Patent Grant
12178116
This application claims the benefit of and priority to Korean Patent Application No. 10-2020-0019077, filed on Feb. 17, 2020, in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. § 119, the content of which is incorporated herein in its entirety by reference.
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-emission devices, which have improved characteristics in terms of viewing angles, response times, brightness, 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 disposed between the anode and the cathode, wherein the organic layer includes an emission layer. A hole transport region may be disposed between the anode and the emission layer, and an electron transport region may be disposed 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 transit from an excited state to a ground state, thereby generating 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, provided is an organometallic compound represented by Formula 1.
M(L1)n1(L2)n2 Formula 1
In Formula 1,
In Formula 2,
According to another aspect, provided is an organic light-emitting device including a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode and including an emission layer, wherein the organic layer includes at least one organometallic compound represented by Formula 1.
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.
According to another aspect, provided is 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 FIGURE, which shows 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. 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.
The terminology used herein is for the purpose of describing 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.” 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.
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 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.
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.
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 aspect of the present disclosure provides an organometallic compound represented by Formula 1 below:
M(L1)n1(L2)n2 Formula 1
In Formula 1, M may be a transition metal.
For example, M may be a first-row transition metal of the Periodic Table of Elements, a second-row transition metal of the Periodic Table of Elements, or a third-row transition metal of the Periodic Table of Elements.
In an embodiment, M may be iridium (Ir), platinum (Pt), osmium (Os), titanium (Ti), zirconium (Zr), hafnium (Hf), europium (Eu), terbium (Tb), thulium (Tm)), or rhodium (Rh).
In an embodiment, M may be Ir, Pt, Os, or Rh.
In Formula 1, L1 may be a ligand represented by Formula 2:
The groups X1 to X8, R1, R2, CY2, Y2, a1, and a2 of Formula 2 are the same as described in the present specification.
In Formula 1, n1 indicates the number of ligands L1 and may be 1, 2, or 3. When n1 is 2 or greater, two or more of ligands L1 may be identical to or different from each other. For example, n1 may be 1 or 2. As used herein, the term “ligand L1” is interchangeable with the term “L1 ligand” and both refer to an L1 group in Formula 1.
In Formula 1, L2 may be a monodentate ligand, a bidentate ligand, a tridentate ligand, or a tetradentate ligand. L2 is the same as described in the present specification.
In Formula 1, n2 indicates the number of ligands L2 and may be 0, 1, 2, 3, or 4. When n2 is 2 or greater, two or more ligands L2 may be identical to or different from each other. For example, n2 may be 0, 1, or 2. As used herein, the term “ligand L2” is interchangeable with the term “L2 ligand” and both refer to an L2 group in Formula 1.
In an embodiment, in Formula 1, i) M may be Ir or Os, and the sum of n1 and n2 may be 3 or 4; or ii) M may be Pt, and the sum of n1 and n2 may be 2.
In Formula 1, L1 and L2 may be different from each other.
In Formula 2, X1 to X8 may each independently be C or N, and at least one of X1 to X8 may be N.
In an embodiment, one or two of X1 to X8 in Formula 2 may be N.
In one or more embodiments, X2 in Formula 2 may be N.
In one or more embodiments, in Formula 2, 1) X2 may be N, 2) X2 and X6 may be N, or 3) X2 and X7 may be N.
In Formula 1, Y2 may be C or N.
For example, Y2 in Formula 2 may be C.
In Formula 2, ring CY2 may be a first ring or a condensed ring in which a first ring and at least one second ring are condensed with each other, wherein the first ring is a 6-membered ring, and the second ring is a C5-C30 carbocyclic group or a C1-C30 heterocyclic group, wherein one ring-forming atom of the first ring may be Y2 in Formula 2. Accordingly, one of the ring-forming atoms of the first ring, which may be a first ring alone or a first ring that is condensed with the at least one second ring, may be Y2 in Formula 2 and thus Y2 represents a ring-forming atom of the first ring.
