Patent Application
20240334810
This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0038973, filed on Mar. 24, 2023, and Korean Patent Application No. 10-2023-0053528, filed on Apr. 24, 2023, in the Korean Intellectual Property Office, the content of each of which is incorporated by reference herein in its entirety.
One or more embodiments of the present disclosure relate to a light-emitting device including an organometallic compound, an electronic apparatus including the light-emitting device, and the organometallic compound.
Among light-emitting devices, self-emissive devices (e.g., organic light-emitting devices) have relatively wide viewing angles, high contrast ratios, short response times, and excellent or suitable characteristics in terms of luminance, driving voltage, and response speed.
In a light-emitting device, 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 arranged 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 the holes and electrons, recombine in the emission layer to produce excitons. These excitons transition (e.g., relax) from an excited state to a ground state to thereby generate light.
One or more aspects of embodiments of the present disclosure are directed toward a light-emitting device including an organometallic compound, an electronic apparatus including the light-emitting device, and the organometallic compound.
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 presented embodiments of the disclosure.
According to one or more embodiments of the present disclosure, a light-emitting device includes:
According to one or more embodiments of the present disclosure, an electronic apparatus includes the light-emitting device.
According to one or more embodiments of the present disclosure, electronic equipment includes the light-emitting device.
According to one or more embodiments of the present disclosure, provided is the organometallic compound represented by Formula 1.
The accompanying drawings are included to provide a further understanding of the present disclosure and are incorporated in and constitute a part of the present disclosure. The drawings illustrate embodiments of the present disclosure and, together with the description, serve to explain principles of the present disclosure. The above and other aspects, features, and advantages of certain embodiments of the disclosure will be more apparent from the following description taken in conjunction with the accompanying drawings, in which:
Reference will now be made in more detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout the present disclosure, and duplicative descriptions thereof may not be provided for conciseness. In this regard, the embodiments of the present disclosure may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments of the present disclosure are merely described, by referring to the drawings, to explain aspects of the present disclosure. As utilized herein, the term “and/or” or “or” may include any and all combinations of one or more of the associated listed items. Throughout the disclosure, the expressions such as “at least one of,” “one of,” and “selected from,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list. For example, “at least one of a, b or c”, “at least one selected from a, b, and c”, “at least one selected from among a to c”, etc., may indicate only a, only b, only c, both (e.g., simultaneously) a and b, both (e.g., simultaneously) a and c, both (e.g., simultaneously) b and c, all of a, b, and c, or variations thereof. The “/” utilized herein may be interpreted as “and” or as “or” depending on the situation.
According to one or more embodiments of the present disclosure, a light-emitting device may include:
Details on Formula 1 may be the same as described elsewhere herein.
In one or more embodiments,
In one or more embodiments, the interlayer of the light-emitting device may include the organometallic compound represented by Formula 1.
In one or more embodiments, the emission layer of the light-emitting device may include the organometallic compound represented by Formula 1 (e.g., as a first compound).
In one or more embodiments, the emission layer of the light-emitting device may include a dopant and a host, and the organometallic compound represented by Formula 1 may be included in the dopant. For example, in some embodiments, the organometallic compound may act as a dopant. For example, in some embodiments, the emission layer may be to emit blue light. The blue light may have a maximum emission wavelength in a range of, for example, about 430 nm to about 480 nm.
In one or more embodiments, the electron transport region of the light-emitting device may include a hole blocking layer, and the hole blocking layer may include a phosphine oxide-containing compound, a silicon-containing compound, or any combination thereof. For example, in one or more embodiments, the hole blocking layer may directly contact the emission layer.
In one or more embodiments, the light-emitting device may further include a second compound including at least one π electron-deficient nitrogen-containing C1-C60 heterocyclic group, a third compound including a group represented by Formula 3, a fourth compound capable of emitting delayed fluorescence, or any combination thereof, and
In Formula 3,
In one or more embodiments, the organometallic compound may include at least one deuterium.
In one or more embodiments, the second compound, the third compound, and the fourth compound may each include at least one deuterium.
In one or more embodiments, the second compound may include at least one silicon.
In one or more embodiments, the third compound may include at least one silicon.
In one or more embodiments, the light-emitting device may further include a second compound and a third compound, in addition to the organometallic compound represented by Formula 1, and at least one selected from among the second compound and the third compound may include at least one deuterium, at least one silicon, or a combination thereof.
In one or more embodiments, the light-emitting device (e.g., the emission layer in the light-emitting device) may further include a second compound, in addition to the organometallic compound. At least one selected from among the organometallic compound and the second compound may include at least one deuterium. For example, in some embodiments, the light-emitting device (e.g., the emission layer in the light-emitting device) may further include a third compound, a fourth compound, or any combination thereof, in addition to the organometallic compound and the second compound.
In one or more embodiments, the light-emitting device (e.g., the emission layer in the light-emitting device) may further include a third compound, in addition to the organometallic compound. At least one selected from among the organometallic compound and the third compound may include at least one deuterium. For example, in some embodiments, the light-emitting device (e.g., the emission layer in the light-emitting device) may further include a second compound, a fourth compound, or any combination thereof, in addition to the organometallic compound and the third compound.
In one or more embodiments, the light-emitting device (e.g., the emission layer in the light-emitting device) may further include a fourth compound, in addition to the organometallic compound. At least one selected from among the organometallic compound and the fourth compound may include at least one deuterium. The fourth compound may serve to improve color purity, luminescence efficiency, and lifespan characteristics of the light-emitting device. For example, in some embodiments, the light-emitting device (e.g., the emission layer in the light-emitting device) may further include a second compound, a third compound, or any combination thereof, in addition to the organometallic compound and the fourth compound.
In one or more embodiments, the light-emitting device (e.g., the emission layer in the light-emitting device) may further include a second compound and a third compound, in addition to the organometallic compound. The second compound and the third compound may form an exciplex. At least one selected from among the organometallic compound, the second compound, and the third compound may include at least one deuterium.
In one or more embodiments, the emission layer of the light-emitting device may include: i) the organometallic compound; and ii) the second compound, the third compound, the fourth compound, or any combination thereof, and the emission layer may be to emit blue light.
In one or more embodiments, the blue light may have a maximum emission wavelength in a range of about 430 nm to about 480 nm, about 430 nm to about 475 nm, about 440 nm to about 475 nm, about 450 nm to about 475 nm, about 430 nm to about 470 nm, about 440 nm to about 470 nm, about 450 nm to about 470 nm, about 430 nm to about 465 nm, about 440 nm to about 465 nm, about 450 nm to about 465 nm, about 430 nm to about 460 nm, about 440 nm to about 460 nm, or about 450 nm to about 460 nm.
In one or more embodiments, the second compound may include a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, or any combination thereof.
In one or more embodiments, the following compounds may be excluded from the third compound:
In one or more embodiments, a difference between a triplet energy level (eV) of the fourth compound and a singlet energy level (eV) of the fourth compound may be greater than or equal to 0 eV and less than or equal to 0.5 eV (or, greater than or equal to 0 eV and less than or equal to 0.3 eV).
In one or more embodiments, the fourth compound may be a compound including at least one cyclic group including boron (B) and nitrogen (N) as ring-forming atoms.
In one or more embodiments, the fourth compound may be a C8-C60 polycyclic group-containing compound including at least two condensed cyclic groups that share B (e.g., one being a first ring and another being a second ring).
In one or more embodiments, the fourth compound may include a condensed ring in which at least one third ring is condensed with at least one fourth ring, for example, to form the condensed ring including four or more rings,
In one or more embodiments, the third compound may not include (e.g., may exclude) a (e.g., any) compound represented by Formula 3-1 described herein.
In one or more embodiments, the second compound may include a compound represented by Formula 2:
In Formula 2,
In one or more embodiments, the third compound may include a compound represented by Formula 3-1, a compound represented by Formula 3-2, a compound represented by Formula 3-3, a compound represented by Formula 3-4, a compound represented by Formula 3-5, or any combination thereof:
In Formulae 3-1 to 3-5,
In one or more embodiments, the fourth compound may include a compound represented by Formula 502, a compound represented by Formula 503, or any combination thereof:
In Formulae 502 and 503,
In one or more embodiments, the light-emitting device may satisfy at least one selected from among Conditions 1 to 4:
lowest unoccupied molecular orbital (LUMO) energy level (eV) of third compound>LUMO energy level (eV) of organometallic compound
LUMO energy level (eV) of organometallic compound>LUMO energy level (eV) of second compound
highest occupied molecular orbital (HOMO) energy level (eV) of organometallic compound>HOMO energy level (eV) of third compound
HOMO energy level (eV) of third compound>HOMO energy level (eV) of second compound.
Each of the HOMO energy level and LUMO energy level of each of the organometallic compound, the second compound, and the third compound may be a negative value, and may be measured according to a suitable method.
In one or more embodiments, an absolute value of a difference between the LUMO energy level of the organometallic compound and the LUMO energy level of the second compound may be greater than or equal to about 0.1 eV and less than or equal to about 1.0 eV or an absolute value of a difference between the LUMO energy level of the organometallic compound and the LUMO energy level of the third compound may be greater than or equal to about 0.1 eV and less than or equal to about 1.0 eV, and an absolute value of a difference between the HOMO energy level of the organometallic compound and the HOMO energy level of the second compound may be less than or equal to about 1.25 eV (e.g., less than or equal to about 1.25 eV and greater than or equal to about 0.2 eV) or an absolute value of a difference between the HOMO energy level of the organometallic compound and the HOMO energy level of the third compound may be less than or equal to about 1.25 eV (e.g., less than or equal to about 1.25 eV and greater than or equal to about 0.2 eV).
When the relationships between the LUMO energy level and the HOMO energy level satisfy the conditions described above, a balance between holes and electrons injected into the emission layer may be obtained.
The light-emitting device may have a structure of a first embodiment or a second embodiment.
According to the first embodiment, the organometallic compound may be included in the emission layer in the interlayer of the light-emitting device, wherein the emission layer may further include a host, the organometallic compound may be different from the host, and the emission layer may be to emit phosphorescence or fluorescence emitted from the organometallic compound. For example, according to the first embodiment, the organometallic compound may be a dopant or an emitter. For example, in one or more embodiments, the organometallic compound may be a phosphorescent dopant or a phosphorescent emitter.
Phosphorescence or fluorescence emitted from the organometallic compound may be blue light.
In one or more embodiments, The emission layer may further include an auxiliary dopant. The auxiliary dopant may serve to improve luminescence efficiency of the organometallic compound by effectively transferring energy to the organometallic compound as a dopant or an emitter.
The auxiliary dopant may be different from the organometallic compound and the host.
In one or more embodiments, the auxiliary dopant may be a delayed fluorescence-emitting compound.
In one or more embodiments, the auxiliary dopant may be a compound including at least one cyclic group including boron (B) and nitrogen (N) as ring-forming atoms.
According to the second embodiment, the organometallic compound may be included in the emission layer in the interlayer of the light-emitting device, wherein the emission layer may further include a host and a dopant, the organometallic compound, the host, and the dopant may be different from one another, and the emission layer may be to emit phosphorescence or fluorescence (e.g., delayed fluorescence) emitted from the dopant.
In one or more embodiments, the organometallic compound in the second embodiment may serve not as a dopant, but as an auxiliary dopant that transfers energy to a dopant (or an emitter).
In one or more embodiments, the organometallic compound in the second embodiment may serve as an emitter and also as an auxiliary dopant that transfers energy to a dopant (or an emitter).
In one or more embodiments, phosphorescence or fluorescence emitted from the dopant (or the emitter) in the second embodiment may be blue phosphorescence or blue fluorescence (e.g., blue delayed fluorescence).
The dopant (or the emitter) in the second embodiment may be a phosphorescent dopant material (e.g., the organometallic compound represented by Formula 1, an organometallic compound represented by Formula 401, or any combination thereof) or any fluorescent dopant material (e.g., a compound represented by Formula 501, a compound represented by Formula 502, a compound represented by Formula 503, or any combination thereof).
The blue light in the first embodiment and the second embodiment may be blue light having a maximum emission wavelength in a range of about 390 nm to about 500 nm, about 410 nm to about 490 nm, about 430 nm to about 480 nm, about 440 nm to about 475 nm, or about 455 nm to about 470 nm.
The auxiliary dopant in the first embodiment may include, for example, the fourth compound represented by Formula 502 or Formula 503.
The host in the first embodiment and the second embodiment may be any host material (e.g., a compound represented by Formula 301, a compound represented by 301-1, a compound represented by Formula 301-2, or any combination thereof).
In one or more embodiments, the host in the first embodiment and the second embodiment may be the second compound, the third compound, or any combination thereof.
In one or more embodiments, the light-emitting device may further include a capping layer arranged outside (e.g., on) the first electrode and/or outside (e.g., on) the second electrode.
In one or more embodiments, the light-emitting device may further include at least one of a first capping layer arranged outside (e.g., on) the first electrode or a second capping layer arranged outside (e.g., on) the second electrode, and the organometallic compound represented by Formula 1 may be included in at least one of the first capping layer or the second capping layer. More details on the first capping layer and/or second capping layer may be the same as described herein.
In one or more embodiments, the light-emitting device may include:
The expression “(interlayer and/or capping layer) includes the organometallic compound represented by Formula 1” as utilized herein may be understood as “(interlayer and/or capping layer) may include one kind or type of organometallic compound represented by Formula 1 or two different kinds or types of organometallic compounds, each represented by Formula 1.”
In one or more embodiments, the interlayer and/or the capping layer may include Compound 1 only as the organometallic compound. In this regard, Compound 1 may be present in the emission layer of the light-emitting device. In one or more embodiments, the interlayer may include, as the organometallic compound, Compound 1 and Compound 2. In this regard, Compound 1 and Compound 2 may be present in substantially the same layer (e.g., both (e.g., simultaneously) Compound 1 and Compound 2 may be present in the emission layer), or may be present in different layers (e.g., Compound 1 may be present in the emission layer, and Compound 2 may be present in the electron transport region).
The term “interlayer” as utilized herein refers to a single layer and/or all of a plurality of layers between the first electrode and the second electrode of the light-emitting device.
According to one or more embodiments of the present disclosure, an electronic apparatus may include the light-emitting device. In one or more embodiments, the electronic apparatus may further include a thin-film transistor. For example, in some embodiments, the electronic apparatus may further include a thin-film transistor including a source electrode and a drain electrode, wherein the first electrode of the light-emitting device may be electrically connected to the source electrode or the drain electrode of the thin-film transistor. In some embodiments, the electronic apparatus may further include a color filter, a color conversion layer, a touch screen layer, a polarizing layer, or any combination thereof. More details on the electronic apparatus may be the same as described herein.
According to one or more embodiments of the present disclosure, electronic equipment may include the light-emitting device.
For example, the electronic equipment may be at least one of a flat panel display, a curved display, a computer monitor, a medical monitor, a television, a billboard, an indoor or outdoor light and/or light for signal, a head-up display, a fully or 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 or augmented reality display, a vehicle, a video wall with multiple displays tiled together, a theater or stadium screen, a phototherapy device, or a signboard.
According to one or more embodiments of the present disclosure, provided is the organometallic compound represented by Formula 1. Details on Formula 1 may be the same as described herein.
Synthesis methods of the organometallic compound may be recognizable by one of ordinary skill in the art by referring to Synthesis Examples and/or Examples provided.
