sodium bicarbonate was added thereto for neutralization. 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 4.2 g (9.9 mmol) of the target compound.
4.2 g (9.9 mmol) of Intermediate [43-2], 2.9 g (14.9 mmol) of 1-bromo-3-fluorobenzene, and 4.6 g (19.8 mmol) of potassium phosphate tribasic were added to a reaction container, and suspended in 100 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 12 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 4.7 g (8.1 mmol) of the target compound.
4.7 g (8.1 mmol) of Intermediate [43-3], 2.7 g (8.1 mmol) of N1-([1,1′: 3′,1″-terphenyl]-2′-nyl)benzene-1,2-diamine, SPhos (0.61 mmol), Pd2(dba)3 (0.41 mmol), and sodium t-butoxide (16.2 mmol) were suspended in 80 mL of toluene solvent, and stirred for 4 hours after raising the temperature to 110° C. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with an aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 6.0 g (7.1 mmol) of the target compound.
6.0 g (7.1 mmol) of Intermediate [43-4] was dissolved in 60 mmol of triethyl orthoformate, and 8.5 mmol of HCl was added dropwise thereto. The reaction mixture was heated to a temperature of 80° C., and stirred for 20 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.0 g (5.7 mmol) of the target compound.
5.0 g (5.7 mmol) of Intermediate [43-5], 2.6 g (6.3 mmol) of potassium tetrachloroplatinate, and 2.4 g (23.0 mmol) of 2,6-lutidine were suspended in 120 mL of 1,2-dichlorobenzene. The reaction mixture was heated to 120° C., and stirred for 18 hours. After completion of the reaction, the resulting product was cooled to room temperature, the solvent was removed therefrom, and the residue was separated by column chromatography to obtain 2.3 g (2.2 mmol) of the target compound.
6.3 g (18 mmol) of Intermediate [65-1], 5.8 g (27 mmol) of 2-bromo-4(tert-butyl)pyridine, 8.3 g (36 mmol) of potassium phosphate tribasic, 0.66 g (3.6 mmol) of CuI, and 0.4 g (3.6 mmol) of picolinic acid were added to a reaction container, and suspended in 100 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 7.1 g (14.7 mmol) of the target compound.
7.1 g (14.7 mmol) of Intermediate [65-2] was suspended in an excess of bromic acid solution. The reaction mixture was heated to 110° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, and an appropriate amount of sodium bicarbonate was added thereto for neutralization. 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.2 g (11.1 mmol) of the target compound.
5.2 g (11.1 mmol) of Intermediate [65-3], 2.9 g (16.7 mmol) of 1-bromo-3-fluorobenzene, and 5.2 g (22.2 mmol) of potassium phosphate tribasic were added to a reaction container, and suspended in 110 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 12 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.1 g (8.2 mmol) of the target compound.
5.1 g (8.2 mmol) of Intermediate [65-4], 4.2 g (8.2 mmol) of Intermediate [A-5], SPhos (0.63 mmol), Pd2(dba)3 (0.41 mmol), and sodium t-butoxide (16.4 mmol) were suspended in 80 mL of toluene solvent, and stirred for 4 hours after raising the temperature to 110° C. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 7.2 g (7.2 mmol) of the target compound.
7.2 g (7.2 mmol) of Intermediate [65-5] was dissolved in 60 mmol of triethyl orthoformate, and 8.6 mmol of HCl was added dropwise thereto. The reaction mixture was heated to a temperature of 80° C., and stirred for 20 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 6.6 g (6.3 mmol) of the target compound.
6.6 g (6.3 mmol) of Intermediate [65-6], 2.8 g (6.8 mmol) of potassium tetrachloroplatinate, and 2.6 g (25.5 mmol) of 2,6-lutidine were suspended in 120 mL of 1,2-dichlorobenzene. The reaction mixture was heated to a temperature of 120° C. and stirred for 18 hours. After completion of the reaction, the resulting product was cooled to room temperature, the solvent was removed therefrom, and the residue was separated by column chromatography to obtain 3.6 g (3.0 mmol) of the target compound.