For example,
In an embodiment, ring CY2 in Formula 2 may be a cyclohexene group, a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a cyclopentadiene group, a 1,2,3,4-tetrahydronaphthalene group, an indene group, a benzosilole group, a benzogermole group, a benzothiophene group, a benzoselenophene group, a benzofuran group, a carbazole group, a dibenzoborole group, a dibenzophosphole group, a fluorene group, a dibenzosilole group, a dibenzogermole group, a dibenzothiophene group, a dibenzoselenophene group, a dibenzofuran group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, or a 5,6,7,8-tetrahydroquinoline group.
In one or more embodiments, ring CY2 in Formula 2 may be a benzene group, a naphthalene group, a 1,2,3,4-tetrahydronaphthalene group, a carbazole group, a fluorene group, a dibenzosilole group, a dibenzothiophene group, a dibenzofuran group, an azacarbazole group, an azafluorene group, an azadibenzosilole group, an azadibenzothiophene group, an azadibenzofuran group, a pyridine group, a pyrimidine group, a pyrazine group, or a pyridazine group.
In Formula 2, R1 and R2 may each independently be 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 C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C7-C60 alkylaryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C7-C60 arylalkyl group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted C2-C60 heteroarylalkyl group, a substituted or unsubstituted C2-C60 alkylheteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —Ge(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q9), or —P(Q8)(Q9).
For example, R1 and R2 may each independently be:
In one or more embodiments, R1 and R2 in Formula 2 may each independently be hydrogen, deuterium, —F, —CH3, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a C2-C10 alkenyl group, a C1-C10 alkoxy group, a C1-C10 alkylthio group, a group represented by one of Formulae 9-1 to 9-39, a group represented by one of Formulae 9-1 to 9-39 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 9-1 to 9-39 in which at least one hydrogen is substituted with —F, a group represented by one of Formulae 9-201- to 9-237, a group represented by one of Formulae 9-201 to 9-237 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 9-201 to 9-237 in which at least one hydrogen is substituted with —F, a group represented by one of Formulae 10-1 to 10-129, a group represented by one of Formulae 10-1 to 10-129 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 10-1 to 10-129 in which at least one hydrogen is substituted with —F, a group represented by one of Formulae 10-201 to 10-350, a group represented by one of Formulae 10-201 to 10-350 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 10-201 to 10-350 in which at least one hydrogen is substituted with —F, —Si(Q3)(Q4)(Q5), or —Ge(Q3)(Q4)(Q5) (wherein Q3 to Q5 are the same as described in the present specification):
In Formulae 9-1 to 9-39, 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 is a phenyl group, TMS is a trimethylsilyl group, and TMG is a trimethylgermyl group.
The “group represented by one of Formulae 9-1 to 9-39 in which at least one hydrogen is substituted with deuterium” and the “group represented by one of Formulae 9-201 to 9-237 in which at least one hydrogen is substituted with deuterium” may be, for example, a group represented by one of Formulae 9-501 to 9-514 and 9-601 to 9-636:
The “group represented by one of Formulae 9-1 to 9-39 in which at least one hydrogen is substituted with —F” and the “group represented by one of Formulae 9-201 to 9-237 in which at least one hydrogen is substituted with —F” may be, for example, a group represented by one of Formulae 9-701 to 9-710:
The “group represented by one of Formulae 10-1 to 10-129 in which at least one hydrogen is substituted with deuterium” and the “group represented by one of Formulae 10-201 to 10-350 in which at least one hydrogen is substituted with deuterium” may be, for example, a group represented by one of Formulae 10-501 to 10-553:
The “group represented by one of Formulae 10-1 to 10-129 in which at least one hydrogen is substituted with —F” and the “group represented by one of Formulae 10-201 to 10-350 in which at least one hydrogen is substituted with —F” may be, for example, a group represented by one of Formulae 10-601 to 10-617:
In Formula 2, 1) two or more of a plurality of groups R1 may optionally be linked to each other to form a C5-C30 carbocyclic group that is unsubstituted or substituted with at least one R10a or a C1-C30 heterocyclic group that is unsubstituted or substituted with at least one R10a, and 2) two or more of a plurality of groups R2 may optionally be linked to each other to form a C5-C30 carbocyclic group that is unsubstituted or substituted with at least one R10a or a C1-C30 heterocyclic group that is unsubstituted or substituted with at least one R10a. Here, R10a is the same as described in connection with R2 in the present specification.