In Formula 1, M may be platinum (Pt), palladium (Pd), copper (Cu), silver (Ag), gold (Au), rhodium (Rh), ruthenium (Ru), osmium (Os), titanium (Ti), zirconium (Zr), hafnium (Hf), europium (Eu), terbium (Tb), or thulium (Tm).
In one or more embodiments, M may be platinum (Pt) or palladium (Pd).
In Formula 1, X1 may be carbon (C) of a carbene moiety.
In Formula 1, X12 may be C(R12) or N, and X13 may be C(R13) or N.
R12 and R13 may each be the same as described herein.
In Formula 1, X2 to X4 may each independently be C or N.
In one or more embodiments, X2 and X3 may each be C, and X4 may be N.
In one or more embodiments, i) a bond between X1 and M may be a coordinate bond, ii) one selected from a bond between X2 and M, a bond between X3 and M, and a bond between X4 and M may be a coordinate bond, and the other two may each be a covalent bond.
In one or more embodiments, a bond between X1 and M and a bond between X4 and M may each be a coordinate bond, and a bond between X2 and M and a bond between X3 and M may each be a covalent bond.
In Formula 1, ring CY2, ring CY31, ring CY32, and ring CY4 may each independently be a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
In one or more embodiments, ring CY2, ring CY31, ring CY32, and ring CY4 may each independently be:
In one or more embodiments, ring CY2 may be a benzene group, a pyridine group, a pyrimidine group, a naphthalene group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a fluorene group, or a dibenzosilole group.
In one or more embodiments, ring CY31 and ring CY32 may each independently be a benzene group, a pyridine group, a pyrimidine group, a naphthalene group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a fluorene group, or a dibenzosilole group.
In one or more embodiments, ring CY4 may be a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, a benzopyrazole group, a benzimidazole group, or a benzothiazole group.
In Formula 1, L1 to L3 may each independently be a single bond, *—C(R1a)(R1b)—*′, *—C(R1a)═*′, *═C(R1a)→*′, *—C(R1a)═C(R1b)—*′, *—C(═O)→*′, *—C(═S)→*′, *—C≡C—*′, *—B(Ria)→*′, *—N(R1a)→*′, *—O—*′, *—P(R1a)→*′, *—Al(R1a)→*, *—Si(R1a)(R1b)—*′, *—P(═O)(R1a)→*′, *—S*′, *—Se*′, *—S(═O)*′, *—S(═O)2—*′, or *—Ge(R1a)(R1b)*′, wherein * and *′ each indicate a binding site to a neighboring atom.
In Formula 1, R1a and R1b may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkenyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkynyl group unsubstituted or substituted with at least one R10a, a C1-C60 alkoxy group unsubstituted or substituted with at least one R10a, a C1-C60 alkylthio group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, a C6-C60 aryloxy group unsubstituted or substituted with at least one R10a, a C6-C60 arylthio group unsubstituted or substituted with at least one R10a, —C(Q1)(Q2)(Q3), —Si(Q1)(Q2)(Q3), —N(Q1)(Q2), —B(Q1)(Q2), —C(═O)(Q1), —S(═O)2(Q1), or —P(═O)(Q1)(Q2).
R10a and Q1 to Q3 may each be the same as described herein.
In Formula 1, n1 to n3 indicate the number of L1 to the number of L3, respectively, and may each independently be an integer from 1 to 5. When n1 is 2 or more, two or more of L1(s) may be identical to or different from each other, when n2 is 2 or more, two or more of L2(s) may be identical to or different from each other, and when n3 is 2 or more, two or more of L3(s) may be identical to or different from each other.
In one or more embodiments, L1 and L3 may each be a single bond.
In one or more embodiments, L2 may be *—O—*′ or *—S—*′, and n2 may be 1.
In one or more embodiments, R1a and R1b may each independently be:
In Formula 1, T1 may be *—Si(Z1)(Z2)→*′ or *—Ge(Z1)(Z2)→*′, wherein * and *′ each indicate a binding site to a neighboring atom.
In Formula 1, Z1 and Z2 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkenyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkynyl group unsubstituted or substituted with at least one R10a, a C1-C60 alkoxy group unsubstituted or substituted with at least one R10a, a C1-C60 alkylthio group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, a C6-C60 aryloxy group unsubstituted or substituted with at least one R10a, a C6-C60 arylthio group unsubstituted or substituted with at least one R10a, —C(Q1)(Q2)(Q3), —Si(Q1)(Q2)(Q3), —N(Q1)(Q2), —B(Q1)(Q2), —C(═O)(Q1), —S(═O)2(Q1), or —P(═O)(Q1)(Q2).
R10a and Q1 to Q3 may each be the same as described herein.
In one or more embodiments, Z1 and Z2 may each independently be:
Q1 to Q3 and Q31 to Q33 may each be the same as described herein.
In one or more embodiments, Z1 and Z2 may each independently be:
In one or more embodiments, Z1 and Z2 may each independently be:
In one or more embodiments, Z1 and Z2 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, Z1 or Z2 may optionally be bonded to ring CY31 to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, Z1 or Z2 may optionally be bonded to ring CY32 to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
R10a may be the same as described herein.
In Formula 1, R11 to R13, R2, R31, R32, and R4 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkenyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkynyl group unsubstituted or substituted with at least one R10a, a C1-C60 alkoxy group unsubstituted or substituted with at least one R10a, a C1-C60 alkylthio group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, a C6-C60 aryloxy group unsubstituted or substituted with at least one R10a, a C6-C60 arylthio group unsubstituted or substituted with at least one R10a, —C(Q1)(Q2)(Q3), —Si(Q1)(Q2)(Q3), —N(Q1)(Q2), —B(Q1)(Q2), —C(═O)(Q1), —S(═O)2(Q1), or —P(═O)(Q1)(Q2).
R10a and Q1 to Q3 may each be the same as described herein.
In Formula 1, a2, a31, a32, and a4 indicate the number of R2, the number of R31, the number of R32, and the number of R4, respectively, and may each independently be an integer from 1 to 20. When a2 is 2 or more, two or more of R2(s) may be identical to or different from each other, when a31 is 2 or more, two or more of R31(s) may be identical to or different from each other, when a32 is 2 or more, two or more of R32(s) may be identical to or different from each other, and when a4 is 2 or more, two or more of R4(s) may be identical to or different from each other.
In one or more embodiments, two or more neighboring groups selected from among R11 to R13, R2, R31, R32, and R4 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, two or more neighboring groups selected from among R11 to R13 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, a2 may be 2 or more, and two or more neighboring groups of R2(s) in the number of a2 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, a31 may be 2 or more, and two or more neighboring groups of R31(s) in the number of a31 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, a32 may be 2 or more, and two or more neighboring groups of R32(s) in the number of a32 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, a4 may be 2 or more, and two or more neighboring groups of R4(s) in the number of a4 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
R10a may be the same as described herein.
In one or more embodiments, R11 to R13, R2, R31, R32, and R4 may each independently be:
Q1 to Q3 and Q31 to Q33 may each be the same as described herein.
In one or more embodiments, R11 to R13, R2, R31, R32, and R4 may each independently be:
In one or more embodiments, R11 to R13, R2, R31, R32, and R4 may each independently be:
In one or more embodiments, R11 may be a group represented by Formula S1:
In Formula S1,
In one or more embodiments, the organometallic compound may be substituted with at least one deuterium.
In one or more embodiments, a group represented by * in Formula 1 may be selected from groups represented by Formulae CY1-1 to CY1-7:
In Formulae CY1-1 to CY1-7,
In one or more embodiments, a group represented by
in Formula 1 may be selected from groups represented by Formulae CY2-1 to CY2-6:
In Formulae CY2-1 to CY2-6,
In one or more embodiments, a group represented by
in Formula 1 may be selected from groups represented by Formulae CY3-1 to CY3-7:
In Formulae CY3-1 to CY3-7,
In one or more embodiments, a group represented by
in Formula 1 may be selected from groups represented by Formulae CY4-1 to CY4-6:
In Formulae CY4-1 to CY4-6,
In one or more embodiments, the organometallic compound may be a group represented by Formula 1-1:
In Formula 1-1,
In one or more embodiments, two or more neighboring groups selected from R11 to R13, R21 to R23, R311, R312, R321 to R324, and R41 to R44 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, in Formula 1-1, two or more neighboring groups selected from R11 to R13 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, in Formula 1-1, two or more neighboring groups selected from R21 to R23 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, in Formula 1-1, R311 and R312 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, in Formula 1-1, two or more neighboring groups selected from R321 to R324 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, in Formula 1-1, two or more neighboring groups selected from R41 to R44 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
R10a may be the same as described herein.
In one or more embodiments, the organometallic compound may be selected from groups represented by Formulae 1-1a to 1-1e:
In Formulae 1-1a to 1-1e,
In one or more embodiments, in Formulae 1-1a to 1-1e, two or more neighboring groups selected from R11 to R13, R21 to R23, R311, R312, R321 to R324, R331 to R335, R341 to R345, and R41 to R44 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, in Formulae 1-1a to 1-1e, two or more neighboring groups selected from R11 to R13 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, in Formulae 1-1a to 1-1e, two or more neighboring groups selected from R21 to R23 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, in Formulae 1-1a to 1-1e, R311 and R312 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, in Formulae 1-1a to 1-1e, two or more neighboring groups selected from R321 to R324 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, in Formulae 1-1a to 1-1e, two or more neighboring groups selected from R331 to R335 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, in Formulae 1-1a to 1-1e, two or more neighboring groups selected from R341 to R345 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In one or more embodiments, in Formulae 1-1a to 1-1e, two or more neighboring groups selected from R41 to R44 may optionally be bonded to each other to form a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
R10a may be the same as described herein.
Unless defined otherwise herein, for example, R10a in the description of Formula 1 may be:
Unless defined otherwise herein, for example, Q1 to Q3, Q11 to Q13, Q21 to Q23, and Q31 to Q33 in the description of Formula 1 may each independently be: hydrogen; deuterium; —F; —Cl; —Br; —I; a hydroxyl group; a cyano group; a nitro group; a C1-C60 alkyl group; a C2-C60 alkenyl group; a C2-C60 alkynyl group; a C1-C60 alkoxy group; a C3-C60 carbocyclic group or a C1-C60 heterocyclic group, each unsubstituted or substituted with deuterium, —F, a cyano group, a C1-C60 alkyl group, a C1-C60 alkoxy group, a phenyl group, a biphenyl group, or any combination thereof; a C7-C60 arylalkyl group; or a C2-C60 heteroarylalkyl group.
In the organometallic compound represented by Formula 1, due to a T1 linking group represented by *—Si(Z1)(Z2)→*′ or *—Ge(Z1)(Z2)→*′ which links ring CY31 and ring CY32 to each other, a HOMO energy level may be decreased and an existence ratio of triplet metal-to-ligand charge transfer state (3MLCT) may be increased, resulting in improvement in overall color purity and an increase in lifespan. In some embodiments, due to the presence of the T1 linking group, overall material stability may be improved. Accordingly, by utilizing the organometallic compound represented by Formula 1, an electronic device (e.g., an organic light-emitting device) having decreased driving voltage, improved color purity and efficiency, and increased lifespan may be implemented.
In Formula 2, L51 to L53 may each independently be a single bond, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In Formula 2, b51 to b53 indicate the number of L51 to the number of L53, respectively, and may each be an integer from 1 to 5. When b51 is 2 or more, two or more of L51(s) may be identical to or different from each other, when b52 is 2 or more, two or more of L52(s) may be identical to or different from each other, and when b53 is 2 or more, two or more of L53(s) may be identical to or different from each other. For example, in some embodiments, b51 to b53 may each independently be 1 or 2.
In one or more embodiments, in Formula 2, L51 to L53 may each independently be:
In one or more embodiments, in Formula 2, a bond between L51 and R51, a bond between L52 and R52, a bond between L53 and R53, a bond between two L51(s), a bond between two L52(s), a bond between two L53(s), a bond between L51 and carbon between X54 and X55 in Formula 2, a bond between L52 and carbon between X54 and X56 in Formula 2, and a bond between L53 and carbon between X55 and X56 in Formula 2 may each be a “carbon-carbon single bond.”
In Formula 2, X54 may be N or C(R54), X55 may be N or C(R55), X56 may be N or C(R56), and at least one selected from X54 to X56 may be N. R54 to R56 may each be the same as described herein. For example, in some embodiments, two or three selected from X54 to X56 may each be N.
In Formula 2, R51 to R56 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkenyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkynyl group unsubstituted or substituted with at least one R10a, a C1-C60 alkoxy group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, a C6-C60 aryloxy group unsubstituted or substituted with at least one R10a, a C6-C60 arylthio group unsubstituted or substituted with at least one R10a, a C7-C60 arylalkyl group unsubstituted or substituted with at least one R10a, a C2-C60 heteroarylalkyl group unsubstituted or substituted with at least one R10a, —C(Q1)(Q2)(Q3), —Si(Q1)(Q2)(Q3), —N(Q1)(Q2), —B(Q1)(Q2), —C(═O)(Q1), —S(═O)2(Q1), or —P(═O)(Q1)(Q2). Q1 to Q3 may each be the same as described herein.
In one or more embodiments, in Formula 2, R51 to R56 may each independently be:
In Formula 91,
For example, in some embodiments, in Formula 91,
hydrogen or a C1-C10 alkyl group; or
In one or more embodiments, in Formula 2, a group represented by *-(L51)b51-R51 and a group represented by *-(L52)b52-R52 may each not be a phenyl group.
In one or more embodiments, in Formula 2, a group represented by *-(L51)b51-R51 and a group represented by *-(L52)b52-R52 may be identical to each other.
In one or more embodiments, in Formula 2, a group represented by *-(L51)b51-R51 and a group represented by *-(L52)b52-R52 may be different from each other.
In one or more embodiments, in Formula 2, b51 and b52 may each be 1, 2, or 3, and L51 and L52 may each independently be a benzene group, a pyridine group, a pyrimidine group, a pyridazine group, a pyrazine group, or a triazine group, each unsubstituted or substituted with at least one R10a.
For example, in some embodiments, in Formula 2, R51 and R52 may each independently be a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, a C6-C60 aryloxy group unsubstituted or substituted with at least one R10a, a C6-C60 arylthio group unsubstituted or substituted with at least one R10a, —C(Q1)(Q2)(Q3), or —Si(Q1)(Q2)(Q3), and
In one or more embodiments,
In Formulae CY51-1 to CY51-26, CY52-1 to CY52-26, and CY53-1 to CY53-27,
For example, in one or more embodiments, in Formulae CY51-1 to CY51-26 and CY52-1 to 52-26, R51a to R51e and R52a to R52e may each independently be:
a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a phenyl group, a biphenyl group, a (C1-C10 alkyl)phenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an isoindolyl group, an indolyl group, an indazolyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a carbazolyl group, a phenanthrolinyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzoisothiazolyl group, a benzoxazolyl group, a benzoisoxazolyl group, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, a triazinyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an azacarbazolyl group, an azadibenzofuranyl group, an azadibenzothiophenyl group, an azafluorenyl group, an azadibenzosilolyl group, or a group represented by Formula 91, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a phenyl group, a biphenyl group, a (C1-C10 alkyl)phenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an isoindolyl group, an indolyl group, an indazolyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a carbazolyl group, a phenanthrolinyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzoisothiazolyl group, a benzoxazolyl group, a benzoisoxazolyl group, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, a triazinyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, or any combination thereof; or
In Formula 3, ring CY71 and ring CY72 may each independently be a π electron-rich C3-C60 cyclic group or a pyridine group.
