Patent Grant
11912724
This application claims priority to and the benefit of Korean Patent Applications Nos. 10-2021-0016842, filed on Feb. 5, 2021, and 10-2022-0006178, filed on Jan. 14, 2022 in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. § 119, the content of which are incorporated by reference herein in their entireties.
One or more embodiments relate to an organometallic compound, an organic light-emitting device including the same, and an electronic apparatus including the organic light-emitting device.
Organic light-emitting devices (OLEDs) are self-emissive devices, which have improved characteristics in terms of viewing angles, response time, luminance, driving voltage, and response speed, and produce full-color images.
In an example, an organic light-emitting device includes an anode, a cathode, and an organic layer between the anode and the cathode, wherein the organic layer includes an emission layer. A hole transport region may be located between the anode and the emission layer, and an electron transport region may be located between the emission layer and the cathode. Holes provided from the anode may move toward the emission layer through the hole transport region, and electrons provided from the cathode may move toward the emission layer through the electron transport region. The holes and the electrons recombine in the emission layer to produce excitons. These excitons transition from an excited state to a ground state to thereby generate light, for example visible light.
One or more embodiments relate to an organometallic compound, an organic light-emitting device including the same, and an electronic apparatus including the organic light-emitting device.
Additional aspects will be set forth in part in the description, which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.
According to an aspect, one or more embodiments provide an organometallic compound represented by Formula 1.
M1(Ln1)n1(Ln2)n2 Formula 1
In Formula 1,
Another aspect of the present disclosure provides an organic light-emitting device including a first electrode, a second electrode, and an organic layer located between the first electrode and the second electrode, wherein the organic layer includes an emission layer, and wherein the organic layer further includes at least one of the organometallic compounds.
The organometallic compound may be included in the emission layer of the organic layer, and the organometallic compound included in the emission layer may act as a dopant.
Another aspect of the present disclosure provides an electronic apparatus including the organic light-emitting device.
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 drawing, in which
FIGURE is a schematic cross-sectional view of an organic light-emitting device according to one or more embodiments.
Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout the specification. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the FIGURES, to explain aspects. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
The terminology used herein is for the purpose of describing one or more exemplary embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. The term “or” means “and/or.” It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
It will be understood that, although the terms first, second, third etc. may be used herein to describe various elements, components, regions, layers, and/or sections, these elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of the present embodiments.
Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
It will be understood that when an element is referred to as being “on” another element, it can be directly in contact with the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this general inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
“About” or “approximately” 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” can mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.
An organometallic compound according to one or more embodiments of the present disclosure is represented by Formula 1:
M1(Ln1)n1(Ln2)n2 Formula 1
wherein, in Formula 1, M1 is a transition metal.
In one or more embodiments, M1 in Formula 1 may be a Period 1 transition metal (a Period 4 metal element of the Periodic Table), a Period 2 transition metal (a Period 5 metal element of the Periodic Table), or a Period 3 transition metal (a Period 6 metal element of the Periodic Table). As used herein, “Period” refers to the Period of the transition metal as defined in the Periodic Table of the Elements.
In one or more embodiments, M1 may be iridium (Ir), platinum (Pt), palladium (Pd), gold (Au), osmium (Os), titanium (Ti), zirconium (Zr), hafnium (Hf), europium (Eu), terbium (Tb), thulium (Tm), or rhodium (Rh).
In one or more embodiments, M1 may be Ir, Os, Pt, Pd, or Au.
In one or more embodiments, M1 may be Ir.
Ln1 in Formula 1 is a ligand represented by Formula 1-1.
In Formula 1-1, X1 is C or N, and X2 is C or N.
In Formula 1-1, X11 is C(R1) or N, X12 is C(R2) or N, X13 is C(R3) or N, and X14 is C(R4) or N.
In one or more embodiments, one of X11 to X14 may not be N.
In one or more embodiments, at least one of X1 to X14 may not be N.
In one or more embodiments, each of X11 to X14 may not be N. In one or more embodiments, X11 may be C(R1), X12 may be C(R2), X13 may be C(R3), and X14 may be C(R4).
A bond between M1 and X1 may be a covalent bond or a coordinate bond.
A bond between M1 and X2 may be a covalent bond or a coordinate bond.
In one or more embodiments, X1 may be N, X2 may be C, a bond between X1 and M1 may be a coordinate bond, and a bond between X2 and M1 may be a covalent bond.
Y1 in Formula 1-1 is O, S, Se, C(R5)(R6), or N(R5).
CY2 in Formula 1-1 is a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
In one or more embodiments, CY2 may be i) a first ring, ii) a second ring, iii) a condensed cyclic group in which two or more first rings are condensed with each other, iv) a condensed cyclic group in which two or more second rings are condensed with each other, or v) a condensed cyclic group in which at least one first ring is condensed with at least one second ring,
In one or more embodiments, CY2 may be:
wherein, in Formulae 8-1 and 8-2,
In one or more embodiments, Y81 to Y84 in Formulae 8-1 and 8-2 may each independently be a single bond, O, S, N(R81), C(R81)(R82), or Si(R81)(R82).
In one or more embodiments, Y81 and Y82 may not be a single bond at the same time, and Y83 and Y84 may not be a single bond at the same time. That is, at least one of Y81 and Y82 may not be a single bond, and at least one of Y83 and Y84 may not be a single bond.
In one or more embodiments, CY81 to CY83 may each independently be a benzene group, a naphthalene group, a pyridine group, or a pyrimidine group.
In one or more embodiments, CY81 to CY83 may each independently be a benzene group or a naphthalene group.
In one or more embodiments, CY2 may be:
In one or more embodiments, CY2 may be represented by one of Formulae CY2-1 to CY2-22:
wherein, in Formulae CY2-1 to CY2-22,
In one or more embodiments, two or more adjacent groups of R21 to R23, R29a, and R29b may optionally be linked to each other to form a cyclopentane group, a cyclopentene group, a cyclopentadiene group, a furan group, a thiophene group, a pyrrole group, a silole group, an adamantane group, a norbornane group, a norbornene group, a cyclohexane group, a cyclohexene group, a benzene group, a naphthalene group, an indene group, an indole group, a benzofuran group, a benzothiophene group, a benzosilole group, a fluorene group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, or a dibenzosilole group, each unsubstituted or substituted with at least one R10a. R10a is as defined in connection with R1.
R1 to R6, R10, and R20 in Formula 1-1 are each independently a group represented by one of Formulae 2-1 or 2-2, hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C2-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C7-C60 alkyl aryl group, a substituted or unsubstituted C7-C60 aryl alkyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C2-C60 alkyl heteroaryl group, a substituted or unsubstituted C2-C60 heteroaryl alkyl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —N(Q4)(Q5), —B(Q6)(Q7), —P(Q8)(Q9), or —P(═O)(Q8)(Q9),
L1 in Formulae 2-1 and 2-2 is a single bond, a substituted or unsubstituted C5-C30 carbocyclic group, or a substituted or unsubstituted C1-C30 heterocyclic group.
a1 in Formulae 2-1 and 2-2 is 0, 1, 2, 3, 4, or 5.