In Formula 2, “*” and “*” each indicate a binding site to M in Formula 1.
In an embodiment, a1 in Formula 2 may be an integer from 1 to 7, and R1 may not be hydrogen.
In one or more embodiments, a group represented by
in Formula 2 may be represented by one of Formulae CY1-A to CY1-C:
In Formulae CY1-A to CY1-C,
For example, ring CY11 in Formulae CY1-A to CY1-C may be a cyclohexane group, a benzene group, a naphthalene group, a pyridine group, or a pyrimidine group.
In one or more embodiments, a group represented by
in Formula 2 may be represented by one of Formulae CY1-A(1) to CY1-C(1):
In Formulae CY1-A(1) to CY1-C(1),
For example, X9 to X12 in Formulae CY1-A(1) to CY1-C(1) may be C.
In one or more embodiments, a group represented by
in Formula 2 may be represented by one of Formulae CY1(1) to CY1(27):
In Formulae CY1(1) to CY1(27), *′ indicates a binding site to M in Formula 1, and *″ indicates a binding site to ring CY2 in Formula 2.
In one or more embodiments, a group represented by
in Formula 2 may be represented by one of Formulae CY1-1 to CY1-128:
In Formulae CY1-1 to CY1-128,
In one or more embodiments, the ligand represented by Formula 2 may include:
In one or more embodiments, group R1 in the number of a1 in Formula 2 may each independently be:
In one or more embodiments, group R2 in the number of a2 in Formula 2 may each independently be:
In one or more embodiments, Formula 2 may satisfy at least one of Condition A to Condition G:
Condition A
In one or more embodiments, a group represented by:
in Formula 2 may be a group represented by one of Formulae CY2-1 to CY2-31:
In Formulae CY2-1 to CY2-31,
In one or more embodiments, a group represented by
in Formula 2 may be a group represented by one of Formulae CY2(1) to CY2(68):
In Formulae CY2(1) to CY2(68),
In one or more embodiments, at least one group R2 in the number of a2 in Formula 2 may be a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted phenyl group.
In one or more embodiments, R2 in Formula 2 may not be hydrogen, and a2 may be 1, 2, or 3.
In one or more embodiments, R2 in Formula 2 may not include a fluoro group and a cyano group.
In one or more embodiments, a group represented by
in Formula 2 may be a group represented by Formula CY2(10).
For example, R22 and R24 in Formula CY2(10) may each independently be a C1-C20alkyl group or a C3-C10 cycloalkyl group, each unsubstituted or substituted with at least one of deuterium, a C1-C20 alkyl group, or a C3-C10 cycloalkyl group.
In an embodiment, R22 and R24 in Formula CY2(10) may be identical to each other.
In an embodiment, R22 and R24 in Formula CY2(10) may be different from each other.
In an embodiment, in Formula CY2(10), the number of carbons included in R22 may be greater than the number of carbons included in R24.
L2 in Formula may be a bidentate ligand of which two atoms are each bonded with M in Formula 1 via O, S, N, C, P, Si, or As.
For example, L2 in Formula 1 may be a bidentate ligand represented by Formula 3:
In Formula 3,
For example, in Formula 3, i) X31 and X32 may be O; ii) X31 may be O, and X32 may be N, or iii) X31 may be N, and X32 may be C.
In one or more embodiments, L2 in Formula 1 may be a monodentate ligand, for example, I−, Br−, Cl−, sulfide, nitrate, azide, hydroxide, cyanate, isocyanate, thiocyanate, water, acetonitrile, pyridine, ammonia, carbon monoxide, P(Ph)3, P(Ph)2CH3, PPh(CH3)2, P(CH3)3, or a combination thereof.
In one or more embodiments, L2 in Formula 1 may be bidentate ligands, for example, oxalate, acetylacetonate, picolinic acid, 1,2-bis(diphenylphosphino)ethane, 1,1-bis(diphenylphosphino)methane, glycinate, or ethylenediamine.
In one or more embodiments, L2 in Formula 1 may be a group represented by one of Formulae 3A to 3F:
In Formulae 3A to 3F,
For example, L2 in Formula 1 may be a group represented by one of Formulae 3A to 3C.