In Formula 3, X71 may be a single bond, or a linking group including O, S, N, B, C, Si, or any combination thereof.
In Formula 3, * indicates a binding site to any atom included in a remaining portion of the third compound other than the group represented by Formula 3.
In Formulae 3-1 to 3-5, ring CY71 to ring CY74 may each independently be a π electron-rich C3-C60 cyclic group or a pyridine group.
In Formulae 3-1 to 3-5, X82 may be a single bond, O, S, N-[(L82)b82-R82], C(R82a)(R82b), or Si(R82a)(R82b).
In Formulae 3-1 to 3-5, X83 may be a single bond, O, S, N-[(L83)b83-R83], C(R83a)(R83b), or Si(R83a)(R83b).
In Formulae 3-1 to 3-5, X84 may be O, S, N-[(L84)b84-R84], C(R84a)(R84b), or Si(R84a)(R84b).
In Formulae 3-1 to 3-5, X85 may be C or Si.
In Formulae 3-1 to 3-5, L81 to L85 may each independently be a single bond, *—C(Q4)(Q5)→*′, *—Si(Q4)(Q5)→*′, a π electron-rich C3-C60 cyclic group unsubstituted or substituted with at least one R10a, or a pyridine group unsubstituted or substituted with at least one R10a.
Q4 and Q5 may each be the same as described with respect to Q1.
In Formulae 3-1 to 3-5, b81 to b85 may each independently be an integer from 1 to 5.
In Formulae 3-1 to 3-5, R71 to R74, R81 to R85, R82a, R82b, R83a, R83b, R84a, and R84b may each be the same as described herein.
In Formulae 3-1 to 3-5, a71 to a74 indicate the number of R71 to the number of R74, respectively, and may each independently be an integer from 0 to 20. When a71 is 2 or more, two or more of R71(s) may be identical to or different from each other, when a72 is 2 or more, two or more of R72(s) may be identical to or different from each other, when a73 is 2 or more, two or more of R73(s) may be identical to or different from each other, and when a74 is 2 or more, two or more of R74(s) may be identical to or different from each other. In some embodiments, a71 to a74 may each independently be an integer from 0 to 8.
R10a may be the same as described herein.
In Formulae 3-1 to 3-5, L81 to L85 may each independently be:
In one or more embodiments, a group represented by
in Formulae 3-1 and 3-2 may be a group represented by one selected from among Formulae CY71-1(1) to CY71-1(8), and/or
In Formulae CY71-1(1) to CY71-1(8), CY71-2(1) to CY71-2(8), CY71-3(1) to CY71-3(32), CY71-4(1) to CY71-4(32), and CY71-5(1) to CY71-5(8),
In Formulae 502 and 503, ring A501 to ring A504 may each independently be a C3-C60 carbocyclic group or a C1-C60 heterocyclic group.
In Formulae 502 and 503, Y505 may be O, S, N(R505), B(R505), C(R505a)(R505b), or Si(R505a)(R505b).
In Formulae 502 and 503, Y506 may be O, S, N(R506), B(R506), C(R506a)(R506b), or Si(R506a)(R506b).
In Formulae 502 and 503, Y507 may be O, S, N(R507), B(R507), C(R507a)(R507b), or Si(R507a)(R507b).
In Formulae 502 and 503, Y505 may be O, S, N(R508), B(R508), C(R508a)(R508b), or Si(R508a)(R508b).
In Formulae 502 and 503, Y51 and Y52 may each independently be B, P(═O), or S(═O).
In Formulae 502 and 503, R500a, R500b, R501 to R508, R505a, R505b, R506a, R506b, R507a, R507b, R508a, and R508b may each be the same as described herein.
In Formulae 502 and 503, a501 to a504 indicate the number of R501 to the number of R504, respectively, and may each independently be an integer from 0 to 20. When a501 is 2 or more, two or more of R501 (s) may be identical to or different from each other, when a502 is 2 or more, two or more of R502(s) may be identical to or different from each other, when a503 is 2 or more, two or more of R503(s) may be identical to or different from each other, and when a504 is 2 or more, two or more of R504(s) may be identical to or different from each other. In some embodiments, a501 to a504 may each independently be an integer from 0 to 8.
In the present disclosure, R51 to R56, R71 to R74, R81 to R85, R82a, R82b, R83a, R83b, R84a, R84b, R500a, R500b, R501 to R508, R505a, R505b, R506a, R506b, R507a, R507b, R508a, and R508b may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkenyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkynyl group unsubstituted or substituted with at least one R10a, a C1-C60 alkoxy group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, a C6-C60 aryloxy group unsubstituted or substituted with at least one R10a, a C6-C60 arylthio group unsubstituted or substituted with at least one R10a, a C7-C60 arylalkyl group unsubstituted or substituted with at least one R10a, a C2-C60 heteroarylalkyl group unsubstituted or substituted with at least one R10a, —C(Q1)(Q2)(Q3), —Si(Q1)(Q2)(Q3), —N(Q1)(Q2), —B(Q1)(Q2), —C(═O)(Q1), —S(═O)2(Q1), or —P(═O)(Q1)(Q2). Q1 to Q3 may each be the same as described herein.
In one or more embodiments, i) R51 to R56, R71 to R74, R81 to R85, R82a, R82b, R83a, R83b, R84a, R84b, R500a, R500b, R501 to R508, R505a, R505b, R506a, R506b, R507a, R507b, R508a, and R508b in Formulae 2, 3-1 to 3-5, 502, and 503 and ii) R10a may each independently be:
In one or more embodiments, i) R11 to R13, R2, R31, R32, R4, Z1, and Z2 in Formula 1, ii) R51 to R56, R71 to R74, R81 to R85, R82a, R82b, R83a, R83b, R84a, R84b, R500a, R500b, R501 to R508, R505a, R505b, R506a, R506b, R507a, R507b, R508a, and R508b in Formulae 2, 3-1 to 3-5, 502, and 503, and iii) R10a may each independently be:
In Formulae 9-1 to 9-19 and 10-1 to 10-246, * indicates a binding site to a neighboring atom, “Ph” represents a phenyl group, “D” represents deuterium, and “TMS” represents a trimethylsilyl group.
In one or more embodiments, the organometallic compound represented by Formula 1 may be one selected from among Compounds 1 to 180:
For example, in one or more embodiments, the second compound may be at least one selected from among Compounds ETH1 to ETH100:
For example, in one or more embodiments, the third compound may be at least one selected from among Compounds HTH1 to HTH40:
For example, in one or more embodiments, the fourth compound may be at east one selected from among Compounds DFD1 to DFD29:
In the compounds above, “Ph” represents a phenyl group, “D5” represents substitution with five deuterium atoms, and “D4” represents substitution with four deuterium atoms. For example, a group represented by
may be identical to a group represented by
Hereinafter, the structure of the light-emitting device 10 according to one or more embodiments and a method of manufacturing the light-emitting device 10 will be described in more detail with reference to
In
The first electrode 110 may be formed by, for example, depositing or sputtering a material for forming the first electrode 110 on the substrate. When the first electrode 110 is an anode, a material for forming the first electrode 110 may be a high-work function material that facilitates injection of holes.
The first electrode 110 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. In one or more embodiments, when the first electrode 110 is a transmissive electrode, a material for forming the first electrode 110 may include indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), or any combination thereof. In one or more embodiments, when the first electrode 110 is a semi-transmissive electrode or a reflective electrode, a material for forming the first electrode 110 may include magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), or any combination thereof.
The first electrode 110 may have a single-layer structure including (e.g., consisting of) a single layer or a multi-layer structure including multiple layers. For example, in some embodiments, the first electrode 110 may have a three-layer structure of ITO/Ag/ITO.
The interlayer 130 may be on the first electrode 110. The interlayer 130 may include an emission layer.
In one or more embodiments, the interlayer 130 may further include a hole transport region arranged between the first electrode 110 and the emission layer, and an electron transport region arranged between the emission layer and the second electrode 150.
In one or more embodiments, the interlayer 130 may further include, in addition to one or more suitable organic materials, a metal-containing compound such as an organometallic compound, for example, the organometallic compound represented by Formula 1, an inorganic material such as one or more quantum dots, and/or the like.
In one or more embodiments, the interlayer 130 may include, i) two or more emitting units sequentially stacked between the first electrode 110 and the second electrode 150, and ii) a charge generation layer between the two or more emitting units. When the interlayer 130 includes the two or more emitting units and the charge generation layer, the light-emitting device 10 may be a tandem light-emitting device.
The hole transport region may have: i) a single-layer structure including (e.g., consisting of) a single layer including (e.g., consisting of) a single material, ii) a single-layer structure including (e.g., consisting of) a single layer including (e.g., consisting of) multiple materials that are different from each other, or iii) a multi-layer structure including multiple layers including multiple materials that are different from each other.
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.
For example, in one or more 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 constituent layers of each structure are stacked sequentially from the first electrode 110 in each stated order.
In one or more embodiments, the hole transport region may include a compound represented by Formula 201, a compound represented by Formula 202, or any combination thereof:
In Formulae 201 and 202,
For example, in some embodiments, each of Formulae 201 and 202 may include at least one selected from groups represented by Formulae CY201 to CY217:
In Formulae CY201 to CY217, R10b and R10c may each be the same as described with respect to R10a, ring CY201 to ring CY204 may each independently be a C3-C20 carbocyclic group or a C1-C20 heterocyclic group, and at least one hydrogen in Formulae CY201 to CY217 may be unsubstituted or substituted with R10a.
In one or more embodiments, ring CY201 to ring CY204 in Formulae CY201 to CY217 may each independently be a benzene group, a naphthalene group, a phenanthrene group, or an anthracene group.
In one or more embodiments, each of Formulae 201 and 202 may include at least one selected from the groups represented by Formulae CY201 to CY203.
In one or more embodiments, Formula 201 may include at least one selected from the groups represented by Formulae CY201 to CY203 and at least one selected from the groups represented by Formulae CY204 to CY217.
In one or more embodiments, in Formula 201, xa1 may be 1, R201 may be one selected from the groups represented by Formulae CY201 to CY203, xa2 may be 0, and R202 may be one selected from the groups represented by Formulae CY204 to CY207.
In one or more embodiments, each of Formulae 201 and 202 may not include (e.g., may exclude any) the groups represented by Formulae CY201 to CY203.
In one or more embodiments, each of Formulae 201 and 202 may not include (e.g., may exclude any) the groups represented by Formulae CY201 to CY203, and may include at least one selected from the groups represented by Formulae CY204 to CY217.
In one or more embodiments, each of Formulae 201 and 202 may not include (e.g., may exclude any) the groups represented by Formulae CY201 to CY217.
For example, in some embodiments, the hole transport region may include: at least one selected from Compounds HT1 to HT46; 4,4′,4″-[tris(3-methylphenyl)phenylamino] triphenylamine (m-MTDATA); 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (TDATA); 4,4′,4″-tris[N-(2-naphthyl)-N-phenylamino]-triphenylamine (2-TNATA); N,N′-di(naphthalen-1-yl)-N,N′-diphenyl-benzidine (NPB(NPD)); β-NPB; N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (TPD); spiro-TPD; spiro-NPB; methylated NPB; 4,4′-cyclohexylidene bis[N,N-bis(4-methylphenyl)benzenamine] (TAPC); 4,4′-bis[N,N′-(3-tolyl)amino]-3,3′-dimethylbiphenyl (HMTPD); 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA); polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA); poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS); polyaniline/camphor sulfonic acid (PANI/CSA); polyaniline/poly(4-styrenesulfonate) (PANI/PSS); and/or any combination thereof:
A thickness of the hole transport region may be in a range of about 50 Å to about 10,000 Å, for example, about 100 Å to about 4,000 Å. When the hole transport region includes a hole injection layer, a hole transport layer, or any combination thereof, a thickness of the hole injection layer may be in a range of about 100 Å to about 9,000 Å, for example, about 100 Å to about 1,000 Å, and a thickness of the hole transport layer may be in a range of about 50 Å to about 2,000 Å, for example, about 100 Å to about 1,500 Å. When the thicknesses of the hole transport region, the hole injection layer, and the hole transport layer are within these ranges, satisfactory hole transporting characteristics may be obtained without a substantial increase in driving voltage.
The emission auxiliary layer may increase light-emission efficiency by compensating for an optical resonance distance according to the wavelength of light emitted by the emission layer, and the electron blocking layer may block or reduce 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
In one or more embodiments, the hole transport region may further include, in addition to these aforementioned materials, a charge-generation material for the improvement of conductive properties. The charge-generation material may be substantially uniformly or non-uniformly dispersed in the hole transport region (e.g., in the form of a single layer including (e.g., consisting of) a charge-generation material).
The charge-generation material may be, for example, a p-dopant.
For example, in some embodiments, the p-dopant may have a LUMO energy level of less than or equal to −3.5 eV.
In one or more embodiments, the p-dopant may include a quinone derivative, a cyano group-containing compound, a compound including element EL1 and element EL2, or any combination thereof.
Non-limiting examples of the quinone derivative may be tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), and/or the like.
Non-limiting examples of the cyano group-containing compound may be dipyrazino[2,3-f: 2′,3′-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN), a compound represented by Formula 221, and/or the like:
In Formula 221,
In the compound including element EL1 and element EL2, element EL1 may be metal, metalloid, or any combination thereof, and element EL2 may be non-metal, metalloid, or any combination thereof.
Non-limiting examples of the metal may be: 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/or the like.
Non-limiting examples of the metalloid may be silicon (Si), antimony (Sb), tellurium (Te), and/or the like.
Non-limiting examples of the non-metal may be oxygen (O), a halogen (e.g., F, Cl, Br, I, etc.), and/or the like.
For example, in one or more embodiments, the compound containing element EL1 and element EL2 may include metal oxides, metal halides (e.g., metal fluorides, metal chlorides, metal bromides, metal iodides, etc.), metalloid halides (e.g., metalloid fluorides, metalloid chlorides, metalloid bromides, metalloid iodides, etc.), metal tellurides, or any combination thereof.
Non-limiting examples of the metal oxide may be tungsten oxides (e.g., WO, W2O3, WO2, WO3, W2O5, etc.), vanadium oxides (e.g., VO, V2O3, VO2, V2O5, etc.), molybdenum oxides (e.g., MoO, Mo2O3, MoO2, MoO3, Mo2O5, etc.), rhenium oxides (e.g., ReO3, etc.), and/or the like.
Non-limiting examples of the metal halide may be alkali metal halides, alkaline earth metal halides, transition metal halides, post-transition metal halides, lanthanide metal halides, and/or the like.
Non-limiting examples of the alkali metal halide may be LiF, NaF, KF, RbF, CsF, LiCl, NaCl, KCl, RbCl, CsCl, LiBr, NaBr, KBr, RbBr, CsBr, LiI, NaI, KI, RbI, CsI, and/or the like.
Non-limiting examples of the alkaline earth metal halide may be BeF2, MgF2, CaF2, SrF2, BaF2, BeCl2, MgCl2, CaCl2), SrCl2, BaCl2, BeBr2, MgBr2, CaBr2, SrBr2, BaBr2, Be12, Mg12, CaI2, Sr12, BaI2, and/or the like.