In one or more embodiments, L1 may be:
In Formula 1-1, the ring group CY2 is a benzene group or is a group that is different than a benzene group (i.e., a group that is not a benzene group). As used herein, it is to be understood that a benzene group is synonymous with a “phenyl group” and may be abbreviated as “-Ph” for the sake of convenience.
In Formula 1-1, when CY2 is a benzene group, at least one of R1 to R4 is a group represented by Formula 2-1 or a group represented by Formula 2-2, or at least one of R10 and R20 is a group represented by Formula 2-2.
In one or more embodiments, CY2 in Formula 1-1 is a group represented by Formula CY2-1 (i.e., an unsubstituted or substituted benzene group), and at least one of R1 to R4 is a group represented by Formula 2-1 or a group represented by Formula 2-2, or at least one of R10 and R20 is a group represented by Formula 2-2. In some embodiments, when CY2 in Formula 1-1 is a group represented by Formula CY2-1, if one or more of R1 to R4 is a group represented by Formula 2-1 or a group represented by Formula 2-2, then none of R10 to R20 may be a group represented by Formula 2-1 or a group represented by Formula 2-2. Similarly, in some embodiments, when CY2 in Formula 1-1 is a group represented by Formula CY2-1, if one or more of R10 to R20 is a group represented by Formula 2-1 or a group represented by Formula 2-2, then none of R1 to R4 may be a group represented by Formula 2-1 or a group represented by Formula 2-2.
In Formula 1-1, when CY2 in Formula 1-1 is not a benzene group, at least one of R1 to R4, R10, and R20 is a group represented by Formula 2-1 or a group represented by Formula 2-2.
In one or more embodiments, when CY2 in Formula 1-1 is a group represented by one of Formulae CY2-2 to CY2-22, at least one of R1 to R4, R10, and R20 is a group represented by Formula 2-1 or a group represented by Formula 2-2.
In one or more embodiments, at least one of R1 to R4 may be a group represented by one of Formulae 2-1 or 2-2.
In one or more embodiments, at least one of R1 to R4, R10, and R20 may be a group represented by Formula 2-2.
In one or more embodiments, R1 to R6, R10, and R20 may each independently be:
In one or more embodiments, R1 to R6, R10, and R20 may each independently be:
wherein, in Formulae 9-1 to 9-43, 9-201 to 9-237, 10-1 to 10-129, and 10-201 to 10-350, * indicates a binding site to a neighboring atom, Ph may be a phenyl group, TMS may be a trimethylsilyl group, and TMG may be a trimethylgermyl group.
In one or more embodiments, R1 to R4 may each independently be a group represented by one of Formula 2-1 or 2-2, hydrogen, deuterium, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a 2-methylbutyl group, a sec-pentyl group, a tert-pentyl group, a neo-pentyl group, a 3-pentyl group, a 3-methyl-2-butyl group, a phenyl group, a biphenyl group, a C1-C20 alkylphenyl group, or a naphthyl group, and
In one or more embodiments, at least one of R1 to R4 may be:
In one or more embodiments, one of R1 to R4 may be a group represented by one of Formulae 2-1 or 2-2, and the others of R1 to R4 may each be hydrogen.
In one or more embodiments, one of R1 to R4, R10, or R20 may be a group represented by Formula 2-2.
In Formula 1-1, b10 is 1 or 2, and b20 is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
When b10 is 2, two of R10(s) may be identical to or different from each other, and when b20 is 2 or more, two or more of R20(s) may be identical to or different from each other.
In Formula 1-1, two of R10(s); two or more of a plurality of R20(s); or two or more adjacent groups of R5, R6, R10, and R20 may optionally be linked to each other to form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group.
In one or more embodiments, two of R10(s); two or more of a plurality of R20(s); or two or more adjacent groups of R5, R6, R10, and R20 may optionally be linked to each other via a single bond, a double bond, or a first linking group to form a C5-C30 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C30 heterocyclic group unsubstituted or substituted with at least one R10a (for example, a fluorene group, a carbazole group, a dibenzothiophene group, a dibenzofuran group, a dibenzosilole group, a xanthene group, an acridine group, or the like, each unsubstituted or substituted with at least one R10a). R10a is as defined in connection with R1.
In one or more embodiments, two of R10(s); two or more of a plurality of R20(s); or two or more adjacent groups of R5, R6, R10, and R20 may optionally be linked to each other to form a cyclopentane group, a cyclopentene group, a cyclopentadiene group, a furan group, a thiophene group, a pyrrole group, a silole group, an adamantane group, a norbornane group, a norbornene group, a cyclohexane group, a cyclohexene group, a benzene group, a naphthalene group, an indene group, an indole group, a benzofuran group, a benzothiophene group, a benzosilole group, a fluorene group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, or dibenzosilole group, each unsubstituted or substituted with at least one R10a. R10a is as defined in connection with R1.
The first linking group may be *—N(R8)—*′, *—B(R8)—*′, *—P(R8)—*′, *—C(R8)(R9)—*, *—Si(R8)(R9)—*′, *—Ge(R8)(R9)—*′, *—S—*′, *—Se—*′, *—O—*′, *—C(═O)—*′, *—S(═O)—*′, *—S(═O)2—*, C(R8)═*′, *═C(R8)—*′, *—C(R8)═C(R9)—*′, *—C(═S)—*′, or *—C≡C—*′, wherein R8 and R9 are each as defined in connection with R10, and * and *′ each indicate a binding site to a neighboring atom.
In one or more embodiments, Ln1 may be represented by one of Formulae 3-1 to 3-4:
wherein, in Formulae 3-1 to 3-4,
n1 in Formula 1 is 1, 2, or 3.
Ln2 in Formula 1 is a bidentate ligand.
In one or more embodiments, Ln2 may be represented by one of Formulae 5, 6, or 8-1 to 8-11:
wherein, in Formulae 5, 6, and 8-1 to 8-11,
In one or more embodiments, CY3 and CY4 in Formula 5 are each independently as defined in connection with CY2.
In one or more embodiments, CY3 may be a pyridine group, a pyrimidine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrazole group, a triazole group, an imidazole group, an indole group, a benzopyrazole group, a benzimidazole group, an azadibenzothiophene group, an azadibenzofuran group, an azacarbazole group, an azafluorene group, or an azadibenzosilole group.
In one or more embodiments, CY3 may be represented by one of Formulae CY3-1 to CY3-13:
wherein, in Formulae CY3-1 to CY3-13,
In one or more embodiments, two or more adjacent groups of R31 to R38, R39a, and R39b may optionally be linked to each other to form a cyclopentane group, a cyclopentene group, a cyclopentadiene group, a furan group, a thiophene group, a pyrrole group, a silole group, an adamantane group, a norbornane group, a norbornene group, a cyclohexane group, a cyclohexene group, a benzene group, a naphthalene group, an indene group, an indole group, a benzofuran group, a benzothiophene group, a benzosilole group, a fluorene group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, or a dibenzosilole group, each unsubstituted or substituted with at least one R10a. R10a is as defined in connection with R1.