For example, a group represented by
in Formula 3D may be a group represented by Formulae CY11-1 to CY11-34, or a group represented by
in Formulae 3C and 3D may be a group represented by one of Formulae CY12-1 to CY12-34:
In Formulae CY11-1 to CY11-34 and CY12-1 to CY12-34,
In an embodiment, L2 in Formula 1 may be a group represented by one of Formulae 3-1(301) to 3-1(309):
In Formulae 3-1(301) to 3-1(309),
In an embodiment, L2 in Formula 1 may be a group represented by Formula 3-1(301), and Formula 3-1(301) may satisfy at least one of Condition 1 to Condition 3 below:
Condition 1
Z11 to Z16 in Formula 3-1(301) are each independently a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 heterocycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group.
Condition 2
At least one of Z11 to Z16 in Formula 3-1(301) (for example, at least one of Z11 to Z13 and at least one of Z14 to Z16) is each independently a substituted or unsubstituted C2-C60 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 heterocycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group.
Condition 3
Z17 in Formula 3-1(301) is deuterium, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 heterocycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group.
In an embodiment, Formula 3-1(301) may satisfy at least one of above-described Condition 1 and Condition 2.
Without wishing to be bound by theory, since Formula 3-1(301) satisfies at least one of above-described Condition 1 and Condition 2, the organometallic compound represented by Formula 1 may have relatively large steric hindrance, thereby reducing triplet-triplet extinction. As such, an electronic device, such as an organic light-emitting device, including the organometallic compound represented by Formula 1 may have excellent internal quantum emission efficiency.
In one or more embodiments, L2 in Formula 1 may be a group represented by Formula 3-1(301), and Formula 3-1(301) may satisfy at least one of Condition 4 and Condition 5 below:
Condition 4
Two or more of Z1 to Z13 in Formula 3-1(301) are linked to each other such that a group represented by *—C(Z11)(Z12)(Z13) in the group represented by Formula 3-1(301) is a C5-C30 carbocyclic group that is unsubstituted or substituted with at least one R10a or a C1-C30 heterocyclic group that is unsubstituted or substituted with at least one R10a.
Condition 5
Two or more of Z4 to Z6 in Formula 3-1(301) are linked to each other such that a group represented by *—C(Z14)(Z15)(Z16) in the group represented by Formula 3-1(301) is a C5-C30 carbocyclic group that is unsubstituted or substituted with at least one R10a or a C1-C30 heterocyclic group that is unsubstituted or substituted with at least one R10a.
In one or more embodiments, L2 in Formula 1 may be a group represented by Formula 3-1(301), and a group represented by *—C(Z11)(Z12)(Z13) in Formula 3-1(301) and a group represented by *—C(Z14)(Z15)(Z16) in Formula 3-1(301) may be identical to each other.
In one or more embodiments, L2 in Formula 1 may be a group represented by Formula 3-1(301), and a group represented by *—C(Z11)(Z12)(Z13) in Formula 3-1(301) and a group represented by *—C(Z14)(Z15)(Z16) in Formula 3-1(301) may be different from each other.
In one or more embodiments, L2 in Formula 1 may be a group represented by Formula 3-1(301), and the number of carbons included in a group represented by *—C(Z11)(Z12)(Z13) in Formula 3-1(301) may be 4 or more, 5 or more, or 6 or more.
In one or more embodiments, L2 in Formula 1 may be a group represented by Formula 3-1(301), and the number of carbons included in a group represented by *—C(Z14)(Z15)(Z16) in Formula 3-1(301) may be 4 or more, 5 or more, or 6 or more.
In one or more embodiments, L2 in Formula 1 may be a group represented by Formula 3-1(301), and a case in which, in Formula 3-1(301), 1) Z17 is hydrogen, and 2) both a group represented by *—C(Z11)(Z12)(Z13) and a group represented by *—C(Z14)(Z15)(Z16) are methyl groups, may be excluded.
In one or more embodiments, L2 in Formula 1 may be a group represented by Formula 3-1(301), and a case in which, in Formula 3-1(301), 1) Z17 is hydrogen, and 2) each of Z1 to Z16 is a methyl group, may be excluded.