Non-limiting examples of the transition metal halide may be titanium halides (e.g., TiF4, TiCl4, TiBr4, TiI4, etc.), zirconium halides (e.g., ZrF4, ZrCl4, ZrBr4, Zr14, etc.), hafnium halides (e.g., HfF4, HfC14, HfBr4, HfI4, etc.), vanadium halides (e.g., VF3, VCl3, VBr3, VI3, etc.), niobium halides (e.g., NbF3, NbCl3, NbBr3, NbI3, etc.), tantalum halides (e.g., TaF3, TaCl3, TaBr3, TaI3, etc.), chromium halides (e.g., CrF3, CrCl3, CrBr3, Cr13, etc.), molybdenum halides (e.g., MoF3, MoCl3, MoBr3, MoI3, etc.), tungsten halides (e.g., WF3, WCl3, WBr3, WI3, etc.), manganese halides (e.g., MnF2, MnCl2, MnBr2, Mn12, etc.), technetium halides (e.g., TcF2, TcCl2, TcBr2, Tc12, etc.), rhenium halides (e.g., ReF2, ReCl2, ReBr2, Re12, etc.), ferrous halides (e.g., FeF2, FeCl2, FeBr2, Fe12, etc.), ruthenium halides (e.g., RuF2, RuCl2, RuBr2, RuI2, etc.), osmium halides (e.g., OsF2, OsC12, OsBr2, Os12, etc.), cobalt halides (e.g., CoF2, CoC12, CoBr2, CoI2, etc.), rhodium halides (e.g., RhF2, RhCl2, RhBr2, Rh12, etc.), iridium halides (e.g., IrF2, IrCl2, IrBr2, IrI2, etc.), nickel halides (e.g., NiF2, NiCl2, NiBr2, NiI2, etc.), palladium halides (e.g., PdF2, PdC12, PdBr2, Pd12, etc.), platinum halides (e.g., PtF2, PtCl2, PtBr2, PtI2, etc.), cuprous halides (e.g., CuF, CuCl, CuBr, CuI, etc.), silver halides (e.g., AgF, AgCl, AgBr, AgI, etc.), gold halides (e.g., AuF, AuCl, AuBr, AuI, etc.), and/or the like.
Non-limiting examples of the post-transition metal halide may be zinc halides (e.g., ZnF2, ZnCl2, ZnBr2, ZnI2, etc.), indium halides (e.g., InI3, etc.), tin halides (e.g., SnI2, etc.), and/or the like.
Non-limiting examples of the lanthanide metal halide may be YbF, YbF2, YbF3, SmF3, YbCl, YbCl2, YbCl3, SmCl3, YbBr, YbBr2, YbBr3, SmBr3, YbI, YbI2, YbI3, SmI3, and/or the like.
Non-limiting examples of the metalloid halide may be antimony halides (e.g., SbCl5, etc.) and/or the like.
Non-limiting examples of the metal telluride may be alkali metal tellurides (e.g., Li2Te, Na2Te, K2Te, Rb2Te, Cs2Te, etc.), alkaline earth metal tellurides (e.g., BeTe, MgTe, CaTe, SrTe, BaTe, etc.), transition metal tellurides (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.), post-transition metal tellurides (e.g., ZnTe, etc.), lanthanide metal tellurides (e.g., LaTe, CeTe, PrTe, NdTe, PmTe, EuTe, GdTe, TbTe, DyTe, HoTe, ErTe, TmTe, YbTe, LuTe, etc.), and/or the like.
When the light-emitting device 10 is a full-color light-emitting device, the emission layer may be patterned into a red emission layer, a green emission layer, and/or a blue emission layer, according to a sub-pixel. In one or more embodiments, the emission layer may have a stacked structure of two or more layers selected from a red emission layer, a green emission layer, and a blue emission layer, in which the two or more layers contact each other or are separated from each other, to emit white light (e.g., combined white light). In one or more embodiments, the emission layer may include two or more materials selected from a red light-emitting material, a green light-emitting material, and a blue light-emitting material, in which the two or more materials are mixed with each other in a single layer, to emit white light (e.g., combined white light).
In one or more embodiments, the emission layer may include a host and a dopant (or an emitter). In one or more embodiments, the emission layer may further include an auxiliary dopant that promotes energy transfer to the dopant (or the emitter), in addition to the host and the dopant (or the emitter). When the emission layer includes the dopant (or the emitter) and the auxiliary dopant, the dopant (or the emitter) and the auxiliary dopant are different from each other.
The organometallic compound represented by Formula 1 may serve as the dopant (or the emitter), or may serve as the auxiliary dopant.
An amount (weight) of the dopant (or the emitter) 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.
The organometallic compound represented by Formula 1 may be included in the emission layer. An amount (weight) of the organometallic compound in the emission layer may be in a range of about 0.01 parts by weight to about 30 parts by weight, about 0.1 parts by weight to about 20 parts by weight, or about 0.1 parts by weight to about 15 parts by weight, based on 100 parts by weight of the emission layer.
In one or more embodiments, the emission layer may include a quantum dot.
In one or more embodiments, the emission layer may include a delayed fluorescence material. The delayed fluorescence material may act as a host or a dopant in the emission layer.
A thickness of the emission layer may be in a range of about 100 Å to about 1,000 Å, for example, about 200 Å to about 600 Å. When the thickness of the emission layer is within these ranges, excellent or suitable luminescence characteristics may be obtained without a substantial increase in driving voltage.
In one or more embodiments, the host in the emission layer may include the second compound or the third compound described herein, or any combination thereof.
In one or more embodiments, the host may include a compound represented by Formula 301:
In Formula 301,
For example, in some embodiments, when xb11 in Formula 301 is 2 or more, two or more of Ar301(s) may be linked to each other via a single bond.
In one or more embodiments, the host may include a compound represented by Formula 301-1, a compound represented by Formula 301-2, or any combination thereof:
In Formulae 301-1 and 301-2,
In one or more embodiments, the host may include an alkaline earth metal complex, a post-transition metal complex, or any combination thereof. In one or more embodiments, the host may include a Be complex (e.g., Compound H55), a Mg complex, a Zn complex, or any combination thereof.
In one or more embodiments, the host may include: at least one selected from among Compounds H1 to H128; 9,10-di(2-naphthyl)anthracene (ADN); 2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN); 9,10-di(2-naphthyl)-2-t-butyl-anthracene (TBADN); 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP); 1,3-di(carbazol-9-yl)benzene (mCP); 1,3,5-tri(carbazol-9-yl) benzene (TCP); and/or any combination thereof:
In one or more embodiments, the host may include a silicon-containing compound, a phosphine oxide-containing compound, or any combination thereof.
The host may have one or more suitable modifications. For example, the host may include only one kind of compound, or may include two or more kinds of different compounds.
The emission layer may include, as a phosphorescent dopant, the organometallic compound represented by Formula 1.
In one or more embodiments, the emission layer may include the organometallic compound represented by Formula 1, and when the organometallic compound represented by Formula 1 serves as an auxiliary dopant, the emission layer may include a phosphorescent dopant.
The phosphorescent dopant may include at least one transition metal as a central metal.
The phosphorescent dopant may include a monodentate ligand, a bidentate ligand, a tridentate ligand, a tetradentate ligand, a pentadentate ligand, a hexadentate ligand, or any combination thereof.
The phosphorescent dopant may be electrically neutral.
For example, in some embodiments, the phosphorescent dopant may include an organometallic compound represented by Formula 401:
In Formulae 401 and 402,
For example, in some embodiments, in Formula 402, i) X401 may be nitrogen and X402 may be carbon, or ii) each of X401 and X402 may be nitrogen.
In one or more embodiments, when xc1 in Formula 401 is 2 or more, two ring A401 (s) among two or more of L401 (s) may optionally be linked to each other via T402, which is a linking group, and/or two ring A402(s) among two or more of 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 be the same as described with respect to T401.
In Formula 401, L402 may be an organic ligand. For example, L402 may include a halogen, 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-containing group (e.g., a phosphine group, a phosphite group, etc.), or any combination thereof.
In one or more embodiments, the phosphorescent dopant may include, for example, one selected from among Compounds PD1 to PD39, or any combination thereof:
In one or more embodiments, the emission layer may include the organometallic compound represented by Formula 1, and when the organometallic compound represented by Formula 1 serves as an auxiliary dopant, the emission layer may further include a fluorescent dopant.
In one or more embodiments, the emission layer may include the organometallic compound represented by Formula 1, and when the organometallic compound represented by Formula 1 serves as a phosphorescent dopant, the emission layer may further include an auxiliary dopant.
The fluorescent dopant and the auxiliary dopant may each independently include an arylamine compound, a styrylamine compound, a boron-containing compound, or any combination thereof.
For example, in one or more embodiments, the fluorescent dopant and the auxiliary dopant may each independently include a compound represented by Formula 501:
In Formula 501,
For example, in some embodiments, Ar501 in Formula 501 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 some embodiments, xd4 in Formula 501 may be 2.
For example, in one or more embodiments, the fluorescent dopant and the auxiliary dopant may each include at least one selected from among Compounds FD1 to FD37, 4,4′-bis(2,2-diphenylvinyl)-1,1′-biphenyl (DPVBi), 4,4′-bis[4-(N,N-diphenylamino)styryl]biphenyl (DPAVBi), or any combination thereof:
In one or more embodiments, the emission layer may include a delayed fluorescence material.
In the present disclosure, the delayed fluorescence material may be selected from compounds capable of emitting delayed fluorescence based on a delayed fluorescence emission mechanism.
The delayed fluorescent material may include, for example, the fourth compound described herein.
The delayed fluorescence material included in the emission layer may act as a host or a dopant depending on the type or kind of other materials included in the emission layer.
In one or more embodiments, a difference between a triplet energy level (eV) of the delayed fluorescence material and a singlet energy level (eV) of the delayed fluorescence material may be greater than or equal to 0 eV and less than or equal to 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.
For example, in one or more embodiments, the delayed fluorescence material may include i) 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 heterocyclic group, etc.), and/or ii) a material including a C8-C60 polycyclic group in which two or more cyclic groups are condensed while sharing boron (B).
Non-limiting examples of the delayed fluorescence material may include at least one selected from Compounds DF1 to DF14:
In one or more embodiments, the emission layer may include one or more quantum dots.
The term “quantum dot” as utilized herein refers to a crystal of a semiconductor compound, and may include any material capable of emitting light of one or more suitable emission wavelengths according to the size of the crystal.
A diameter of the quantum dots 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 of a quantum dot with an organic solvent and then 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 or selected through a process which costs lower and is easier 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.
Non-limiting examples of the Group II-VI semiconductor compound may include: a binary compound, such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, etc.; 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, etc.; a quaternary compound, such as CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, etc.; or any combination thereof.
Non-limiting examples of the Group III-V semiconductor compound may include: a binary compound, such as GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, 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 some embodiments, the Group III-V semiconductor compound may further include a Group II element. Non-limiting examples of the Group III-V semiconductor compound further including a Group II element may include InZnP, InGaZnP, InAlZnP, etc.
Non-limiting examples of the Group III-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, InGaSe3, etc.; or any combination thereof.
Non-limiting examples of the 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.
Non-limiting examples of the Group IV-VI semiconductor compound may include: a binary compound, such as SnS, SnSe, SnTe, PbS, PbSe, or PbTe; a ternary compound, such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, etc.; a quaternary compound, such as SnPbSSe, SnPbSeTe, SnPbSTe, etc.; or any combination thereof.
The Group IV element or compound may include: a single element compound, 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 the binary compound, the ternary compound, and the quaternary compound may be present at a substantially uniform concentration or non-substantially uniform concentration in a particle.
In some embodiments, the quantum dots may have a single structure in which the concentration of each element in the quantum dots is substantially uniform, or a core-shell dual structure. For example, in some embodiments, materials included in the core and materials included in the shell may be different from each other.
The shell of the quantum dots (e.g., the shell of (e.g., the shell around the core of) each of the quantum dots) may act as a protective layer that prevents chemical degeneration of the core to maintain semiconductor characteristics, and/or as a charging layer that imparts electrophoretic characteristics to the quantum dots. The shell may be a single layer or a multi-layer. The interface between the core and the shell may have a concentration gradient in which the concentration of an element existing in the shell decreases toward the center of the core.
Non-limiting examples of the shell of the quantum dots may include: oxides of metal, metalloid, or non-metal, semiconductor compounds; or any combination thereof. Non-limiting examples of the oxide of metal, metalloid, or non-metal may include: a binary compound, such as SiO2, Al2O3, TiO2, ZnO, MnO, Mn2O3, Mn3O4, CuO, FeO, Fe2O3, Fe3O4, CoO, Co3O4, NiO, etc.; a ternary compound, such as MgAl2O4, CoFe2O4, NiFe2O4, CoMn2O4, etc.; or any combination thereof. Non-limiting examples of the semiconductor compound may include: as described herein, a Group II-VI semiconductor compound; a Group III-V semiconductor compound; a Group III-VI semiconductor compound; a Group I-III-VI semiconductor compound; a Group IV-VI semiconductor compound; or any combination thereof. For example, the semiconductor compound suitable as a shell 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 the emission spectrum of the quantum dots may be less than or equal to about 45 nm, for example, less than or equal to about 40 nm, or for example, less than or equal to about 30 nm, and within these ranges, color purity or color reproducibility of the quantum dots may be improved. In some embodiments, because light emitted through the quantum dots is emitted in all directions, the wide viewing angle may be improved.
In some embodiments, the quantum dots may (e.g., may each) 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, and/or the like.
Because the energy band gap of the quantum dot may be adjusted by controlling the size of the quantum dots, light having one or more suitable wavelength bands may be obtained from a quantum dot-containing emission layer. Accordingly, by utilizing quantum dots of different sizes, a light-emitting device that emits light of one or more suitable wavelengths may be implemented. In one or more embodiments, the sizes of the quantum dots may be selected to enable the quantum dots to emit red light, green light, and/or blue light. In some embodiments, the quantum dots with suitable sizes may be configured to emit white light by combination of light of one or more suitable colors.
The electron transport region may have: i) a single-layered structure including (e.g., consisting of) a single layer including (e.g., consisting of) a single material, ii) a single-layered structure including (e.g., consisting of) a single layer including (e.g., consisting of) multiple materials that are different from each other, or iii) a multi-layered structure including multiple layers including multiple materials that are different from each other.
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.
For example, in one or more 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 constituent layers of each structure are stacked sequentially from the emission layer in each stated order.
The electron transport region (e.g., the buffer layer, the hole blocking layer, the electron control layer, or the electron transport layer in the electron transport region) may include a metal-free compound including at least one π electron-deficient nitrogen-containing C1-C60 heterocyclic group.
For example, in one or more embodiments, the electron transport region may include a compound represented by Formula 601:
In Formula 601,
For example, in some embodiments, when xe11 in Formula 601 is 2 or more, two or more of Ar601(s) may be linked to each other via a single bond.
In one or more embodiments, Ar601 in Formula 601 may be a substituted or unsubstituted anthracene group.
In one or more embodiments, the electron transport region may include a compound represented by Formula 601-1:
In Formula 601-1,
For example, in some embodiments, xe1 and xe611 to xe613 in Formulae 601 and 601-1 may each independently be 0, 1, or 2.