In one or more embodiments, CY4 may be a benzene group, a naphthalene group, a 1,2,3,4-tetrahydronaphthalene group, a benzothiophene group, a benzofuran group, an indole group, an indene group, a benzosilole group, a dibenzothiophene group, a dibenzofuran group, a carbazole group, a fluorene group, a dibenzosilole group, an azadibenzothiophene group, an azadibenzofuran group, an azacarbazole group, an azafluorene group, or an azadibenzosilole group.
In one or more embodiments, CY4 may be represented by one of Formulae CY4-1 to CY4-13:
wherein, in Formulae CY4-1 to CY4-13,
In one or more embodiments, two or more adjacent groups of R41 to R43, R49a, and R49b may optionally be linked to each other to form a cyclopentane group, a cyclopentene group, a cyclopentadiene group, a furan group, a thiophene group, a pyrrole group, a silole group, an adamantane group, a norbornane group, a norbornene group, a cyclohexane group, a cyclohexene group, a benzene group, a naphthalene group, an indene group, an indole group, a benzofuran group, a benzothiophene group, a benzosilole group, a fluorene group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, or a dibenzosilole group, each unsubstituted or substituted with at least one R10a. R10a is as defined in connection with R1.
In one or more embodiments, X3 may be N, and X4 may be C,
In one or more embodiments, X5 and X6 may each be O,
R30 and R40 are each independently as defined in connection with R5, R6, R10, or R20.
When b30 is 2 or more, two or more of R30(s) may be identical to or different from each other, and when b40 is 2 or more, two or more of R40(s) may be identical to or different from each other.
In one or more embodiments, Ln2 may be represented by one of Formulae 5-1 to 5-129:
wherein, in Formulae 5-1 to 5-129,
n2 in Formula 1-1 may be 0, 1, or 2.
In one or more embodiments, the organometallic compound may be a compound represented by one of Formulae 11-1 to 11-8:
X6 and X6 may each independently be O or S,
In one or more embodiments, the organometallic compound may be electrically neutral.
In one or more embodiments, M1 may be Ir, and the sum of n1 and n2 may be 3.
In one or more embodiments, the organometallic compound may be one of Compounds 1 to 196:
The organometallic compound represented by Formula 1 satisfies the structure of Formula 1 as described above. In detail, the ligand represented by Formula 1-1 has a structure in which heterorings including heteroatoms Y1 are condensed. Among the condensed heterorings, when CY2 is a benzene group, at least one of R1 to R4, which are substituents of a benzene ring, is a group represented by Formula 2-1 or Formula 2-2, that is, a substituent including a Si atom or a Ge atom, or at least one of R10 and R20 is a group represented by Formula 2-2, that is, a substituent including a Ge atom, and when CY2 is not a benzene group, at least one of R1 to R4, R10, and R20 is a group represented by Formula 2-1 or Formula 2-2, that is, a substituent including a Si atom or a Ge atom. Without wishing to bound to theory, due to such a structure, an electronic device, for example, an organic light-emitting device, including the organometallic compound represented by Formula 1 may show a low driving voltage, high efficiency, a long lifespan, and a reduced roll-off phenomenon.
The highest occupied molecular orbital (HOMO) energy level, lowest unoccupied molecular orbital (LUMO) energy level, energy gap (electron volts, eV), lowest triplet (Ti) energy level, and lowest singlet (Si) energy level of selected organometallic compounds represented by Formula 1 were evaluated by density functional theory (DFT) using a Gaussian 09 program with the molecular structure optimization obtained at the B3LYP level, and results thereof are shown in Table 1.
From Table 1, it was confirmed that the organometallic compounds represented by Formula 1 have such electric characteristics that are suitable for use as a dopant for an electronic device, for example, an organic light-emitting device.
In one or more embodiments, the full width at half maximum (FWHM) of the emission peak of the emission spectrum or the electroluminescence (EL) spectrum of the organometallic compound may be 75 nm or less. For example, the FWHM of the emission peak of the emission spectrum or the electroluminescence spectrum of the organometallic compound may be from about 30 nm to about 75 nm, from about 40 nm to about 70 nm, or from about 45 nm to about 68 nm.
In one or more embodiments, the maximum emission wavelength (emission peak wavelength, λmax) of the emission peak of the emission spectrum or the electroluminescence spectrum of the organometallic compound may be from about 500 nm to about 750 nm.
Synthesis methods of the organometallic compound represented by Formula 1 may be recognizable by one of ordinary skill in the art by referring to Synthesis Examples provided herein.
The organometallic compound represented by Formula 1 is suitable for use in an organic layer of an organic light-emitting device, for example, for use as a dopant in an emission layer of the organic layer. Thus, another aspect provides an organic light-emitting device that includes: a first electrode; a second electrode; and an organic layer that is located between the first electrode and the second electrode, wherein the organic layer includes an emission layer, and wherein the organic layer further includes at least one of the organometallic compounds represented by Formula 1.
Since the organic light-emitting device has an organic layer including the organometallic compound represented by Formula 1 as described herein, excellent characteristics may be obtained with respect to driving voltage, current efficiency, external quantum efficiency, a roll-off ratio, and lifespan, and the FWHM of the emission peak of the EL spectrum is relatively narrow.
The organometallic compound of Formula 1 may be used between a pair of electrodes of an organic light-emitting device. In one or more embodiments, the organometallic compound represented by Formula 1 may be included in the emission layer. In this regard, the organometallic compound may act as a dopant, and the emission layer may further include a host (that is, an amount of the organometallic compound represented by Formula 1 in the emission layer is smaller than an amount of the host).
In one or more embodiments, the emission layer may emit green light. For example, the emission layer may emit green light having a maximum emission wavelength of about 500 nm to about 600 nm.
In one or more embodiments, the emission layer may emit red light. For example, the emission layer may emit red light having a maximum emission wavelength of about 600 nm to about 750 nm.
The expression “(an organic layer) includes at least one of organometallic compounds” used herein may include a case in which “(an organic layer) includes identical organometallic compounds represented by Formula 1” and a case in which “(an organic layer) includes two or more different organometallic compounds represented by Formula 1.”
In one or more embodiments, the organic layer may include, as the organometallic compound, only Compound 1. In this regard, Compound 1 may be present in the emission layer of the organic light-emitting device. In one or more embodiments, the organic layer may include, as the organometallic compound, Compound 1 and Compound 2, wherein Compound 1 and Compound 2 are different from each other. In this regard, Compound 1 and Compound 2 may be present in an identical layer (for example, both Compound 1 and Compound 2 may be present in an emission layer).
The first electrode may be an anode, which is a hole injection electrode, and the second electrode may be a cathode, which is an electron injection electrode; or the first electrode may be a cathode, which is an electron injection electrode, and the second electrode may be an anode, which is a hole injection electrode.