In an embodiment, the organometallic compound represented by Formula 1 may emit red light or green light, for example, red or green light having a maximum emission wavelength of about 500 nm or more, for example, about 500 nm or more and about 650 nm or less.
In one or more embodiments, the organometallic compound may be one of Compounds 1 to 694 below:
In the organometallic compound represented by Formula 1, L1 is a ligand represented by Formula 2, and n1 indicating the number groups L1 is 1, 2, or 3. That is, the organometallic compound essentially includes at least one ligand represented by Formula 2, as a ligand linked to metal.
In a ligand represented by Formula 2, ring CY2 is a first ring or a condensed ring in which a first ring and at least one second ring are condensed with each other, wherein the first ring is a 6-membered ring, and the second ring is a C5-C30 carbocyclic group or a C1-C30 heterocyclic group, wherein one ring-forming atom of the first ring, which may be a first ring or a first ring that is condensed with the second ring, is Y2 in Formula 2. In addition, at least one of X1 to X8 in Formula 2 is N. Furthermore, in a ligand represented by Formula 2, a benzo ring 1 is condensed at the same position as in Formula 2′ below. Without wishing to be bound by theory, since transition dipole moment increases in the direction of the orientation axis of Formula 2, a conjugation length of the organometallic compound represented by Formula 1 relatively increases, and sterical rigidity of the organometallic compound represented by Formula 1 increases, thereby reducing non-radiative transition of the organometallic compound represented by Formula 1. As such, an electronic device, such as an organic light-emitting device, including the organometallic compound represented by Formula 1 may have improved emission efficiency and improved lifespan.
With respect to some of organometallic compounds represented by Formula 1, highest occupied molecular orbital (HOMO) energy levels, lowest unoccupied molecular orbital (LUMO) energy levels, S1 energy levels, and T1 energy levels were evaluated using Gaussian 09 program with molecular structure optimization by density functional theory (DFT) based on B3LYP, and results thereof are as follows in Table 1.
Referring to Table 1, it is confirmed that organometallic compounds represented by Formula 1 have such electrical characteristics that are suitable for use as a material for an electronic device, for example a dopant for an organic light-emitting device.
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 below.
The organometallic compound represented by Formula 1 is suitable for use as a material for an organic layer, for example a dopant for an emission layer of the organic layer, of an organic light-emitting device. Thus, according to another aspect, provided is an organic light-emitting device including: a first electrode; a second electrode; and an organic layer disposed between the first electrode and the second electrode and including an emission layer, wherein the organic layer includes at least one organometallic compound represented by Formula 1.
Since the organic light-emitting device has an organic layer containing the organometallic compound represented by Formula 1 as described above, excellent characteristics may be obtained with respect to driving voltage, external quantum efficiency, and lifespan, and the full width at half maximum (FWHM) of the emission peak in the electroluminescence (EL) spectrum is relatively narrow (or, small).
The organometallic compound of Formula 1 may be disposed between a pair of electrodes of an organic light-emitting device. For example, 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 (weight) of the organometallic compound represented by Formula 1 in the emission layer is smaller than an amount (weight) of the host). The emission layer may emit red light or green light, for example, red or green light having a maximum emission wavelength of about 500 nm or more, for example, about 500 nm or more and about 650 nm or less.
In an embodiment, the emission layer may emit red light.
The expression “(an organic layer) includes at least one organometallic compound” 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”.
For example, in some aspects the organic layer may include, as the organometallic compound, only Compound 1 (where Compound 1 is a hypothetical organometallic compound). In this regard, Compound 1 may be present only 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 (where Compound 2 is another hypothetical organometallic compound that is different from Compound 1). In this regard, Compound 1 and Compound 2 may exist in the same layer (for example, both Compound 1 and Compound 2 may be present in the emission layer). It is to be understood that at least one of Compound 1 or Compound 2 is an organometallic compound represented by Formula 1, and for the case where “(an organic layer) includes two or more different organometallic compounds represented by Formula 1”, it is to be understood that Compound 1 and Compound 2 are each a different organometallic compound represented by Formula 1.