5.6 g (18 mmol) of Intermediate [75-1], 5.8 g (27 mmol) of 2-bromo-4(tert-butyl)pyridine, 8.3 g (36 mmol) of potassium phosphate tribasic, 0.66 g (3.6 mmol) of CuI, and 0.4 g (3.6 mmol) of picolinic acid were added to a reaction container, and suspended in 100 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 6.3 g (14.1 mmol) of the target compound.
6.3 g (14.1 mmol) of Intermediate [75-2] was added to a reaction container, and suspended in 140 mL of dichloromethane. After stirring the reaction mixture at 0° C., boron tribromide was slowly added dropwise thereto. After raising the temperature to room temperature, the resulting mixture was stirred for 2 hours, 200 mL of distilled water was added thereto, and an extraction process was performed thereon by using dichloromethane. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 4.9 g (11.3 mmol) of the target compound.
4.9 g (11. mmol) of Intermediate [75-3], 3.0 g (17.0 mmol) of 1-bromo-3-fluorobenzene, and 5.3 g (22.6 mmol) of potassium phosphate tribasic were added to a reaction container, and suspended in 110 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 12 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.0 g (8.5 mmol) of the target compound.
5.0 g (8.5 mmol) of Intermediate [75-4], 2.8 g (8.5 mmol) of N1-([1,1′: 3′,1″-terphenyl]-2′-nyl)benzene-1,2-diamine, SPhos (0.64 mmol), Pd2(dba)3 (0.43 mmol), and sodium t-butoxide (17.0 mmol) were suspended in 90 ml of toluene solvent, and stirred for 4 hours after raising the temperature to 110° C. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 6.1 g (7.2 mmol) of the target compound.
6.1 g (7.2 mmol) of Intermediate [75-5] was dissolved in 60 mmol of triethyl orthoformate, and 8.6 mmol of HCl was added dropwise thereto. The reaction mixture was heated to a temperature of 80° C., and stirred for 20 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.6 g (6.3 mmol) of the target compound.
5.6 g (6.3 mmol) of Intermediate [75-6], 2.9 g (6.9 mmol) of potassium tetrachloroplatinate, and 2.7 g (25.4 mmol) of 2,6-lutidine were suspended in 120 mL of 1,2-dichlorobenzene. The reaction mixture was heated to 120° C., and stirred for 18 hours. After completion of the reaction, the resulting product was cooled to room temperature, the solvent was removed therefrom, and the residue was separated by column chromatography to obtain 2.7 g (2.6 mmol) of the target compound.
5.6 g (18 mmol) of Intermediate [85-1], 5.8 g (27 mmol) of 2-bromo-4(tert-butyl) pyridine, 8.3 g (36 mmol) of potassium phosphate tribasic, 0.66 g (3.6 mmol) of CuI, and 0.4 g (3.6 mmol) of picolinic acid were added to a reaction container, and suspended in 100 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 6.4 g (14.5 mmol) of the target compound.
6.4 g (14.5 mmol) of Intermediate [85-2] was suspended in an excess of bromic acid solution. The reaction mixture was heated to 110° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, and an appropriate amount of sodium bicarbonate was added thereto for neutralization. 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.0 g (11.7 mmol) of the target compound.
5.0 g (11.7 mmol) of Intermediate [85-3], 3.1 g (17.6 mmol) of 1-bromo-3-fluorobenzene, and 5.5 g (23.4 mmol) of potassium phosphate tribasic were added to a reaction container, and suspended in 120 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 12 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.3 g (9.1 mmol) of the target compound.
5.3 g (9.1 mmol) of Intermediate [85-4], 3.7 g (9.1 mmol) of Intermediate [A-6], SPhos (0.68 mmol), Pd2(dba)3 (0.46 mmol), and sodium t-butoxide (18.2 mmol) were suspended in 90 mL of toluene solvent, and stirred for 4 hours after raising the temperature to 110° C. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 7.1 g (7.8 mmol) of the target compound.