In one or more embodiments, in the organic light-emitting device, the first electrode may be an anode, and the second electrode may be a cathode, and the organic layer may further include a hole transport region located between the first electrode and the emission layer and an electron transport region located between the emission layer and the second electrode, and the hole transport region may include a hole injection layer, a hole transport layer, an electron blocking layer, a buffer layer, or a combination thereof, and the electron transport region may include a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof.
The term “organic layer” as used herein refers to a single layer and/or a plurality of layers located between the first electrode and the second electrode of an organic light-emitting device. The “organic layer” may include, in addition to an organic compound, an organometallic complex including a metal.
The FIGURE is a schematic cross-sectional view of an organic light-emitting device 10 according to one or more embodiments of the present disclosure. Hereinafter, the structure of an organic light-emitting device according to one or more embodiments of the present disclosure and a method of manufacturing an organic light-emitting device according to one or more embodiments of the present disclosure will be described in connection with FIGURE. The organic light-emitting device 10 includes a first electrode 11, an organic layer 15, and a second electrode 19, which are sequentially stacked.
A substrate may be additionally located under the first electrode 11 or above the second electrode 19. For use as the substrate, any substrate that is used in organic light-emitting devices available in the art may be used, and the substrate may be a glass substrate or a transparent plastic substrate, each having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance.
In one or more embodiments, the first electrode 11 may be formed by depositing or sputtering a material for forming the first electrode 11 on the substrate. The first electrode 11 may be an anode. The material for forming the first electrode 11 may be chosen from materials with a high work function to facilitate hole injection. The first electrode 11 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. The material for forming the first electrode 11 may be indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), or zinc oxide (ZnO). In one or more embodiments, the material for forming the first electrode 11 may be metal, such as magnesium (Mg), aluminum (Al), silver (Ag), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), or magnesium-silver (Mg—Ag).
The first electrode 11 may have a single-layered structure or a multi-layered structure including two or more layers. For example, the first electrode 11 may have a three-layered structure of ITO/Ag/ITO, but the structure of the first electrode 11 is not limited thereto.
The organic layer 15 is located on the first electrode 11.
The organic layer 15 may include a hole transport region, an emission layer, and an electron transport region.
The hole transport region may be located between the first electrode 11 and the emission layer.
The hole transport region may include a hole injection layer, a hole transport layer, an electron blocking layer, a buffer layer, or a combination thereof.
The hole transport region may include only either a hole injection layer or a hole transport layer. In one or more embodiments, the hole transport region may have a hole injection layer/hole transport layer structure or a hole injection layer/hole transport layer/electron blocking layer structure, wherein, for each structure, each layer is sequentially stacked in this stated order and extending away from the first electrode 11 and towards the second electrode 19.
When the hole transport region includes a hole injection layer, the hole injection layer may be formed (e.g., deposited or coated) on the first electrode 11 by using one or more suitable methods, for example, vacuum deposition, spin coating, casting, and/or Langmuir-Blodgett (LB) deposition.
When the hole injection layer is formed by vacuum deposition, the deposition conditions may vary according to a material that is used to form the hole injection layer, and the structure and thermal characteristics of the hole injection layer. For example, the deposition conditions may include a deposition temperature of about 100 to about 500° C., a vacuum pressure of about 10−8 torr to about 10−3 torr, and a deposition rate of about 0.01 angstroms per second (A/sec) to about 100 Å/sec. However, the deposition conditions are not limited thereto.
When the hole injection layer is formed using spin coating, coating conditions may vary according to the material used to form the hole injection layer, and the structure and thermal properties of the hole injection layer. For example, a coating speed may be from about 2,000 revolutions per minute (rpm) to about 5,000 rpm, and a temperature at which a heat treatment is performed to remove a solvent after coating may be from about 80° C. to about 200° C. However, the coating conditions are not limited thereto.
The conditions for forming the hole transport layer and the electron blocking layer may be the same as the conditions for forming the hole injection layer.
The hole transport region may include one or more of 4,4′,4″-tris(3-methylphenylphenylamino)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(naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPB), pi-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), or a compound represented by one of Formula 201 or 202:
wherein, in Formula 201, Ar101 and Ar102 may each independently be:
xa and xb in Formula 201 may each independently be an integer from 0 to 5, or 0, 1, or 2. For example, xa may be 1 and xb may be 0, but xa and xb are not limited thereto.
R101 to R108, R111 to R119, and R121 to R124 in Formulae 201 and 202 may each independently be:
R109 in Formula 201 may be:
In one or more embodiments, the compound represented by Formula 201 may be represented by Formula 201A below, but embodiments of the present disclosure are not limited thereto:
wherein, in Formula 201A, R101, R111, R112, and R109 are as defined in the present disclosure.
For example, the compound represented by one of Formulae 201 or 202 may include one of Compounds HT1 to HT20, but are not limited thereto:
A thickness of the hole transport region may be in the range of about 100 angstroms (Å) to about 10,000 Å, for example, about 100 Å to about 1,000 Å. When the hole transport region includes at least one of a hole injection layer and a hole transport layer, a thickness of the hole injection layer may be in a range of about 100 Å to about 10,000 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 hole transport region may further include, in addition to these materials, a charge-generation material for the improvement of conductive properties. The charge-generation material may be homogeneously or non-homogeneously dispersed in the hole transport region.
The charge-generation material may be, for example, a p-dopant. The p-dopant may be a quinone derivative, a metal oxide, or a cyano group-containing compound, but embodiments of the present disclosure are not limited thereto. Non-limiting examples of the p-dopant are a quinone derivative, such as tetracyanoquinonedimethane (TCNQ), 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4-TCNQ), or F6-TCNNQ; a metal oxide, such as a tungsten oxide or a molybdenum oxide; and a cyano group-containing compound, such as Compound HT-D1 or F12, but are not limited thereto.
The hole transport region may further include a buffer layer.
The buffer layer may compensate for an optical resonance distance according to a wavelength of light emitted from the emission layer, and thus, efficiency of a formed organic light-emitting device may be improved.
An emission layer may be formed on the hole transport region by vacuum deposition, spin coating, casting, LB deposition, or the like. When the emission layer is formed by vacuum deposition or spin coating, the deposition or coating conditions may be similar to those applied in forming the hole injection layer although the deposition or coating conditions may vary according to a material that is used to form the emission layer.
Meanwhile, when the hole transport region includes an electron blocking layer, a material for the electron blocking layer may be chosen from materials for the hole transport region described above and materials for a host to be explained later. However, the material for the electron blocking layer is not limited thereto. For example, when the hole transport region includes an electron blocking layer, a material for the electron blocking layer may be mCP, which will be explained later.
The emission layer may include a host and a dopant, and the dopant may include the organometallic compound represented by Formula 1.