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 an embodiment, in the organic light-emitting device, the first electrode is an anode, and the second electrode is a cathode, and the organic layer may further include a hole transport region between the first electrode and the emission layer and an electron transport region disposed between the emission layer and the second electrode, 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” used herein refers to a single layer and/or a plurality of layers disposed between the first electrode and the second electrode of the organic light-emitting device. The “organic layer” may include, in addition to an organic compound, an organometallic complex including metal.
The FIGURE is a schematic cross-sectional view of an organic light-emitting device 10 according to an embodiment. Hereinafter, the structure of an organic light-emitting device according to an embodiment and a method of manufacturing an organic light-emitting device according to an embodiment 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 include 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 include indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), or any combination thereof. In one or more embodiments, the material for forming the first electrode 11 may include a metal or a metal alloy, such as magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), or any combination thereof.
The first electrode 11 may have a single-layered structure or a multi-layered structure including two or more different layers. For example, the first electrode 11 may have a three-layered structure of ITO/Ag/ITO.
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 disposed 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 from the first electrode 11 in a direction towards the second electrode 19.
When the hole transport region includes a hole injection layer (HIL), the hole injection layer may be formed 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 a 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° C. 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 Angstrom per second (Å/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.
Conditions for forming a hole transport layer and an electron blocking layer may be understood by referring to conditions for forming the hole injection layer.
The hole transport region may include m-MTDATA, TDATA, 2-TNATA, NPB, R-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated-NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonicacid (PANI/CSA), polyaniline/poly(4-styrenesulfonate) (PANI/PSS), a compound represented by Formula 201 below, a compound represented by Formula 202 below, or a combination thereof:
In Formula 201, Ar101 and Ar102 may each independently be a phenylene group, a pentalenylene group, an indenylene group, a naphthylene group, an azulenylene group, a heptalenylene group, an acenaphthylene group, a fluorenylene group, a phenalenylene group, a phenanthrenylene group, an anthracenylene group, a fluoranthenylene group, a triphenylenylene group, a pyrenylene group, a chrysenylenylene group, a naphthacenylene group, a picenylene group, a perylenylene group, or a pentacenylene group, each unsubstituted or substituted with at least one of deuterium, —F, —Cl, —Br, —I, 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 C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C10 cycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C7-C60 alkylaryl group, a C6-C60 aryloxy group, a C3-C10 arylthio group, a C7-C60 arylalkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C2-C60 heteroarylalkyl group, a C2-C60 alkylheteroaryl group, a monovalent non-aromatic condensed polycyclic group, or a monovalent non-aromatic condensed heteropolycyclic group.
In Formula 201, xa and xb 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.
In Formulae 201 and 202, R101 to R108, R111 to R119, and R121 to R124 may each independently be:
In Formula 201, R109 may be a phenyl group, a naphthyl group, an anthracenyl group, or a pyridinyl group, each unsubstituted or substituted with at least one of deuterium, —F, —Cl, —Br, —I, 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 C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a naphthyl group, an anthracenyl group, or a pyridinyl group.
In an embodiment, the compound represented by Formula 201 may be represented by Formula 201A:
In Formula 201A, R101, R111, R112, and R109 are understood by referring to the description provided herein.
For example, the hole transport region may include one of Compounds HT1 to HT21 or a combination thereof:
A thickness of the hole transport region may be in a 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 a hole injection layer, a hole transport layer, an electron blocking layer, or a combination thereof, 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 include a quinone derivative, a metal oxide, a cyano group-containing compound, or a combination thereof. For example, the p-dopant may include: a quinone derivative such as tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4-TCNQ), or F6-TCNNQ; metal oxide such as tungsten oxide and molybdenum oxide; a cyano group-containing compound such as Compound HT-D1; or a combination thereof.
The hole transport region may include a buffer layer.
The buffer layer may compensate for an optical resonance distance according to a wavelength of light emitted from an emission layer, and thus, emission efficiency of an organic light-emitting device may be improved.
Meanwhile, when the hole transport region includes an electron blocking layer, a material for forming the electron blocking layer may include a material that is used in the hole transport region as described above, a host material described below, or a combination thereof. For example, when the hole transport region includes an electron blocking layer, mCP described below, Compound HT21, or a combination thereof may be used as the material for forming the electron blocking layer.