7.1 g (7.8 mmol) of Intermediate [85-5] was dissolved in 62 mmol of triethyl orthoformate, and 8.8 mmol of HCl was added dropwise thereto. The reaction mixture was heated to a temperature of 80° C., and stirred for 20 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 6.7 g (7.0 mmol) of the target compound.
6.7 g (7.0 mmol) of Intermediate [85-6], 3.2 g (7.7 mmol) of potassium tetrachloroplatinate, and 3.0 g (28.2 mmol) of 2,6-lutidine were suspended in 140 mL of 1,2-dichlorobenzene. The reaction mixture was heated to a temperature of 120° C. and stirred for 18 hours. After completion of the reaction, the resulting product was cooled to room temperature, the solvent was removed therefrom, and the residue was separated by column chromatography to obtain 3.2 g (2.9 mmol) of the target compound.
5.1 g (18 mmol) of 7-methoxy-1,3-dipropyl-9H-carbazole, 5.8 g (27 mmol) of 2-bromo-4(tert-butyl)pyridine, 8.3 g (36 mmol) of potassium phosphate tribasic, 0.66 g (3.6 mmol) of CuI, and 0.4 g (3.6 mmol) of picolinic acid were added to a reaction container, and suspended in 100 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 4.6 g (11.1 mmol) of the target compound.
4.6 g (11.1 mmol) of Intermediate [88-1] was suspended in an excess of bromic acid solution. The reaction mixture was heated to 110° C., and stirred for 24 hours. After completion of the reaction, the resulting product was cooled at room temperature, and an appropriate amount of sodium bicarbonate was added thereto for neutralization. 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 3.6 g (9.1 mmol) of the target compound.
3.6 g (9.1 mmol) of Intermediate [88-2], 2.7 g (13.7 mmol) of 1-bromo-3-fluorobenzene, and 4.2 g (18.2 mmol) of potassium phosphate tribasic were added to a reaction container, and suspended in 90 mL of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C., and stirred for 12 hours. After completion of the reaction, the resulting product was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 4.1 g (7.4 mmol) of the target compound.
4.1 g (7.4 mmol) of Intermediate [88-3], 2.6 g (7.4 mmol) of Intermediate [A-7], SPhos (0.56 mmol), Pd2(dba)3 (0.37 mmol), and sodium t-butoxide (14.8 mmol) were suspended in 75 mL of toluene solvent, and stirred for 4 hours after raising the temperature to 110° C. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with an aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.3 g (6.4 mmol) of the target compound.
5.3 g (6.4 mmol) of Intermediate [88-4] was dissolved in 54 mmol of triethyl orthoformate, and 7.7 mmol of HCl was added dropwise thereto. The reaction mixture was heated to a temperature of 80° C., and stirred for 20 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried by using sodium sulfate. The residue from which the solvent was removed was separated by column chromatography to obtain 5.0 g (5.8 mmol) of the target compound.
5.0 g (5.8 mmol) of Intermediate [88-5], 2.6 g (6.2 mmol) of potassium tetrachloroplatinate, and 2.4 g (22.6 mmol) of 2,6-lutidine were suspended in 120 mL of 1,2-dichlorobenzene. The reaction mixture was heated to 120° C., and stirred for 18 hours. After completion of the reaction, the resulting product was cooled to room temperature, the solvent was removed therefrom, and the residue was separated by column chromatography to obtain 2.2 g (2.1 mmol) of the target compound.
As an anode, a glass substrate (product of Corning Inc.) with a 15 Ω/cm2 (1,200 Å) ITO formed thereon was cut to a size of 50 mm×50 mm×0.7 mm, sonicated by using isopropyl alcohol and pure water each for 5 minutes, washed by irradiation of ultraviolet rays and exposure of ozone thereto for 30 minutes, and mounted on a vacuum deposition apparatus.