In one or more embodiments, the electron transport region may include: at least one selected from among Compounds ET1 to ET45; 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP); 4,7-diphenyl-1,10-phenanthroline (Bphen); tris(8-hydroxyquinolinato)aluminum (Alq3); bis(2-methyl-8-quinolinolato-N1,O8)-(1,1′-biphenyl-4-olato)aluminum (BAlq); 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole (TAZ); 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1 2,4-triazole (NTAZ); and/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, 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, for example, about 30 Å to about 300 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, 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.
In one or more embodiments, the electron transport region (e.g., the electron transport layer in the electron transport region) may further include, in addition to the materials described above, a metal-containing material.
The metal-containing material may include an alkali metal complex, an alkaline earth metal complex, or any combination thereof. 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 the metal ion of the alkali metal complex or the alkaline earth-metal complex may include a hydroxyquinoline, a hydroxyisoquinoline, a hydroxybenzoquinoline, a hydroxyacridine, a hydroxyphenanthridine, a hydroxyphenyloxazole, a hydroxyphenylthiazole, a hydroxyphenyloxadiazole, a hydroxyphenylthiadiazole, a hydroxyphenylpyridine, a hydroxyphenylbenzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or any combination thereof.
For example, in some embodiments, the metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 (LiQ) or ET-D2:
In one or more embodiments, the electron transport region may include an electron injection layer that facilitates the injection of electrons from the second electrode 150. The electron injection layer may directly contact the second electrode 150.
The electron injection layer may have: i) a single-layered structure including (e.g., consisting of) a single layer including (e.g., consisting of) a single material, ii) a single-layered structure including (e.g., consisting of) a single layer including (e.g., consisting of) multiple layers that are different from each other, or iii) a multi-layered structure including multiple layers including multiple materials that are different from each other.
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, respectively, or any combination thereof.
The alkali metal-containing compound may include: alkali metal oxides, such as Li2O, Cs2O, K2O, etc.; alkali metal halides, such as LiF, NaF, CsF, KF, LiI, NaI, CsI, KI, etc.; 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/or the like. The rare earth metal-containing compound may include YbF3, ScF3, Sc2O3, Y2O3, Ce2O3, GdF3, TbF3, YbI3, ScI3, TbI3, or any combination thereof. In one or more embodiments, the rare earth metal-containing compound may include lanthanide metal tellurides. Non-limiting examples of the lanthanide metal telluride may be LaTe, CeTe, PrTe, NdTe, PmTe, SmTe, EuTe, GdTe, TbTe, DyTe, HoTe, ErTe, TmTe, YbTe, LuTe, La2Te3, Ce2Te3, Pr2Te3, Nd2Te3, Pm2Te3, Sm2Te3, Eu2Te3, Gd2Te3, Tb2Te3, Dy2Te3, Ho2Te3, Er2Te3, Tm2Te3, Yb2Te3, Lu2Te3, and/or the like.
The alkali metal complex, the alkaline earth-metal complex, and the rare earth metal complex may include i) one of metal ions of the alkali metal, one of metal ions of the alkaline earth metal, and one of metal ions of the rare earth metal, respectively, and ii) a ligand bonded to the metal ions, for example, a hydroxyquinoline, a hydroxyisoquinoline, a hydroxybenzoquinoline, a hydroxyacridine, a hydroxyphenanthridine, a hydroxyphenyloxazole, a hydroxyphenylthiazole, a hydroxyphenyloxadiazole, a hydroxyphenylthiadiazole, a hydroxyphenylpyridine, a hydroxyphenyl benzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or any combination thereof.
In one or more embodiments, the electron injection layer may include (e.g., consist of) an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal-containing compound, an alkaline earth metal-containing compound, a rare earth metal-containing compound, an alkali metal complex, an alkaline earth metal complex, a rare earth metal complex, or any combination thereof, as described above. In one or more embodiments, the electron injection layer may further include an organic material (e.g., the compound represented by Formula 601).
In one or more embodiments, the electron injection layer may include (e.g., consist of) i) an alkali metal-containing compound (e.g., an alkali metal halide), or ii) a) an alkali metal-containing compound (e.g., an alkali metal halide), and b) an alkali metal, an alkaline earth metal, a rare earth metal, or any combination thereof. For example, in some embodiments, the electron injection layer may be a KI:Yb co-deposited layer, an RbI:Yb co-deposited layer, a LiF:Yb co-deposited layer, and/or the like.
When the electron injection layer further includes an organic material, an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal-containing compound, an alkaline earth metal-containing compound, a rare earth metal-containing compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or any combination thereof may be substantially 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, and, for example, about 3 Å to about 90 Å. When the thickness of the electron injection layer is within these ranges, satisfactory or suitable electron injection characteristics may be obtained without a substantial increase in driving voltage.
The second electrode 150 may be arranged on the interlayer 130 having the aforementioned structure. The second electrode 150 may be a cathode, which is an electron injection electrode, and as a material for forming the second electrode 150, a metal, an alloy, an electrically conductive compound, or any combination thereof, each having a low-work function, may be utilized.
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-layered structure or a multi-layered structure including multiple layers.
A first capping layer may be arranged outside (e.g., on) the first electrode 110, and/or a second capping layer may be arranged outside (e.g., on) the second electrode 150. In one or more embodiments, the light-emitting device 10 may have a structure in which the first capping layer, the first electrode 110, the interlayer 130, and the second electrode 150 are sequentially stacked in the stated order, a structure in which the first electrode 110, the interlayer 130, the second electrode 150, and the second capping layer are sequentially stacked in 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 sequentially stacked in the stated order.
In some embodiments, light generated in the emission layer of the interlayer 130 of the light-emitting device 10 may be extracted toward the outside through the first electrode 110, which is a semi-transmissive electrode or a transmissive electrode, and the first capping layer. In some embodiments, light generated in the emission layer of the interlayer 130 of the light-emitting device 10 may be extracted toward the outside through the second electrode 150, which is a semi-transmissive electrode or a transmissive electrode, and the second capping layer.
The first capping layer and the second capping layer may increase external emission efficiency according to the principle of constructive interference. Accordingly, the light extraction efficiency of the light-emitting device 10 is increased, so that the luminescence efficiency of the light-emitting device 10 may be improved.
Each of the first capping layer and the second capping layer may include a material having a refractive index of greater than or equal to 1.6 (e.g., at 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 or the second capping layer may (e.g., 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 each optionally be substituted with a substituent including O, N, S, Se, Si, F, Cl, Br, I, or any combination thereof. In one or more embodiments, at least one of the first capping layer or the second capping layer may (e.g., the first capping layer and the second capping layer may each independently) include an amine group-containing compound.
In one or more embodiments, at least one of the first capping layer or the second capping layer may (e.g., the first capping layer and the second capping layer may each independently) include a compound represented by Formula 201, a compound represented by Formula 202, or any combination thereof.
In one or more embodiments, at least one of the first capping layer or the second capping layer may (e.g., the first capping layer and the second capping layer may each independently) include at least one selected from Compounds HT28 to HT33, Compounds CP1 to CP6, β-NPB, and/or any combination thereof:
The organometallic compound represented by Formula 1 may be included in one or more suitable films. Accordingly, one or more aspects of embodiments of the present disclosure are directed toward a film including the organometallic compound represented by Formula 1. The film may be, for example, an optical member (or a light control member) (e.g., 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, etc.), a light blocking member (e.g., a light reflective layer, a light absorbing layer, etc.), a protective member (e.g., an insulating layer, a dielectric layer, etc.), and/or the like.
The light-emitting device may be included in one or more suitable electronic apparatuses. For example, in one or more embodiments, the electronic apparatus including the light-emitting device may be a light-emitting apparatus, an authentication apparatus, and/or the like.
In one or more embodiments, the electronic apparatus (e.g., a light-emitting apparatus) may further include, in addition to the light-emitting device, i) a color filter, ii) a color conversion layer, or iii) a color filter and a color conversion layer. The color filter and/or the color conversion layer may be arranged in at least one travel direction of light emitted from the light-emitting device. For example, in some embodiments, light emitted from the light-emitting device may be blue light, green light, or white light (e.g., combined white light). Details on the light-emitting device may be the same as described herein. In some embodiments, the color conversion layer may include quantum dots.
The electronic apparatus may include a first substrate. The first substrate may include a plurality of subpixel areas, the color filter may include a plurality of color filter areas respectively corresponding to the subpixel areas, and the color conversion layer may include a plurality of color conversion areas respectively corresponding to the subpixel areas.
A pixel-defining film may be arranged among the subpixel areas to define each of the subpixel areas.
The color filter may further include a plurality of color filter areas and light-shielding patterns arranged among the color filter areas, and the color conversion layer may further include a plurality of color conversion areas and light-shielding patterns arranged among the color conversion areas.
The plurality of color filter areas (or the plurality of color conversion areas) may include a first area configured to emit first color light, a second area configured to emit second color light, and/or a third area configured to emit 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, in one or more embodiments, the first color light may be red light, the second color light may be green light, and the third color light may be blue light. For example, in one or more embodiments, the plurality of color filter areas (or the plurality of color conversion areas) may include quantum dots. In some embodiments, the first area may include a red quantum dot to emit red light, the second area may include a green quantum dot to emit green light, and the third area may not include (e.g., may exclude) (e.g., any) quantum dots. Details on the quantum dot may be the same as described herein. The first area, the second area, and/or the third area may each further include a scatter.
For example, in one or more embodiments, the light-emitting device may be to emit first light, the first area may be to absorb the first light to emit first-first color light, the second area may be to absorb the first light to emit second-first color light, and the third area may be to absorb the first light to emit third-first color light. In this regard, the first-first color light, the second-first color light, and the third-first color light may have different maximum emission wavelengths. In some embodiments, 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.
In one or more embodiments, the electronic apparatus may further include a thin-film transistor, in addition to the light-emitting device as described above. The thin-film transistor may include a source electrode, a drain electrode, and an activation layer, wherein one selected from the source electrode and the drain electrode may be electrically connected to the first electrode or the second electrode of the light-emitting device.
The thin-film transistor may further include a gate electrode, a gate insulating film, and/or the like.
The activation layer may include crystalline silicon, amorphous silicon, an organic semiconductor, an oxide semiconductor, and/or the like.
In one or more embodiments, the electronic apparatus may further include a sealing portion for sealing the light-emitting device. The sealing portion may be arranged between the color filter and/or the color conversion layer and the light-emitting device. The sealing portion allows light from the light-emitting device to be extracted to the outside, and concurrently (e.g., simultaneously) prevents ambient air and moisture from penetrating into the light-emitting device. The sealing portion may be a sealing substrate including a transparent glass substrate or a plastic substrate. The sealing portion may be a thin-film encapsulation layer including at least one layer of an organic layer and/or an inorganic layer. When the sealing portion is a thin-film encapsulation layer, the electronic apparatus may be flexible.
Various functional layers may be additionally arranged on the sealing portion, in addition to the color filter and/or the color conversion layer, according to the utilize of the electronic apparatus. Non-limiting examples of the functional layers may include a touch screen layer, a polarizing layer, and/or the like. The touch screen layer may be a pressure-sensitive touch screen layer, a capacitive touch screen layer, or an infrared touch screen layer.
The authentication apparatus may be, for example, a biometric authentication apparatus that authenticates an individual by utilizing biometric information of a living body (e.g., fingertips, pupils, etc.). The authentication apparatus may further include, in addition to the light-emitting device as described above, a biometric information collector.
The electronic apparatus may be applied to one or more of displays, light sources, lighting, personal computers (e.g., a mobile personal computer), 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, one or more suitable measuring instruments, meters (e.g., meters for a vehicle, an aircraft, and a vessel), projectors, and/or the like.
The light-emitting device may be included in one or more suitable electronic equipment.
For example, the electronic equipment including the light-emitting device may be at least one of a flat panel display, a curved display, a computer monitor, a medical monitor, a television, a billboard, an indoor or outdoor light and/or light for signal, a head-up display, a fully or 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 PDA, a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro display, a 3D display, a virtual reality or augmented reality display, a vehicle, a video wall with multiple displays tiled together, a theater or stadium screen, a phototherapy device, or a signboard.
Because the light-emitting device of the present disclosure has excellent or suitable effects in terms of luminescence efficiency and long lifespan, the electronic equipment including the light-emitting device may have characteristics with high luminance, high resolution, and low power consumption.
The 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 on the substrate 100. The buffer layer 210 may prevent or reduce penetration of impurities through the substrate 100 and may provide a flat surface on the substrate 100.
The TFT may be on the buffer layer 210. The TFT may include an activation layer 220, a gate electrode 240, a source electrode 260, and a drain electrode 270.
The activation layer 220 may include an inorganic semiconductor such as silicon or polysilicon, an organic semiconductor, or an oxide semiconductor, and may include a source region, a drain region, and a channel region.
A gate insulating film 230 for insulating the activation layer 220 from the gate electrode 240 may be on the activation layer 220, and the gate electrode 240 may be on the gate insulating film 230.
An interlayer insulating film 250 may be 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 from one another.
The source electrode 260 and the drain electrode 270 may be on the interlayer insulating film 250. The interlayer insulating film 250 and the gate insulating film 230 may be formed to expose the source region and the drain region of the activation layer 220, and the source electrode 260 and the drain electrode 270 may be arranged in contact with the exposed portions of the source region and the drain region of the activation layer 220, respectively.
The TFT may be electrically connected to the light-emitting device to drive the 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 any combination thereof. The light-emitting device may be provided on the passivation layer 280. The light-emitting device may include a first electrode 110, an interlayer 130, and a second electrode 150.
The first electrode 110 may be on the passivation layer 280. The passivation layer 280 may be arranged to expose a portion of the drain electrode 270, not fully covering the drain electrode 270, and the first electrode 110 may be arranged to be connected to the exposed portion of the drain electrode 270.
A pixel defining layer 290 including an insulating material may be on the first electrode 110. The pixel defining layer 290 may expose a certain region of the first electrode 110, and the interlayer 130 may be formed in 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. In some embodiments, at least some layers of the interlayer 130 may extend beyond the upper portion of the pixel defining layer 290 to be arranged in the form of a common layer.
The second electrode 150 may be on the interlayer 130, and a second capping layer 170 may be additionally formed on the second electrode 150. The second capping layer 170 may be formed to cover the second electrode 150.
The encapsulation portion 300 may be on the second capping layer 170. The encapsulation portion 300 may be arranged on the light-emitting device to protect the light-emitting device from moisture and/or oxygen. The encapsulation portion 300 may include: an inorganic film including silicon nitride (SiNx), silicon oxide (SiOx), indium tin oxide, indium zinc oxide, or any combination thereof; an organic film including polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyethylene sulfonate, polyoxymethylene, polyarylate, hexamethyldisiloxane, an acrylic resin (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 light-emitting apparatus of
The electronic equipment 1 may include a display area DA and a non-display area NDA outside the display area DA. A display device of the electronic equipment 1 may implement an image through an array of a plurality of pixels that are two-dimensionally arranged in the display area DA.
The non-display area NDA is an area that does not display an image, and may entirely surround the display area DA. On the non-display area NDA, a driver for providing electrical signals or power to display devices arranged on the display area DA may be arranged. On the non-display area NDA, a pad, which is an area to which an electronic element or a printing circuit board may be electrically connected, may be arranged.