The host may include at least one of 1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBi), 3-tert-butyl-9,10-di(naphth-2-yl)anthracene (TBADN), 9,10-di(naphthalene-2-yl)anthracene (ADN) (also referred to as “DNA”), 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP), 4,4′-bis(9-carbazolyl)-2,2′-dimethyl-biphenyl (CDBP), TCP, mCP, Compound H50, or Compound H51:
In one or more embodiments, the host may include a compound represented by Formula 301:
Ar113 to Ar116 in Formula 301 may each independently be:
g, h, i, and j in Formula 301 may each independently be an integer from 0 to 4, and may be, for example, 0, 1, or 2.
Ar113 and Ar116 in Formula 301 may each independently be:
In one or more embodiments, the host may include a compound represented by Formula 302 below:
wherein, in Formula 302, Ar122 to Ar125 are as defined in connection with Ar113 in Formula 301.
Ar126 and Ar127 in Formula 302 may each independently be a C1-C10 alkyl group (for example, a methyl group, an ethyl group, or a propyl group).
k and l in Formula 302 may each independently be an integer from 0 to 4. For example, k and l may each be 0, 1, or 2.
When the organic light-emitting device is a full-color organic light-emitting device, the emission layer may be patterned into a red emission layer, a green emission layer, and a blue emission layer. In one or more embodiments, due to a stacked structure including a red emission layer, a green emission layer, and/or a blue emission layer, the emission layer may emit white light.
When the emission layer includes a host and a dopant, an amount of the dopant 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, but embodiments of the present disclosure are not limited thereto.
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 the range described above, excellent light-emission characteristics may be obtained without a substantial increase in driving voltage.
Then, an electron transport region may be located on the emission layer.
The electron transport region may include a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof.
For example, the electron transport region may have a hole blocking layer/electron transport layer/electron injection layer structure or an electron transport layer/electron injection layer structure, and the structure of the electron transport region is not limited thereto. The electron transport layer may have a single-layered structure or a multi-layered structure including two or more different materials.
Conditions for forming the hole blocking layer, the electron transport layer, and the electron injection layer which may constitute the electron transport region may be understood by referring to the conditions for forming the hole injection layer.
When the electron transport region includes a hole blocking layer, the hole blocking layer may include, for example, at least one of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), bis(2-methyl-8-quinolinolato-N1,08)-(1,1′-biphenyl-4-olato)aluminum (Bphen), and bis(2-methyl-8-quinolinolato-N1,08)-(1,1′-biphenyl-4-olato)aluminum (BAlq), but embodiments of the present disclosure are not limited thereto.
A thickness of the hole blocking layer may be in a range of about 20 Å to about 1,000 Å, for example, about 30 Å to about 300 Å. When the thickness of the hole blocking layer is within the range described above, excellent hole blocking characteristics may be obtained without a substantial increase in driving voltage.
The electron transport layer may further include at least one of BCP, Bphen, tris(8-hydroxy-quinolinato)aluminum (Alq3), BAlq, 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole (TAZ), or 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole (NTAZ).
In one or more embodiments, the electron transport layer may include at least one of ET1 to ET25, but embodiments of the present disclosure are not limited thereto:
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 thickness of the electron transport layer is within the range described above, satisfactory electron transporting characteristics may be obtained without a substantial increase in driving voltage.
The electron transport layer may include a metal-containing material in addition to the material as described above.
The metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 (lithium quinolate, LiQ) or ET-D2:
Also, the electron transport region may include an electron injection layer that facilitates injection of electrons from the second electrode 19.
The electron injection layer may include LiF, NaCl, CsF, Li2O, BaO, or a combination thereof.
A thickness of the electron injection layer may be in a range of about 1 Å to about 100 Å, for example, about 3 Å to about 90 Å. When the thickness of the electron injection layer is within the range described above, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.
The second electrode 19 is located on the organic layer 15. The second electrode 19 may be a cathode. A material for forming the second electrode 19 may be a metal, an alloy, an electrically conductive compound, or a combination thereof, which have a relatively low work function. For example, lithium (Li), magnesium (Mg), aluminum (Al), silver (Ag), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), or magnesium-silver (Mg—Ag) may be used as the material for forming the second electrode 19. In one or more embodiments, to manufacture a top-emission type light-emitting device, a transmissive electrode formed using ITO or IZO may be used as the second electrode 19.
Hereinbefore, the organic light-emitting device has been described with reference to FIGURE, but embodiments of the present disclosure are not limited thereto.
Another aspect provides a diagnostic composition including at least one organometallic compound represented by Formula 1.
The organometallic compound represented by Formula 1 provides high luminescence efficiency. Accordingly, a diagnostic composition including the organometallic compound may have high diagnostic efficiency.
The diagnostic composition may be used in various applications including a diagnosis kit, a diagnosis reagent, a biosensor, and a biomarker.
The term “C1-C60 alkyl group” as used herein refers to a linear or branched saturated aliphatic hydrocarbon monovalent group having 1 to 60 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, and a hexyl group. The term “C1-C60 alkylene group” as used herein refers to a divalent group having the same structure as the C1-C60 alkyl group.
The term “C1-C60 alkoxy group” as used herein refers to a monovalent group represented by —OA101 (wherein A101 is the C1-C60 alkyl group), and examples thereof include a methoxy group, an ethoxy group, and an isopropyloxy group. The term “C1-C60 alkylthio group” as used herein refers to a monovalent group represented by —SA102 (wherein A102 is the C1-C60 alkyl group).
The term “C2-C60 alkenyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethenyl group, a propenyl group, and a butenyl group. The term “C2-C60 alkenylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethynyl group and a propynyl group. The term “C2-C60 alkynylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkynyl group.
The term “C3-C10 cycloalkyl group” as used herein refers to a monovalent saturated hydrocarbon monocyclic group having 3 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. The term “C3-C10 cycloalkylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkyl group.
The term “C1-C10 heterocycloalkyl group” as used herein refers to a monovalent saturated monocyclic group having at least one heteroatom chosen from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and 1 to 10 carbon atoms, and examples thereof include a tetrahydrofuranyl group and a tetrahydrothiophenyl group. The term “C1-C10 heterocycloalkylene group” as used herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkyl group.
The term “C3-C10 cycloalkenyl group” as used herein refers to a monovalent monocyclic group that has 3 to 10 carbon atoms and at least one carbon-carbon double bond in the ring thereof and no aromaticity, and examples thereof include a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group. The term “C3-C10 cycloalkenylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkenyl group.
The term “C2-C10 heterocycloalkenyl group” as used herein refers to a monovalent monocyclic group that has at least one heteroatom chosen from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom, 1 to 10 carbon atoms, and at least one carbon-carbon double bond in its ring. Examples of the C2-C10 heterocycloalkenyl group include a 2,3-dihydrofuranyl group and a 2,3-dihydrothiophenyl group. The term “C2-C10 heterocycloalkenylene group” as used herein refers to a divalent group having the same structure as the C2-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as used herein refers to a monovalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms, and the term “C6-C60 arylene group” as used herein refers to a divalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms. Examples of the C6-C60 aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a chrysenyl group. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the rings may be fused to each other.