2-TNATA was vacuum-deposited on the anode to form a hole injection layer having a thickness of 600 Å, and 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter, referred as “NPB”) was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 300 Å.
Compound ETH2 (second compound), Compound HTH29 (third compound), and Compound 9 (dopant, first compound) were vacuum-deposited on the hole transport layer to form an emission layer having a thickness of 400 Å. Here, the amount of Compound 1 was 13 wt % per a total weight (100 wt %) of the emission layer, and the weight ratio of Compound ETH2 to Compound HTH29 was adjusted to 3:7.
Compound ETH2 was vacuum-deposited on the emission layer to form a hole blocking layer having a thickness of 50 Å, and Compound ET46 and LiQ were vacuum-deposited on the hole blocking layer at a weight ratio of 4:6 to form an electron transport layer having a thickness of 300 Å. Yb was vacuum-deposited on the electron transport layer to form an electron injection layer having a thickness of 15 Å, and Mg was vacuum-deposited thereon to form a cathode having a thickness of 800 Å, thereby completing manufacture of an organic light-emitting device.
Organic light-emitting devices were manufactured in the same manner as in Example 1, except that compounds shown in Table 2 were each used as a dopant in forming an emission layer.
For Compounds 9, 20, 31, 43, 65, 75, 85, and 88 and Compounds A, B, C, and D for comparison, HOMO energy level (eV), LUMO energy level (eV), actual maximum emission wavelength (Δmaxexp), and existence ratio (%) of triplet metal-to-ligand charge transfer state (3MLCT) were evaluated by using a DFT method of the Gaussian09 program having the structural optimization at B3LYP/6-311g(d,p)/LANL2DZ level, and the results are shown in Table 1.
3MLCT [%]
Referring to the results of Table 1, it was confirmed that the compounds of the Examples emitted blue light in a short wavelength region compared to the compounds of the Comparative Examples. It was also confirmed that, compared to the compounds of the Comparative Examples, the compounds of the Examples had a higher 3MLCT percentage leading to relatively high luminescence efficiency.
Table 2 shows results of evaluating the organic light-emitting devices of the Examples and Comparative Examples. For the organic light-emitting devices of the Examples and Comparative Examples, driving voltage (V) at luminance of 1,000 cd/cm2, color purity (CIEx,y), luminescence efficiency (cd/A), color conversion efficiency (cd/A/y), maximum emission wavelength (nm), and lifespan (T95) were each measured by using Keithley MU 236 and a luminance meter PR650, and the results are shown in Table 2. Lifespan (T95) is a measure of the time (hr) taken for the luminance to reach 95% of the initial luminance.
Referring to Table 2, it was confirmed that the organic light-emitting devices of Examples 1 to 8 had low driving voltage, equivalent or high luminescence efficiency, high color conversion efficiency, and long lifespan, compared to the organic light-emitting devices of Comparative Examples 1 to 4.
According to the embodiments, an organometallic compound represented by Formula 1 may have excellent heat resistance stability and may be able to emit blue light with high efficiency and high color purity. An organic light-emitting device including the organometallic compound may then have low driving voltage, high luminescence efficiency, high color conversion efficiency, and long lifespan. In this regard, an electronic apparatus including the organic light-emitting device and electronic equipment including the electronic apparatus may have improved display quality.
Embodiments have been disclosed herein, and although terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for the purposes of limitation. In some instances, as would be apparent by one of ordinary skill in the art, features, characteristics, and/or elements described in connection with an embodiment may be used singly or in combination with features, characteristics, and/or elements described in connection with other embodiments unless otherwise specifically indicated. Accordingly, it will be understood by those of ordinary skill in the art that various changes in form and details may be made without departing from the spirit and scope of the disclosure as set forth in the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2023-0145425 | Oct 2023 | KR | national |