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 some embodiments, as shown in
Referring to
In one or more embodiments, the vehicle 1000 may travel on a road or a track. The vehicle 1000 may move in a set or predetermined direction according to the rotation of at least one wheel thereof. For example, the vehicle 1000 may include a three-wheeled or four-wheeled vehicle, a construction machine, a two-wheeled vehicle, a prime mover device, a bicycle, or a train running on a track.
The vehicle 1000 may include a body having an interior and an exterior, and a chassis in which mechanical apparatuses necessary for driving are installed as other parts except for the body. The exterior of the vehicle body may include a front panel, a bonnet, a roof panel, a rear panel, a trunk, a pillar provided at a boundary between doors, and/or 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 and rear wheels, left and right wheels, and/or 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 some embodiments, the side window glass 1100 may be installed on a door of the vehicle 1000. A plurality of side window glasses 1100 may be provided and may face each other. In some embodiments, the side window glass 1100 may include a first side window glass 1110 and a second side window glass 1120. In some embodiments, the first side window glass 1110 may be arranged adjacent to the cluster 1400. The second side window glass 1120 may be arranged adjacent to the passenger seat dashboard 1600.
In one or more embodiments, the side window glasses 1100 may be spaced apart from each other in the x-direction or the −x-direction. For example, in some embodiments, 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. In other words, an imaginary straight line L connecting the side window glasses 1100 may extend in the x-direction or the −x-direction. For example, in some embodiments, an imaginary 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 the 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 vehicle body. In an embodiment, a plurality of side mirrors 1300 may be provided. Any one of the plurality of side mirrors 1300 may be arranged outside the first side window glass 1110. The other one of the plurality of 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 turn indicator, a high beam indicator, a warning light, a seat belt warning light, an odometer, a hodometer, an automatic shift selector indicator, 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 a plurality of buttons for adjusting an audio device, an air conditioning device, and/or a heater of a seat are arranged. The center fascia 1500 may be arranged on one side of the cluster 1400.
The passenger seat dashboard 1600 may be spaced apart from the cluster 1400 with the center fascia 1500 arranged therebetween. In some embodiments, the cluster 1400 may be arranged to correspond to a driver seat, and the passenger seat dashboard 1600 may be arranged to correspond to a passenger seat. In some embodiments, 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 one or more embodiments, 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 some embodiments, 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, or the passenger seat dashboard 1600.
The display device 2 may include an organic light-emitting display device, an inorganic light-emitting display device, a quantum dot display device, and/or the like. Hereinafter, as the display device 2 according to one or more embodiments, an organic light-emitting display apparatus including the aforementioned light-emitting device will be described as an example, but one or more suitable types (kinds) of the aforementioned display apparatus may be utilized in embodiments.
Referring to
Referring to
Referring to
Respective layers included in the hole transport region, the emission layer, and respective layers included in the electron transport region may be formed in a certain region by utilizing one or more suitable methods such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) deposition, ink-jet printing, laser-printing, laser-induced thermal imaging, and/or the like.
When respective layers included in the hole transport region, the emission layer, and respective layers included in the electron transport region are each formed by vacuum deposition, the deposition may be performed at a deposition temperature of about 100° C. to about 500° C., a vacuum degree of about 10−8 torr to about 10-3 torr, and a deposition speed of about 0.01 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 utilized herein refers to a cyclic group including (e.g., consisting of) carbon only as a ring-forming atom and having 3 to 60 carbon atoms, and the term “C1-C60 heterocyclic group” as utilized herein refers to a cyclic group that has 1 to 60 carbon atoms and further has, in addition to carbon, a heteroatom as a ring-forming atom. The C3-C60 carbocyclic group and the C1-C60 heterocyclic group may each be a monocyclic group including (e.g., consisting of) one (e.g., only 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 of the C1-C60 heterocyclic group may be from 3 to 61.
The term “cyclic group” as utilized herein may include both (e.g., simultaneously) the C3-C60 carbocyclic group and the C1-C60 heterocyclic group.
The term “π electron-rich C3-C60 cyclic group” as utilized herein refers to a cyclic group that has 3 to 60 carbon atoms and does not include *—N═*′ as a ring-forming moiety, and the term “π electron-deficient nitrogen-containing C1-C60 heterocyclic group” as utilized herein refers to a heterocyclic group that has 1 to 60 carbon atoms and includes *—N═*′ as a ring-forming moiety.
For example,
The term “cyclic group,” “C3-C60 carbocyclic group,” “C1-C60 heterocyclic group,” “π electron-rich C3-C60 cyclic group,” or “π electron-deficient nitrogen-containing C1-C60 heterocyclic group” as utilized herein may refer to a group condensed to any cyclic group, a monovalent group, or a polyvalent group (e.g., a divalent group, a trivalent group, a tetravalent group, etc.) according to the structure of a formula for which the corresponding term is utilized. For example, the “benzene group” may be a benzo group, a phenyl group, a phenylene group, and/or the like, which may be easily understood by one of ordinary skill in the art according to the structure of a formula including the “benzene group.”
Depending on context, in the present disclosure, a divalent group may refer or be a polyvalent group (e.g., trivalent, tetravalent, etc., and not just divalent) per, e.g., the structure of a formula in connection with which of the terms are utilized.
Non-limiting examples of the monovalent C3-C60 carbocyclic group and the monovalent C1-C60 heterocyclic group may be 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. Non-limiting examples of the divalent C3-C60 carbocyclic group and the divalent C1-C60 heterocyclic group may be a C3-C10 cycloalkylene group, a C1-C10 heterocycloalkylene group, a C3-C10 cycloalkenylene group, a C1-C10 heterocycloalkenylene group, a C6-C60 arylene group, a C1-C60 heteroarylene group, a divalent non-aromatic condensed polycyclic group, and a substituted or unsubstituted divalent non-aromatic condensed heteropolycyclic group.
The term “C1-C60 alkyl group” as utilized herein refers to a linear or branched aliphatic hydrocarbon monovalent group that has 1 to 60 carbon atoms, and non-limiting examples thereof may be 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, a tert-decyl group, and/or the like. The term “C1-C60 alkylene group” as utilized herein refers to a divalent group having substantially the same structure as the C1-C60 alkyl group.
The term “C2-C60 alkenyl group” as utilized herein refers to a monovalent hydrocarbon group having at least one carbon-carbon double bond in the middle or at the terminus of a C2-C60 alkyl group, and non-limiting examples thereof may be an ethenyl group, a propenyl group, a butenyl group, and/or the like. The term “C2-C60 alkenylene group” as utilized herein refers to a divalent group having substantially the same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as utilized herein refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond in the middle or at the terminus of a C2-C60 alkyl group, and non-limiting examples thereof may be an ethynyl group, a propynyl group, and/or the like. The term “C2-C60 alkynylene group” as utilized herein refers to a divalent group having substantially the same structure as the C2-C60 alkynyl group.
The term “C1-C60 alkoxy group” as utilized herein refers to a monovalent group represented by —OA101 (wherein A101 is a C1-C60 alkyl group), and non-limiting examples thereof may be a methoxy group, an ethoxy group, an isopropyloxy group, and/or the like.
The term “C3-C10 cycloalkyl group” as utilized herein refers to a monovalent saturated hydrocarbon cyclic group having 3 to 10 carbon atoms, and non-limiting 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/or the like. The term “C3-C10 cycloalkylene group” as utilized herein refers to a divalent group having substantially the same structure as the C3-C10 cycloalkyl group.
The term “C1-C10 heterocycloalkyl group” as utilized herein refers to a monovalent cyclic group of 1 to 10 carbon atoms, further including, in addition to carbon atoms, at least one heteroatom, as ring-forming atoms, and non-limiting examples thereof may be a 1,2,3,4-oxatriazolidinyl group, a tetrahydrofuranyl group, a tetrahydrothiophenyl group, and/or the like. The term “C1-C10 heterocycloalkylene group” as utilized herein refers to a divalent group having substantially the same structure as the C1-C10 heterocycloalkyl group.
The term “C3-C10 cycloalkenyl group” as utilized herein refers to a monovalent cyclic group that has three to ten carbon atoms and at least one carbon-carbon double bond in the ring thereof and no aromaticity, and non-limiting examples thereof may be a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and/or the like. The term “C3-C10 cycloalkenylene group” as utilized herein refers to a divalent group having substantially the same structure as the C3-C10 cycloalkenyl group.
The term “C1-C10 heterocycloalkenyl group” as utilized herein refers to a monovalent cyclic group of 1 to 10 carbon atoms, further including, in addition to carbon atoms, at least one heteroatom, as ring-forming atoms, and having at least one carbon-carbon double bond in the cyclic structure thereof. Non-limiting examples of the C1-C10 heterocycloalkenyl group may be a 4,5-dihydro-1,2,3,4-oxatriazolyl group, a 2,3-dihydrofuranyl group, a 2,3-dihydrothiophenyl group, and/or the like. The term “C1-C10 heterocycloalkenylene group” as utilized herein refers to a divalent group having substantially the same structure as the C1-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as utilized herein refers to a monovalent group having a carbocyclic aromatic system of 6 to 60 carbon atoms, and the term “C6-C60 arylene group” as utilized herein refers to a divalent group having a carbocyclic aromatic system of 6 to 60 carbon atoms. Non-limiting examples of the C6-C60 aryl group may be 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/or the like. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the rings may be condensed with each other.
The term “C1-C60 heteroaryl group” as utilized herein refers to 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 utilized herein refers to 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. Non-limiting examples of the C1-C60 heteroaryl group may be 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/or the like. When the C1-C60 heteroaryl group and the C1-C60 heteroarylene group each include two or more rings, the rings may be condensed with each other.
The term “monovalent non-aromatic condensed polycyclic group” as utilized herein refers to a monovalent group (e.g., having 8 to 60 carbon atoms) having two or more rings condensed to each other, only carbon atoms as ring-forming atoms, and no aromaticity in its entire molecular structure as a whole. Non-limiting examples of the monovalent non-aromatic condensed polycyclic group may be an indenyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, an indenophenanthrenyl group, an indeno anthracenyl group, and/or the like. The term “divalent non-aromatic condensed polycyclic group” as utilized herein refers to a divalent group having substantially the same structure as the monovalent non-aromatic condensed polycyclic group.
The term “monovalent non-aromatic hetero-condensed polycyclic group” as utilized herein refers to a monovalent group (e.g., having 1 to 60 carbon atoms) having two or more rings condensed to each other, further including, in addition to carbon atoms, at least one heteroatom, as ring-forming atoms, and having non-aromaticity in its entire molecular structure as a whole. Non-limiting examples of the monovalent non-aromatic hetero-condensed polycyclic group may be 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, a benzothienodibenzothiophenyl group, and/or the like. The term “divalent non-aromatic hetero-condensed polycyclic group” as utilized herein refers to a divalent group having substantially the same structure as the monovalent non-aromatic hetero-condensed polycyclic group.
The term “C6-C60 aryloxy group” as utilized herein refers to —OA102 (wherein A102 is a C6-C60 aryl group), and the term “C6-C60 arylthio group” as utilized herein refers to —SA103 (wherein A103 is a C6-C60 aryl group).
The term “C7-C60 arylalkyl group” as utilized herein refers to -A104A105 (wherein A104 is a C1-C54 alkylene group, and A105 is a C6-C59 aryl group), and the term “C2-C60 heteroarylalkyl group” as utilized herein refers to -A106A107 (wherein A106 is a C1-C59 alkylene group, and A107 is a C1-C59 heteroaryl group).
The term “R10a” as utilized herein may be:
In the present disclosure, Q1 to Q3, Q11 to Q13, Q21 to Q23, and Q31 to Q33 may each independently be: hydrogen; deuterium; —F; —Cl; —Br; —I; a hydroxyl group; a cyano group; a nitro group; a C1-C60 alkyl group; a C2-C60 alkenyl group; a C2-C60 alkynyl group; a C1-C60 alkoxy group; a C3-C60 carbocyclic group or a C1-C60 heterocyclic group, each unsubstituted or substituted with deuterium, —F, a cyano group, a C1-C60 alkyl group, a C1-C60 alkoxy group, a phenyl group, a biphenyl group, or any combination thereof; a C7-C60 arylalkyl group; or a C2-C60 heteroarylalkyl group.
The term “heteroatom” as utilized herein refers to any atom other than a carbon atom. Non-limiting examples of the heteroatom may include O, S, N, P, Si, B, Ge, Se, or any combination thereof.
The term “transition metal” as utilized herein may include hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and/or the like.
“Ph” as utilized herein refers to a phenyl group, “Me” as utilized herein refers to a methyl group, “Et” as utilized herein refers to an ethyl group, “tert-Bu” or “But” as utilized herein refers to a tert-butyl group, and “OMe” as utilized herein refers to a methoxy group.
The term “biphenyl group” as utilized herein refers to “a phenyl group substituted with a phenyl group.” In some embodiments, the “biphenyl group” may be a substituted phenyl group having a C6-C60 aryl group as a substituent.
The term “terphenyl group” as utilized herein refers to “a phenyl group substituted with a biphenyl group.” In some embodiments, the “terphenyl group” may be a substituted phenyl group having, as a substituent, a C6-C60 aryl group substituted with a C6-C60 aryl group.
* and *′ as utilized herein, unless defined otherwise, each refer to a binding site to a neighboring atom in a corresponding formula or moiety.
In the present disclosure, the x-axis, y-axis, and z-axis are not limited to three axes in an orthogonal coordinate system, and may be interpreted in a broad sense including these axes. For example, the x-axis, y-axis, and z-axis may refer to those orthogonal to each other, or may refer to those in different directions that are not orthogonal to each other.
Hereinafter, compounds according to one or more embodiments and light-emitting devices according to one or more embodiments will be described in more detail with reference to the following Synthesis Examples and Examples. The wording “B was utilized instead of A” utilized in describing Synthesis Examples refers to that an identical molar equivalent of B was utilized in place of A.
2-bromo-5-methoxyaniline (1.2 eq), 1-bromo-2-iodobenzene (1.0 eq), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) (5 mol %), [1,1′-binaphthalene]-2,2′-diyl)bis(diphenylphosphane) (BINAP) (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M) and then stirred at 110° C. for 15 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature, subjected to reduced pressure of 8 mbar to remove the toluene solvent therefrom, and then subjected to an extraction process three times by utilizing dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of methylene chloride (MC):hexane (as an eluent) was 1:4) to thereby synthesize Intermediate Compound 1-a (yield of 91%).
In a nitrogen atmosphere, NaH (1.1 eq) was added to dimethylformamide (DMF) (0.3 M) and stirred at room temperature. Intermediate compound 1-a (1.0 eq) dissolved in DMF (0.3 M) was added thereto, followed by stirring at room temperature for 1 hour. 4-methoxybenzyl chloride (1.0 eq) dissolved in DMF (0.3 M) was added thereto, followed by stirring at room temperature for 15 hours to obtain a reaction mixture. Water was added to the reaction mixture, and the precipitated solid was filtered. The filtered solid was subjected to an extraction process by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 1-b (yield of 85%).
In a nitrogen atmosphere, Intermediate Compound 1-b (1.0 eq) was dissolved in ether (0.5 M). The reaction mixture was cooled to 0° C., and 2.5 M n-butylithium in hexane (2.0 eq) was added thereto, followed by stirring at 0° C. for 30 minutes. Then, 5,5-dichloro-5H-dibenzo[b,d]silole (1.1 eq) dissolved in ether (0.5 M) was added thereto, followed by stirring at room temperature for 2 hours. The reaction mixture was distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and subjected to an extraction process three times by utilizing ethyl acetate (EA) and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 1-c (yield of 87%).