The term “C7-C60 alkyl aryl group” as used herein refers to a C6-C60 aryl group substituted with at least one C1-C60 alkyl group. The term “C7-C60 aryl alkyl group” as used herein refers to a C1-C60 alkyl group substituted with at least one C6-C60 aryl group.
The term “C1-C60 heteroaryl group” as used herein refers to a monovalent group having a carbocyclic aromatic system that has at least one heteroatom chosen from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom, and 1 to 60 carbon atoms. The term “C1-C60 heteroarylene group” as used herein refers to a divalent group having a carbocyclic aromatic system that has at least one heteroatom chosen from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom, and 1 to 60 carbon atoms. Examples of the C1-C60 heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, and an isoquinolinyl group. When the C6-C60 heteroaryl group and the C6-C60 heteroarylene group each include two or more rings, the rings may be fused to each other. The C2-C60 alkylheteroaryl group refers to a C1-C60 heteroaryl group substituted with at least one C1-C60 alkyl group.
The term “C2-C60 alkyl heteroaryl group” as used herein refers to a C1-C60 heteroaryl group substituted with at least one C1-C60 alkyl group. The term “C2-C60 heteroaryl alkyl group” as used herein refers to a C1-C60 alkyl group substituted with at least one C1-C60 heteroaryl group.
The term “C6-C60 aryloxy group” as used herein indicates —OA103 (wherein A103 is the C6-C60 aryl group). The term “C6-C60 arylthio group” as used herein indicates —SA104 (wherein A104 is the C6-C60 aryl group).
The term “C1-C60 heteroaryloxy group” as used herein indicates —OA104 (wherein A104 is the C1-C60 heteroaryl group), and the term “C1-C60 heteroarylthio group” as used herein indicates —SA105 (wherein A105 is the C1-C60 heteroaryl group).
The term “monovalent non-aromatic condensed polycyclic group” as used herein refers to a monovalent group (for example, having 8 to 60 carbon atoms) having two or more rings condensed to each other, only carbon atoms as ring-forming atoms, and no aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic condensed polycyclic group include a fluorenyl group. The term “divalent non-aromatic condensed polycyclic group” as used herein refers to a divalent group having the same structure as a monovalent non-aromatic condensed polycyclic group.
The term “monovalent non-aromatic condensed heteropolycyclic group” as used herein refers to a monovalent group (for example, having 2 to 60 carbon atoms) having two or more rings condensed to each other, a heteroatom chosen from N, O, P, Si, S, Se, Ge, and B other than carbon atoms, as a ring-forming atom, and no aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic condensed heteropolycyclic group include a carbazolyl group. The term “divalent non-aromatic condensed heteropolycyclic group” as used herein refers to a divalent group having the same structure as a monovalent non-aromatic condensed heteropolycyclic group.
The term “C5-C30 carbocyclic group” as used herein refers to a saturated or unsaturated cyclic group having, as ring-forming atoms, 5 to 30 carbon atoms only. The C5-C30 carbocyclic group may be a monocyclic group or a polycyclic group.
The term “C1-C30 heterocyclic group” as used herein refers to a saturated or unsaturated cyclic group having, as a ring-forming atom, at least one heteroatom chosen from N, O, Si, P, S, Se, Ge, and B other than the 1 to 30 carbon atoms. The C1-C30 heterocyclic group may be a monocyclic group or a polycyclic group.
At least one substituent of the substituted C5-C30 carbocyclic group, the substituted C1-C30 heterocyclic group, the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted C1-C60 alkylthio group, the substituted C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C2-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C7-C60 alkyl aryl group, the substituted C7-C60 aryl alkyl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl group, the substituted C2-C60 alkyl heteroaryl group, the substituted C2-C60 heteroaryl alkyl group, the substituted C1-C60 heteroaryloxy group, the substituted C1-C60 heteroarylthio group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may be:
Hereinafter, an exemplary compound and an exemplary organic light-emitting device according to one or more embodiments are described in further detail with reference to Synthesis Example and Examples. However, the organic light-emitting device is not limited thereto. The wording “‘B’ was used instead of ‘A’” used in describing Synthesis Examples means that an amount of ‘A’ used was identical to an amount of ‘B’ used, in terms of a molar equivalent.
(1) Synthesis of Compound 1A(1)
2-phenylpyridine (7.5 grams (g), 33.1 millimoles (mmol)) and iridium chloride hydrate (5.2 g, 14.7 mmol) were mixed with 120 milliliters (mL) of ethoxyethanol and 40 mL of deionized (DI) water, the resultant mixture was stirred while refluxing for 24 hours, and then, the temperature was lowered to room temperature. The resulting solid was separated by filtration, washed sufficiently with water, methanol, and hexane, in this stated order, and then dried in a vacuum oven to obtain 8.2 g (yield of 82%) of Compound 1A(1).
(2) Synthesis of Compound 1A
Compound 1A(1) (1.6 g, 1.2 mmol) and 45 mL of methylene chloride were mixed, and then, silver triflate (AgOTf) (0.6 g, 2.3 mmol) was added thereto after being mixed with 15 mL of methanol (MeOH). Thereafter, the mixture was stirred for 18 hours at room temperature while light was blocked with aluminum foil, and then filtered through Celite to remove the resulting solid, and the filtrate was subjected to reduced pressure to obtain a solid (Compound 1A). Compound 1A was used in the next reaction without an additional purification process.
(3) Synthesis of Compound 1B
In a nitrogen environment, phenyl boronic acid (0.5 g, 3.75 mmol) and 3-chloro-6-(trimethylgermyl)benzofuro[3,2-c]pyridine (1.0 g, 3.1 mmol) were dissolved in 75 mL of 1,4-dioxane to form a reaction mixture. Then, potassium carbonate (K2CO3) (1.0 g, 9.37 mmol) was dissolved in 25 mL of DI water, and then, the resultant solution was added to the reaction mixture, and a palladium catalyst (Pd(PPh3)4) (0.18 g, 0.16 mmol) was then added thereto. Then, the reaction mixture was stirred while heating at reflux at 100° C.
After allowing the reaction to cool and subsequent extraction, the obtained solid was subjected to column chromatography (eluent: methylene chloride (MC) and hexanes) to obtain 1.0 g (yield of 88%) of Compound 1B (3-phenyl-6-(trimethylgermyl)benzofuro[3,2-c]pyridine). The obtained compound was identified by high resolution mass spectrometry (HRMS, using matrix assisted laser desorption ionization (MALDI)) and high-performance liquid chromatography (HPLC) analysis.
HRMS (MALDI) calcd for C20H19GeNO: m/z: 362.01 Found: 364.08.
(4) Synthesis of Compound 1
Compound 1A (1.3 g, 1.8 mmol) and Compound 1B (0.7 g, 2.0 mmol) were mixed with 35 mL of 2-ethoxyethanol and 35 mL of N,N-dimethylformamide, the resultant mixture was stirred while heating at reflux for 24 hours, and then, the temperature was lowered to room temperature. An extraction process was performed thereon with methylene chloride and water, and then, the water layer was removed therefrom. The resultant was treated with anhydrous magnesium sulfate, followed by filtration and then concentration under reduced pressure. After extraction, the obtained solid was subjected to column chromatography (eluent: methylene chloride (MC) and hexanes) to obtain 0.66 g (yield of 40%) of Compound 1. The obtained compound was identified by HRMS and HPLC analysis.
HRMS (MALDI) calcd for C43H34GeIrN2O: m/z: 859.61 Found: 862.13.
0.65 g (yield of 46%) of Compound 2 was obtained in a similar manner as used to synthesize Compound 1 of Synthesis Example 1, except that 2-phenyl-5-(trimethylsilyl)pyridine (8.7 g, 38.3 mmol) was used instead of 2-phenylpyridine in synthesizing Compound 2A(1). The obtained compound was identified by HRMS and HPLC analysis.
HRMS (MALDI) calcd for C49H50GeIrN2OSi2: m/z: 1003.97 Found: 1006.33.
(3) Synthesis of Compound 3B
In a nitrogen environment, dibenzo[b,d]furan-4-yl boronic acid (1.0 g, 4.9 mmol) and 3-chloro-6-(trimethylgermyl)benzofuro[3,2-c]pyridine (1.3 g, 4.0 mmol) were dissolved in 90 mL of 1,4-dioxane to form a reaction mixture. Then, potassium carbonate (K2CO3) (1.3 g, 12.2 mmol) was dissolved in 30 mL of DI water, and then, the resultant solution was added to the reaction mixture, and a palladium catalyst (Pd(PPh3)4) (0.23 g, 0.2 mmol) was then added thereto. Then, the reaction mixture was stirred while heating at reflux at 100° C. After cooling to room temperature and subsequent extraction, the obtained solid was subjected to column chromatography (eluent: methylene chloride (MC) and hexane) to obtain 1.5 g (yield of 82%) of Compound 3B (3-(dibenzo[b,d]furan-4-yl)-6-(trimethylgermyl)benzofuro[3,2-c]pyridine). The obtained compound was identified by HRMS and HPLC analysis.
HRMS (MALDI) calcd for C21H25GeNO2: m/z: 452.09 Found: 454.08.
(4) Synthesis of Compound 3
Compound 1A (1.4 g, 2.0 mmol) and Compound 1B (1.0 g, 2.2 mmol) were mixed with 40 mL of 2-ethoxyethanol and 40 mL of N,N-dimethylformamide, the resultant mixture was stirred while heating at reflux for 24 hours, and then, the temperature was lowered to room temperature. An extraction process was performed thereon with methylene chloride and water, and then, the water layer was removed therefrom. The resultant was treated with anhydrous magnesium sulfate, followed by filtration and concentration under reduced pressure. After extraction, the obtained solid was subjected to column chromatography (eluent: methylene chloride (MC) and hexanes) to obtain 0.72 g (yield of 38%) of Compound 3. The obtained compound was identified by HRMS and HPLC analysis.
HRMS (MALDI) calcd for C45H36GeIrN3O2: m/z: 951.68 Found: 954.18.
(1) Synthesis of Compound 64A
In a nitrogen environment, 1-bromo-7-(trimethylgermyl)benzofuro[2,3-c]pyridine (1.5 g, 4.1 mmol) and 2-(3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxoborane (1.1 g, 4.5 mmol) were dissolved in 90 mL of 1,4-dioxane to form a reaction mixture. Then, potassium carbonate (K2CO3) (1.3 g, 12.3 mmol) was dissolved in 30 mL of DI water, and then, the resultant solution was added to the reaction mixture, and a palladium catalyst (Pd(PPh3)4) (0.23 g, 0.2 mmol) was then added thereto. Then, the reaction mixture was stirred while heating at reflux at 110° C. After allowing the reaction to cool to room temperature and subsequent extraction, the obtained solid was subjected to column chromatography (eluent: methylene chloride (MC) and hexanes) to obtain 1.4 g (yield of 87%) of Compound 64A (1-(3,5-dimethylphenyl)-7-(trimethylgermyl)benzofuro[2,3-c]pyridine). The obtained compound was identified by HRMS and HPLC analysis.
HRMS(MALDI) calcd for C22H23GeNO: m/z: 390.06 Found: 392.04.
(2) Synthesis of Compound 64B
Compound 64A (1.4 g, 3.57 mmol) and iridium chloride (0.6 g, 1.70 mmol) were mixed with 15 mL of 2-ethoxyethanol and 5 mL of DI water, and the resultant mixture was stirred while heating at reflux for 24 hours, and then, the temperature was allowed to cool to room temperature. The resulting solid was separated by filtration, washed sufficiently with water, methanol, and hexanes, in this stated order, and the obtained solid was dried in a vacuum oven to obtain 1.5 g of Compound 64B (83% yield). The obtained Compound 64B was used in the next reaction without an additional purification process.
(3) Synthesis of Compound 64
Compound 64B (1.50 g, 0.75 mmol), pentane-2,4-dione (0.19 g, 1.86 mmol), and potassium carbonate (K2CO3) (0.26 g, 1.86 mmol) were mixed with 15 mL of 2-ethoxyethanol, and the mixture was stirred for 18 hours at room temperature. After allowing the reaction to cool and subsequent extraction, the obtained solid was subjected to column chromatography (eluent: methylene chloride (MC) and hexanes) to obtain 0.68 g (yield of 85%) of Compound 64. The obtained compound was identified by HRMS and HPLC analysis.
HRMS(MALDI) calcd for C49H52Ge2IrN2O4: m/z: 1070.44 Found: 1072.83.
0.55 g (yield of 80%) of Compound 66 was obtained in a similar manner as used to synthesize Compound 64 of Synthesis Example 4, except that 8-bromo-2-(trimethylgermyl)furo[2,3-b:5,4-c′]dipyridine (1.5 g, 4.10 mmol) was used instead of 1-bromo-7-(trimethylgermyl)benzofuro[2,3-c]pyridine in synthesizing Compound 66A. The obtained compound was identified by HRMS and HPLC analysis.
HRMS(MALDI) calcd for C47H50Ge2IrN4O4: m/z: 1072.42 Found: 1074.92.
0.62 g (yield of 90%) of Compound 145 was obtained in a similar manner as used to synthesize Compound 64 of Synthesis Example 4, except that 2-(4-(t-butyl)naphthalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxoborolane (1.4 g, 4.52 mmol) was used instead of 2-(3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxoborolane in synthesizing Compound 145A. The obtained compound was identified by HRMS and HPLC analysis.
HRMS(MALDI) calcd for C61H64Ge2IrN2O4: m/z: 1226.67 Found: 1229.31.