Intermediate Compound 1-c (1.0 eq) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (1.0 eq) were dissolved in a mixed solution of toluene and H2O (at a volume ratio of 10:1) (0.1 M) and then stirred at 80° C. for 15 hours. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove toluene therefrom, and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:4) to thereby synthesize Intermediate Compound 1-d (yield of 78%).
Intermediate Compound 1-d (1.0 eq), 2-bromo-4-(tert-butyl)pyridine (1.1 eq), Pd2(dba)3 (5 mol %), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (Sphos) (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M) and then stirred at 110° C. for 12 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:9) to thereby synthesize Intermediate Compound 1-e (yield of 93%).
Intermediate Compound 1-e (1.0 eq), HBr (0.5 M), and acetic acid (0.5 M) were stirred at 120° C. for 12 hours. The reaction mixture was cooled at room temperature, neutralized to pH 4 by utilizing a NaOH aqueous solution, and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate to thereby synthesize Intermediate Compound 1-f (yield of 75%).
1,3-dibromobenzene (1.5 eq), Intermediate Compound 1-f (1.0 eq), CuI (10 mol %), 2-picolinic acid (20 mol %), and potassium phosphate tribasic (2.0 eq) were dissolved in dimethyl sulfoxide (DMSO) (0.1 M) and then stirred at 100° C. for 4 hours. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 1-g (yield of 61%).
2,5-dibromoaniline (1.5 eq), phenyl-d5-boronic acid (1.0 eq), tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) (10 mol %), potassium carbonate (3.0 eq), and tetrabutylammonium bromide (20 mol %) were dissolved in a mixed solution of 1,4-dioxane and H2O (at a volume ratio of 4:1) (0.1 M) and then stirred at 100° C. for 12 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:20) to thereby synthesize Intermediate Compound 1-h (yield of 64%).
Intermediate Compound 1-h (1.0 eq), (3,5-di-tert-butylphenyl)boronic acid (1.1 eq), Pd(PPh3)4 (10 mol %), and potassium carbonate (3.0 eq) were dissolved in a mixed solution of 1,4-dioxane and H2O (at a volume ratio of 4:1) (0.1 M) and then stirred at 100° C. for 12 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:20) to thereby synthesize Intermediate Compound 1-i (yield of 86%).
Intermediate Compound 1-i (1.0 eq), 1-iodo-2-nitrobenzene (2.0 eq), Pd2(dba)3 (10 mol %), Sphos (15 mol %), and sodium tert-butoxide (3.0 eq) were dissolved in toluene (0.1 M) and then stirred at 110° C. for 15 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and then subjected to an extraction process three times by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:4) to thereby synthesize Intermediate Compound 1-j (yield of 75%).
Intermediate Compound 1-j (1.0 eq), Sn (4.5 eq), and HCl (7.5 eq) were dissolved in ethanol (0.1 M) and then stirred at 80° C. for 12 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then neutralized by utilizing a NaOH solution. The neutralized product was subjected to an extraction process by utilizing dichloromethane and water to obtain an organic layer, which was then filtered through celite/silica gel. The filtrate was dried by utilizing magnesium sulfate and then concentrated to thereby synthesize Intermediate Compound 1-k (yield of 98%).
Intermediate Compound 1-g (1.0 eq), Intermediate Compound 1-k (1.2 eq), Pd2(dba)3 (5 mol %), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in dioxane (0.1 M) and then stirred at 110° C. for 2 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and then subjected to an extraction process three times by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 1-l (yield of 88%).
Intermediate Compound 1-l (1.0 eq) was dissolved in triethyl orthoformate (30 eq), and 37% HCl (1.5 eq) was added thereto, followed by stirring at 80° C. for 18 hours to obtain a reaction mixture. After the reaction mixture was cooled at room temperature, triethyl orthoformate therein was concentrated, and an extraction process was performed thereon by utilizing MC and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:methanol (as an eluent) was 95:5) to thereby synthesize Intermediate Compound 1-m (yield of 92%).
Intermediate Compound 1-m (1.0 eq), potassium platinum(II) chloride (1.1 eq), and 2,6-lutidine (4.0 eq) were dissolved in 1,2-dichlorobenzene (0.05 M) and then stirred at 120° C. for 3 days under a nitrogen condition to obtain a reaction mixture. After the reaction mixture was cooled at room temperature, 1,2-dichlorobenzene therein was concentrated and removed, and an extraction process was performed thereon by utilizing dichloromethane and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 3:7) to thereby synthesize Compound 1 (yield of 41%).
In a nitrogen atmosphere, Intermediate Compound 1-b (1.0 eq) was dissolved in ether (0.5 M). The reaction mixture was cooled to 0° C., and 2.5 M n-butylithium in hexane (2.0 eq) was added thereto, followed by stirring at 0° C. for 30 minutes. Dichlorodiphenylsilane (1.1 eq) dissolved in ether (0.5 M) was added to the reaction mixture, followed by stirring at room temperature for 2 hours. The reaction mixture was distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 101-a (yield of 84%).
Intermediate Compound 101-a (1.0 eq) and DDQ (1.0 eq) were dissolved in a mixed solution of toluene and H2O (at a volume ratio of 10:1) (0.1 M) and then stirred at 80° C. for 15 hours. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove toluene therefrom, and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:4) to thereby synthesize Intermediate Compound 101-b (yield of 77%).
Intermediate Compound 101-b (1.0 eq), 2-bromo-4-(tert-butyl)pyridine (1.1 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M) and then stirred at 110° C. for 12 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:9) to thereby synthesize Intermediate Compound 101-c (yield of 92%).
Intermediate Compound 101-c (1.0 eq), HBr (0.5 M), and acetic acid (0.5 M) were stirred at 120° C. for 12 hours. The reaction mixture was cooled at room temperature, neutralized to pH 4 by utilizing a NaOH aqueous solution, and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate to thereby synthesize Intermediate Compound 101-d (yield of 79%).
1,3-dibromobenzene (1.5 eq), Intermediate Compound 101-d (1.0 eq), CuI (10 mol %), 2-picolinic acid (20 mol %), and potassium phosphate tribasic (2.0 eq) were dissolved in DMSO (0.1 M) and then stirred at 100° C. for 4 hours. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 101-e (yield of 60%).
Intermediate Compound 101-e (1.0 eq), Intermediate Compound 1-k (1.2 eq), Pd2(dba)3 (5 mol %), Xphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in dioxane (0.1 M) and then stirred at 110° C. for 2 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and then subjected to an extraction process three times by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 101-f (yield of 70%).
Intermediate Compound 101-f (1.0 eq) was dissolved in triethyl orthoformate (30 eq), and 37% HCl (1.5 eq) was added thereto, followed by stirring at 80° C. for 18 hours to obtain a reaction mixture. After the reaction mixture was cooled at room temperature, triethyl orthoformate therein was concentrated, and an extraction process was performed thereon by utilizing MC and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:methanol (as an eluent) was 95:5) to thereby synthesize Intermediate Compound 101-g (yield of 90%).
Intermediate Compound 101-g (1.0 eq), potassium platinum(II) chloride (1.1 eq), and 2,6-lutidine (4.0 eq) were dissolved in 1,2-dichlorobenzene (0.05 M) and then stirred at 120° C. for 3 days under a nitrogen condition to obtain a reaction mixture. After the reaction mixture was cooled at room temperature, 1,2-dichlorobenzene therein was concentrated and removed, and an extraction process was performed thereon by utilizing dichloromethane and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 3:7) to thereby synthesize Compound 101 (yield of 43%).
2-bromoaniline (1.2 eq), 2-bromo-1-chloro-3-iodo-5-methoxybenzene (1.0 eq), Pd2(dba)3 (5 mol %), BINAP (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M) and then stirred at 110° C. for 15 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature, subjected to reduced pressure of 8 mbar to remove the toluene solvent therefrom, and then subjected to an extraction process three times by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 128-a (yield of 85%).
In a nitrogen atmosphere, NaH (1.1 eq) was added to DMF (0.3 M) and stirred at room temperature. Intermediate compound 128-a (1.0 eq) dissolved in DMF (0.3 M) was added thereto, followed by stirring at room temperature for 1 hour. 4-methoxybenzyl chloride (1.0 eq) dissolved in DMF (0.3 M) was added thereto, followed by stirring at room temperature for 15 hours to obtain a reaction mixture. Water was added to the reaction mixture, and the precipitated solid was filtered. The filtered solid was subjected to an extraction process by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 128-b (yield of 86%).
In a nitrogen atmosphere, Intermediate Compound 128-b (1.0 eq) was dissolved in ether (0.5 M). The reaction mixture was cooled to 0° C., and 2.5 M n-butylithium in hexane (2.0 eq) was added thereto, followed by stirring at 0° C. for 30 minutes. Then, dichlorodiphenylsilane (1.1 eq) dissolved in ether (0.5 M) was added thereto, followed by stirring at room temperature for 2 hours. The reaction mixture was distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 128-c (yield of 80%).
Intermediate Compound 128-c (1.0 eq), chloro(1-tert-butyl-1H-inden-1-yl)(tri-tert-butylphosphine)palladium(II) (CX201) (5 mol %), pivalic acid (10 mol %), and potassium carbonate (2.0 eq) were dissolved in dimethylacetamide (DMAc) (0.1 M) and then stirred at 160° C. for 20 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:3) to thereby synthesize Intermediate Compound 128-d (yield of 66%).
Intermediate Compound 128-d (1.0 eq) and DDQ (1.0 eq) were dissolved in a mixed solution of toluene and H2O (at a volume ratio of 10:1) (0.1 M) and then stirred at 80° C. for 15 hours. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove toluene therefrom, and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:5) to thereby synthesize Intermediate Compound 128-e (yield of 78%).
(6-fluoro-4-methylpyridin-3-yl)boronic acid (1.0 eq), 1-bromo-4-(tert-butyl)benzene (1.2 eq), Pd(PPh3)4 (5 mol %), and K3PO4 (2.0 eq) were dissolved in a mixed solution of 1,4-dioxane and H2O (at a volume ratio of 4:1) (0.1 M) and then stirred at 100° C. for 15 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 128-f (yield of 91%).
Intermediate Compound 128-f (1.0 eq) and potassium tert-butoxide (2.0 eq) were dissolved in DMSO-d6 (0.5 M) and then stirred at 80° C. for 4 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:20) to thereby synthesize Intermediate Compound 128-g (yield of 89%).
Intermediate Compound 128-g (1.0 eq), Intermediate Compound 128-e (1.1 eq), and K3PO4 (2.0 eq) were dissolved in DMF (0.1 M) and then stirred at 160° C. for 12 hours. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove DMF therefrom, and then subjected to an extraction process three times by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 128-h (yield of 90%).
After Intermediate Compound 128-h (1.0 eq) was dissolved in MC (0.1 M), a 1.0 M BBr3 solution in MC (2.0 eq) was slowly added thereto, followed by stirring at 0° C. for 1 hour and then at room temperature for 2 hours. Distilled water (0.1 M) was added to the reaction mixture, followed by stirring at room temperature for 1 hour. Then, an extraction process was performed thereon by utilizing MC and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate to thereby synthesize Intermediate Compound 128-i (yield of 64%).
1,3-dibromobenzene (1.5 eq), Intermediate Compound 128-i (1.0 eq), CuI (10 mol %), 2-picolinic acid (20 mol %), and potassium phosphate tribasic (2.0 eq) were dissolved in DMSO (0.1 M) and then stirred at 100° C. for 4 hours. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 128-j (yield of 55%).
Intermediate Compound 128-j (1.0 eq), Intermediate Compound 1-k (1.2 eq), Pd2(dba)3 (5 mol %), Xphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in dioxane (0.1 M) and then stirred at 110° C. for 2 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and then subjected to an extraction process three times by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 128-k (yield of 70%).
Intermediate Compound 128-k (1.0 eq) was dissolved in triethyl orthoformate (30 eq), and 37% DCI (1.5 eq) was added thereto, followed by stirring at 80° C. for 18 hours to obtain a reaction mixture. After the reaction mixture was cooled at room temperature, triethyl orthoformate therein was distilled under reduced pressure of 8 mbar and concentrated, and an extraction process was performed thereon by utilizing MC and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:methanol (as an eluent) was 95:5) to thereby synthesize Intermediate Compound 128-l (yield of 94%).
Intermediate Compound 128-1 (1.0 eq), potassium platinum(II) chloride (1.1 eq), and 2,6-lutidine (4.0 eq) were dissolved in 1,2-dichlorobenzene (0.05 M) and then stirred at 120° C. for 3 days under a nitrogen condition to obtain a reaction mixture. After the reaction mixture was cooled at room temperature, 1,2-dichlorobenzene therein was concentrated and removed, and an extraction process was performed thereon by utilizing dichloromethane and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 3:7) to thereby synthesize Compound 128 (yield of 40%).
2-bromo-5-methoxyaniline (1.2 eq), 2-bromo-1-chloro-3-iodobenzene (1.0 eq), Pd2(dba)3 (5 mol %), BINAP (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M) and then stirred at 110° C. for 15 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature, subjected to reduced pressure of 8 mbar to remove the toluene solvent therefrom, and then subjected to an extraction process three times by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 157-a (yield of 90%).
In a nitrogen atmosphere, NaH (1.1 eq) was added to DMF (0.3 M) and stirred at room temperature. Intermediate compound 157-a (1.0 eq) dissolved in DMF (0.3 M) was added thereto, followed by stirring at room temperature for 1 hour. 4-methoxybenzyl chloride (1.0 eq) dissolved in DMF (0.3 M) was added thereto, followed by stirring at room temperature for 15 hours to obtain a reaction mixture. Water was added to the reaction mixture, and the precipitated solid was filtered. The filtered solid was subjected to an extraction process by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 157-b (yield of 86%).
In a nitrogen atmosphere, Intermediate Compound 157-b (1.0 eq) was dissolved in ether (0.5 M). The reaction mixture was cooled to 0° C., and 2.5 M n-butylithium in hexane (2.0 eq) was added thereto, followed by stirring at 0° C. for 30 minutes. Then, dichlorodiphenylsilane (1.1 eq) dissolved in ether (0.5 M) was added thereto, followed by stirring at room temperature for 2 hours. The reaction mixture was distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 157-c (yield of 79%).
Intermediate Compound 157-c (1.0 eq), CX201 (5 mol %), pivalic acid (10 mol %), and potassium carbonate (2.0 eq) were dissolved in DMAc (0.1 M) and then stirred at 160° C. for 20 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:3) to thereby synthesize Intermediate Compound 157-d (yield of 70%).
Intermediate Compound 157-d (1.0 eq) and DDQ (1.0 eq) were dissolved in a mixed solution of toluene and H2O (at a volume ratio of 10:1) (0.1 M) and then stirred at 80° C. for 15 hours. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove toluene therefrom, and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:5) to thereby synthesize Intermediate Compound 157-e (yield of 78%).
Intermediate Compound 157-e (1.0 eq), 2-bromo-4-(tert-butyl)pyridine (1.1 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M) and then stirred at 110° C. for 12 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:9) to thereby synthesize Intermediate Compound 157-f (yield of 92%).