0.60 g (yield of 87%) of Compound 155 was obtained in a similar manner as used to synthesize Compound 64 of Synthesis Example 4, except that 1-bromo-6-(trimethylgermyl)benzofuro[2,3-c]pyridine (1.5 g, 4.1 mmol) was used instead of 1-bromo-7-(trimethylgermyl)benzofuro[2,3-c]pyridine in synthesizing Compound 155A. The obtained compound was identified by HRMS and HPLC analysis.
HRMS(MALDI) calcd for C61H64Ge2IrN2O4: m/z: 1226.67 Found: 1228.99.
0.6 g (yield of 80%) of Compound 159 was obtained in a similar manner as used to synthesize Compound 64 of Synthesis Example 4, except that 1-bromo-8-(trimethylgermyl)benzofuro[2,3-c]pyridine (1.5 g, 4.11 mmol) was used instead of 1-bromo-7-(trimethylgermyl)benzofuro[2,3-c]pyridine in synthesizing Compound 159A, and 3,7-diethylnonane-4,6-dione (0.3 g, 1.40 mmol) was used instead of pentane-2,4-dione in synthesizing Compound 159. The obtained compound was identified by HRMS and HPLC analysis.
HRMS(MALDI) calcd for C69H80Ge2IrN2O4: m/z: 1338.89 Found: 1341.30.
As an anode, an ITO-patterned glass substrate was cut to a size of 50 millimeters (mm)×50 mm×0.5 mm, sonicated in isopropyl alcohol and pure water, each for 5 minutes, and then cleaned by exposure to ultraviolet rays and ozone for 30 minutes. The resultant glass substrate was loaded onto a vacuum deposition apparatus.
Compounds HT3 and F12 (p-dopant) were vacuum-codeposited at a weight ratio of 98:2 on the anode to form a hole injection layer having a thickness of 100 angstrom (Å), and Compound HT3 was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 1,650 Å.
Then, GH3 (host) and Compound 1 (dopant) were co-deposited at a weight ratio of 92:8 on the hole transport layer to form an emission layer having a thickness of 400 Å.
Then, Compound ET3 and LiQ (n-dopant) were co-deposited at a volume ratio of 50:50 on the emission layer to form an electron transport layer having a thickness of 350 Å, LiQ (n-dopant) was vacuum-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 cathode having a thickness of 1,000 Å, thereby completing the manufacture of an organic light-emitting device.
Organic light-emitting devices were manufactured in a similar manner as in Example 1, except that Compounds shown in Table 2 were each used instead of Compound 1 as a dopant in forming an emission layer.
The maximum value of external quantum efficiency (Max EQE, %), driving voltage (volts, V), maximum emission wavelength (λmax, nm) of the emission spectrum, and full width at half maximum (FWHM, nm) of each of the organic light-emitting devices manufactured in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated, and the results thereof are shown in Table 2. As evaluation apparatuses, a current-voltage meter (Keithley 2400) and a luminance meter (Minolta Cs-1000A) were used.
Referring to Table 2, it can be seen that the organic light-emitting devices of Examples 1 to 3 have high external quantum efficiency, a low driving voltage, and a narrow FWHM, as compared with the organic light-emitting devices of Comparative Examples 1 and 2.
As an anode, an ITO-patterned glass substrate was cut to a size of 50 millimeter (mm)×50 mm×0.5 mm, sonicated with isopropyl alcohol and DI water, each for 5 minutes, and then cleaned by exposure to Ultraviolet (UV) rays and ozone for 30 minutes. The resultant ITO-patterned glass substrate was loaded onto a vacuum deposition apparatus.
Compounds HT3 and F12(p-dopant) were co-deposited by vacuum on the anode at the weight ratio of 98:2 to form a hole injection layer having a thickness of 100 Å, and Compound HT3 was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 1,600 Å.
Then, RH3 (host) and Compound 64 (dopant) were co-deposited at a weight ratio of 97:3 on the hole transport layer to form an emission layer having a thickness of 400 Å.
Then, Compound ET3 and LiQ (n-dopant) were co-deposited on the emission layer at the volume ratio of 50:50 to form an electron transport layer having a thickness of 350 Å, LiQ was vacuum-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 cathode having a thickness of 1,000 Å, thereby completing the manufacture of an organic light-emitting device.
Organic light-emitting devices were manufactured in a similar manner as in Example 4, except that Compounds shown in Table 3 were each used instead of Compound 64 as a dopant in forming an emission layer.
The maximum value of external quantum efficiency (Max EQE, %), driving voltage (Volt, V), maximum emission wavelength (λmax, nm), and lifespan (relative %) of each of the organic light-emitting devices manufactured according to Examples 4 to 6 and Comparative Example 3, and results thereof are shown in Table 3. As evaluation apparatuses, a current-voltage meter (Keithley 2400) and a luminance meter (Minolta Cs-1000A) were used.
Referring to Table 3, it can be seen that the organic light-emitting devices of Examples 4 to 6 have excellent external quantum efficiency and lifetime characteristics, and low driving voltage. In addition, referring to Table 3, it can be seen that the organic light emitting devices of Examples 4 to 6 have a similar level or higher external quantum efficiency, a lower driving voltage, and a similar level or longer lifespan as compared with the organic light emitting devices of Comparative Example 3. The organometallic compound has excellent electrical characteristics and stability. Thus, an electronic device, for example, an organic light-emitting device, including the organometallic compound may have a low driving voltage, high efficiency, a long lifespan, a reduced roll-off ratio, and a relatively narrow EL spectrum emission peak FWHM. Accordingly, a high-quality organic light-emitting device may be implemented by using the organometallic compound.
It should be understood that exemplary embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each exemplary embodiment should typically be considered as available for other similar features or aspects in other exemplary embodiments. While one or more exemplary embodiments have been described with reference to the FIGURE, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0016842 | Feb 2021 | KR | national |
| 10-2022-0006178 | Jan 2022 | KR | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 9923154 | Oshiyama et al. | Mar 2018 | B2 |
| 20160268519 | Choi | Sep 2016 | A1 |
| 20180138427 | Ji et al. | May 2018 | A1 |
| 20180179238 | Lee | Jun 2018 | A1 |
| 20200313098 | Kim | Oct 2020 | A1 |
| 20210050533 | Choi | Feb 2021 | A1 |
| 20220223803 | Park | Jul 2022 | A1 |
| 20220275013 | Ji | Sep 2022 | A1 |
| Number | Date | Country |
|---|---|---|
| 107759638 | Mar 2018 | CN |
| 109988193 | Jul 2019 | CN |
| 2016219490 | Dec 2016 | JP |
| 1020190060589 | Jun 2019 | KR |
| 2012111548 | Aug 2012 | WO |
| 2016056562 | Apr 2016 | WO |
| Entry |
|---|
| CAS Abstract and Indexed Compounds, W. Choi et al., US 2016/0268519 (2016) (Year: 2016). |
| Number | Date | Country | |
|---|---|---|---|
| 20220348599 A1 | Nov 2022 | US |