Intermediate Compound 157-f (1.0 eq), HBr (0.5 M), and acetic acid (0.5 M) were stirred at 120° C. for 12 hours. The reaction mixture was cooled at room temperature, neutralized to pH 4 by utilizing a NaOH aqueous solution, and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate to thereby synthesize Intermediate Compound 157-g (yield of 75%).
1,3-dibromo-5-(tert-butyl)benzene (1.5 eq), Intermediate Compound 157-g (1.0 eq), CuI (10 mol %), 2-picolinic acid (20 mol %), and potassium phosphate tribasic (2.0 eq) were dissolved in DMSO (0.1 M) and then stirred at 100° C. for 4 hours. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 157-h (yield of 65%).
Intermediate Compound 157-h (1.0 eq), Intermediate Compound 1-k (1.2 eq), Pd2(dba)3 (5 mol %), Xphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in dioxane (0.1 M) and then stirred at 110° C. for 2 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and then subjected to an extraction process three times by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 157-i (yield of 73%).
Intermediate Compound 157-i (1.0 eq) was dissolved in triethyl orthoformate (30 eq), and 37% HCl (1.5 eq) was added thereto, followed by stirring at 80° C. for 18 hours to obtain a reaction mixture. After the reaction mixture was cooled at room temperature, triethyl orthoformate therein was distilled under reduced pressure of 8 mbar and concentrated, and an extraction process was performed thereon by utilizing MC and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:methanol (as an eluent) was 95:5) to thereby synthesize Intermediate Compound 157-j (yield of 90%).
Intermediate Compound 157-j (1.0 eq), potassium platinum(II) chloride (1.1 eq), and 2,6-lutidine (4.0 eq) were dissolved in 1,2-dichlorobenzene (0.05 M) and then stirred at 120° C. for 3 days under a nitrogen condition to obtain a reaction mixture. After the reaction mixture was cooled at room temperature, 1,2-dichlorobenzene therein was concentrated and removed, and an extraction process was performed thereon by utilizing dichloromethane and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 3:7) to thereby synthesize Compound 157 (yield of 40%).
In a nitrogen atmosphere, Intermediate Compound 1-b (1.0 eq) was dissolved in ether (0.5 M). The reaction mixture was cooled to 0° C., and 2.5 M n-butylithium in hexane (2.0 eq) was added thereto, followed by stirring at 0° C. for 30 minutes. Dichlorodimethylsilane (1.1 eq) dissolved in ether (0.5 M) was added to the reaction mixture, followed by stirring at room temperature for 2 hours. The reaction mixture was distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 161-a (yield of 88%).
Intermediate Compound 161-a (1.0 eq) and DDQ (1.0 eq) were dissolved in a mixed solution of toluene and H2O (at a volume ratio of 10:1) (0.1 M) and then stirred at 80° C. for 15 hours. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove toluene therefrom, and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:4) to thereby synthesize Intermediate Compound 161-b (yield of 75%).
Intermediate Compound 161-b (1.0 eq), 2-bromo-4-(tert-butyl)pyridine (1.1 eq), Pd2(dba)3 (5 mol %), Sphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in toluene (0.1 M) and then stirred at 110° C. for 12 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:9) to thereby synthesize Intermediate Compound 161-c (yield of 84%).
Intermediate Compound 161-c (1.0 eq), HBr (0.5 M), and acetic acid (0.5 M) were stirred at 120° C. for 12 hours. The reaction mixture was cooled at room temperature, neutralized to pH 4 by utilizing a NaOH aqueous solution, and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate to thereby synthesize Intermediate Compound 161-d (yield of 78%).
1,3-dibromobenzene (1.5 eq), Intermediate Compound 161-d (1.0 eq), CuI (10 mol %), 2-picolinic acid (20 mol %), and K3PO4 (2.0 eq) were dissolved in DMSO (0.1 M) and then stirred at 100° C. for 4 hours. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 161-e (yield of 60%).
Intermediate Compound 161-e (1.0 eq), Intermediate Compound 1-k (1.2 eq), Pd2(dba)3 (5 mol %), Xphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in dioxane (0.1 M) and then stirred at 110° C. for 2 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and then subjected to an extraction process three times by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 161-f (yield of 85%).
Intermediate Compound 161-f (1.0 eq) was dissolved in triethyl orthoformate (30 eq), and 37% HCl (1.5 eq) was added thereto, followed by stirring at 80° C. for 18 hours to obtain a reaction mixture. After the reaction mixture was cooled at room temperature, triethyl orthoformate therein was concentrated, and an extraction process was performed thereon by utilizing MC and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:methanol (as an eluent) was 95:5) to thereby synthesize Intermediate Compound 161-g (yield of 90%).
Intermediate Compound 161-g (1.0 eq), potassium platinum(II) chloride (1.1 eq), and 2,6-lutidine (4.0 eq) were dissolved in 1,2-dichlorobenzene (0.05 M) and then stirred at 120° C. for 3 days under a nitrogen condition to obtain a reaction mixture. After the reaction mixture was cooled at room temperature, 1,2-dichlorobenzene therein was concentrated and removed, and an extraction process was performed thereon by utilizing dichloromethane and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 3:7) to thereby synthesize Compound 161 (yield of 40%).
2-bromo-4-(tert-butyl)aniline (1.0 eq), phenyl-d5-boronic acid (1.2 eq), Pd(PPh3)4 (5 mol %), and potassium carbonate (2.0 eq) were dissolved in a mixed solution of 1,4-dioxane and H2O (at a volume ratio of 3:1) (0.1 M) and then stirred at 100° C. for 12 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:20) to thereby synthesize Intermediate Compound 163-a (yield of 91%).
After Intermediate Compound 163-a (1.0 eq) was dissolved in MC (0.1 M) at 0° C., N-bromosuccinimide (NBS) (1.1 eq) was added thereto, followed by stirring at room temperature for 2 hours. The reaction mixture was distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and subjected to an extraction process three times by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:20) to thereby synthesize Intermediate Compound 163-b (yield of 90%).
Intermediate Compound 163-b (1.0 eq), (3,5-di-tert-butylphenyl)boronic acid (1.2 eq), Pd(PPh3)4 (5 mol %), and K2C03 (2.0 eq) were dissolved in a mixed solution of 1,4-dioxane and H2O (at a volume ratio of 4:1) (0.1 M) and then stirred at 100° C. for 12 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then subjected to an extraction process three times by utilizing EA and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of EA:hexane (as an eluent) was 1:20) to thereby synthesize Intermediate Compound 163-c (yield of 85%).
Intermediate Compound 163-c (1.0 eq), 1-iodo-2-nitrobenzene (2.0 eq), Pd2(dba)3 (10 mol %), Sphos (15 mol %), and sodium tert-butoxide (3.0 eq) were dissolved in toluene (0.1 M) and then stirred at 110° C. for 15 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and then subjected to an extraction process three times by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:4) to thereby synthesize Intermediate Compound 163-d (yield of 78%).
Intermediate Compound 163-d (1.0 eq), Sn (4.5 eq), and HCl (7.5 eq) were dissolved in ethanol (0.1 M) and then stirred at 80° C. for 12 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature and then neutralized by utilizing a NaOH solution. The neutralized product was subjected to an extraction process by utilizing dichloromethane and water to obtain an organic layer, which was then filtered through celite/silica gel. The filtrate was dried by utilizing magnesium sulfate and then concentrated to thereby synthesize Intermediate Compound 163-e (yield of 98%).
Intermediate Compound 161-e (1.0 eq), Intermediate Compound 163-e (1.2 eq), Pd2(dba)3 (5 mol %), Xphos (7 mol %), and sodium tert-butoxide (2.0 eq) were dissolved in dioxane (0.1 M) and then stirred at 110° C. for 2 hours to obtain a reaction mixture. The reaction mixture was cooled at room temperature, distilled under reduced pressure of 8 mbar to remove the solvent therefrom, and then subjected to an extraction process three times by utilizing MC and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 1:10) to thereby synthesize Intermediate Compound 163-f (yield of 83%).
Intermediate Compound 163-f (1.0 eq) was dissolved in triethyl orthoformate (30 eq), and 37% HCl (1.5 eq) was added thereto, followed by stirring at 80° C. for 18 hours to obtain a reaction mixture. After the reaction mixture was cooled at room temperature, triethyl orthoformate therein was concentrated, and an extraction process was performed thereon by utilizing MC and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:methanol (as an eluent) was 95:5) to thereby synthesize Intermediate Compound 163-g (yield of 91%).
Intermediate Compound 163-g (1.0 eq), potassium platinum(II) chloride (1.1 eq), and 2,6-lutidine (4.0 eq) were dissolved in 1,2-dichlorobenzene (0.05 M) and then stirred at 120° C. for 3 days under a nitrogen condition to obtain a reaction mixture. After the reaction mixture was cooled at room temperature, 1,2-dichlorobenzene therein was concentrated and removed, and an extraction process was performed thereon by utilizing dichloromethane and water three times to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate, concentrated, and then subjected to column chromatography (a volume ratio of MC:hexane (as an eluent) was 3:7) to thereby synthesize Compound 163 (yield of 40%).
1H nuclear magnetic resonance spectroscopy (NMR) and mass spectroscopy/fast atom bombardment (MS/FAB) of the compounds synthesized according to Synthesis Examples are shown in Table 1. Synthesis methods of compounds other than the compounds synthesized in Synthesis Examples above may be easily recognized by those skilled in the art by referring to the synthesis paths and source materials.
1H NMR (CDCl3, 400 MHz)
For Compounds 1, 101, 128, 157, 161, and 163 and Compounds CE1 to CE5, the HOMO energy level (eV), LUMO energy level (eV), simulation (calculation) maximum emission wavelength (λmaxsim), actual maximum emission wavelength (λmaxexp) and existence ratio of 3MLCT (triplet metal-to-ligand charge transfer) (%) were each evaluated utilizing the density functional theory (DFT) method of the Gaussian program, which was structure-optimized at the B3LYP/6-31 G(d,p) level, and results thereof are shown in Table 2.
3MLCT
As an anode, a glass substrate with 15 Ω/cm2 (1,200 Å) ITO deposited thereon (product of Corning Inc.) was cut to a size of 50 mm×50 mm×0.7 mm, sonicated with isopropyl alcohol and (then with) pure water each for 5 minutes, and then cleaned by irradiation of ultraviolet rays and exposure of ozone thereto for 30 minutes. Then, the ITO glass substrate was mounted on a vacuum deposition apparatus.
2-TNATA was vacuum-deposited on the substrate 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.
3,3-di(9H-carbazol-9-yl)biphenyl (mCBP) as a host and Compound 1 as a dopant were co-deposited on the hole transport layer at a weight ratio of 90:10 to form an emission layer having a thickness of 300 Å.
Diphenyl(4-(triphenylsilyl)phenyl)-phosphine oxide (TSPO1) was vacuum-deposited on the emission layer to form a hole blocking layer having a thickness of 50 Å, and Alq3 was deposited on the hole blocking layer to form an electron transport layer having a thickness of 300 Å. LiF as an alkali metal halide was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and Al was vacuum-deposited on the electron injection layer to form a LiF/Al cathode having a thickness of 3,000 Å, thereby completing the manufacture of a light-emitting device.
Light-emitting devices were each manufactured in substantially the same manner as in Example 1, except that Compound 1 as a dopant was changed as shown in Table 3 in forming an emission layer.
The driving voltage (V), efficiency (cd/A), color conversion efficiency (cd/A/y), maximum emission wavelength (nm), and device lifespan (h) of each of the light-emitting devices manufactured according to Examples 1 to 6 and Comparative Examples 1 to 5 at a luminance of 1,000 cd/m2 were measured by utilizing Keithley SMU 236 and luminance meter PR650, and results thereof are shown in Table 3. In Table 3, the device lifespan (T95) is a measure of the time (h) taken until the luminance declines to 95% of the initial luminance.
From Table 3, it was confirmed that the light-emitting devices according to Examples 1 to 6 each had superior driving voltage, luminescence efficiency, and device lifespan compared to those of the light-emitting devices according to Comparative Examples 1 to 5.
According to the one or more embodiments, by utilizing the organometallic compound of the present disclosure, a light-emitting device having decreased driving voltage, improved color purity and efficiency, and increased lifespan and a high-quality electronic apparatus including the light-emitting device may be manufactured.
In the present disclosure, it will be understood that the terms “comprise(s),” “include(s),” or “have/has” specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
Throughout the present disclosure, when a component such as a layer, a film, a region, or a plate is mentioned to be placed “on” another component, it will be understood that it may be directly on another component or that another component may be interposed therebetween. In some embodiments, “directly on” may refer to that there are no additional layers, films, regions, plates, etc., between a layer, a film, a region, a plate, etc. and the other part. For example, “directly on” may refer to two layers or two members are disposed without utilizing an additional member such as an adhesive member therebetween.
In the present disclosure, although the terms “first,” “second,” etc., may be utilized herein to describe one or more elements, components, regions, and/or layers, these elements, components, regions, and/or layers should not be limited by these terms. These terms are only utilized to distinguish one component from another component.
As utilized herein, the singular forms “a,” “an,” “one,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. Further, the use of “may” when describing embodiments of the present disclosure refers to “one or more embodiments of the present disclosure”.
As utilized herein, the terms “substantially,” “about,” or similar terms are used as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art. “About” as used herein, is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” may mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.
Any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range. For example, a range of “1.0 to 10.0” is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein.
In the present disclosure, when particles are spherical, “size” indicates a particle diameter or an average particle diameter, and when the particles are non-spherical, the “size” indicates a major axis length or an average major axis length. The diameter (or size) of the particles may be measured utilizing a scanning electron microscope or a particle size analyzer. As the particle size analyzer, for example, HORIBA, LA-950 laser particle size analyzer, may be utilized. When the size of the particles is measured utilizing a particle size analyzer, the average particle diameter (or size) is referred to as D50. D50 refers to the average diameter (or size) of particles whose cumulative volume corresponds to 50 vol % in the particle size distribution (e.g., cumulative distribution), and refers to the value of the particle size corresponding to 50% from the smallest particle when the total number of particles is 100% in the distribution curve accumulated in the order of the smallest particle size to the largest particle size.
The light-emitting device, the light-emitting apparatus, the display device, the electronic apparatus, the electronic device, or any other relevant devices or components according to embodiments of the present disclosure described herein may be implemented utilizing any suitable hardware, firmware (e.g., an application-specific integrated circuit), software, or a combination of software, firmware, and hardware. For example, the various components of the device may be formed on one integrated circuit (IC) chip or on separate IC chips. Further, the various components of the device may be implemented on a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or formed on one substrate. Further, the various components of the device may be a process or thread, running on one or more processors, in one or more computing devices, executing computer program instructions and interacting with other system components for performing the various functionalities described herein. The computer program instructions are stored in a memory which may be implemented in a computing device using a standard memory device, such as, for example, a random access memory (RAM). The computer program instructions may also be stored in other non-transitory computer readable media such as, for example, a CD-ROM, flash drive, or the like. Also, a person of skill in the art should recognize that the functionality of various computing devices may be combined or integrated into a single computing device, or the functionality of a particular computing device may be distributed across one or more other computing devices without departing from the scope of the embodiments of the present disclosure.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the drawings, it will be understood by those of ordinary skill in the art that one or more suitable changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims and equivalents thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2023-0038973 | Mar 2023 | KR | national |
| 10-2023-0053528 | Apr 2023 | KR | national |