Then, 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 hole transport layer.
The emission layer may include a host and a dopant, and the dopant may include the organometallic compound represented by Formula 1 as described herein.
The host may include TPBi, TBADN, ADN (also referred to as “DNA”), CBP, CDBP, TCP, mCP, Compound H50, Compound H51, Compound H52, or a combination thereof:
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/or 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 this range, 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. 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 comprise 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, BCP, Bphen, BAlq, or any combination thereof.
In one or more embodiments, the hole blocking layer may include the host, a material for forming an electron transport layer as described below, a material for forming an electron injection layer as described below, or a combination thereof.
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 600 Å. Without wishing to be bound by theory, when the thickness of the hole blocking layer is within the range described above, the hole blocking layer may have excellent hole blocking characteristics without a substantial increase in driving voltage.
The electron transport layer may include BCP, Bphen, TPBi, Alq3, BAlq, TAZ, NTAZ, or a combination thereof:
Alternatively, the electron transport layer may include one of Compounds ET1 to ET25 below or a combination thereof:
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. Without wishing to be bound by theory, when the thickness of the electron transport layer is within the range described above, the electron transport layer may have satisfactory electron transport characteristics without a substantial increase in driving voltage.
The electron transport layer may further include, in addition to the materials described above, a metal-containing material.
The metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 or ET-D2:
In some embodiments, the electron transport region may include an electron injection layer that promotes the flow of electrons from the second electrode 19 thereinto.
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, and, for example, about 3 Å to about 90 Å. Without wishing to be bound by theory, when the thickness of the electron injection layer is within the range described above, the electron injection layer may have satisfactory electron injection characteristics without a substantial increase in driving voltage.
The second electrode 19 may be 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 has a relatively low work function. For example, lithium (Li), magnesium (Mg), aluminum (Al), 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 the FIGURE, but embodiments of the present disclosure are not limited thereto.
According to another aspect, the organic light-emitting device may be included in an electronic apparatus. Thus, an electronic apparatus including the organic light-emitting device is provided. The electronic apparatus may include, for example, a display, an illumination, a sensor, and the like.
According to another aspect, provided is a diagnostic composition including at least one organometallic compound represented by Formula 1.
The organometallic compound represented by Formula 1 provides high luminescent 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, for example 1 to 20 carbon atoms, or 1 to 10 carbon atoms. The term “C1-C60 alkylene group” as used herein refers to a divalent group having the same structure as the C1-C60 alkyl group.
Examples of the C1-C60 alkyl group may include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, or a tert-decyl group, each unsubstituted or substituted with at least one of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, or a tert-decyl group. For example, Formula 9-33 is a branched C6 alkyl group, for example, a tert-butyl group that is substituted with two methyl groups.
The term “C1-C60 alkoxy group” used herein refers to a monovalent group represented by —OA101 (wherein A101 is the C1-C60 alkyl group).
Examples of the C1-C60 alkoxy group, the C1-C20 alkoxy group, or the C1-C10 alkoxy group may include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a pentoxy group.
The term “C2-C60 alkenyl group” as used herein has a structure including 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 has a structure including 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. The term “C3-C10 cycloalkylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkyl group.
Examples of the C3-C10 cycloalkyl group 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(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, or the like.
The term “C1-C10 heterocycloalkyl group” as used herein refers to a monovalent saturated monocyclic group having at least one heteroatom selected from N, O, P, Si, S, Se, Ge, As, and B as a ring-forming atom and 1 to 10 carbon atoms, and non-limiting 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.
Examples of the C1-C10 heterocycloalkyl group may include a silolanyl group, a silinanyl group, a tetrahydrofuranyl group, a tetrahydro-2H-pyranyl group, a tetrahydrothiophenyl group, or the like.
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 “C1-C10 heterocycloalkenyl group” as used herein refers to a monovalent monocyclic group that has at least one heteroatom selected from N, O, P, Si, S, Se, Ge, As, 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 C1-C10 heterocycloalkenyl group include a 2,3-dihydrofuranyl group and a 2,3-dihydrothiophenyl group. The term “C1-C10 heterocycloalkenylene group” as used herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as used herein refers to a monovalent group having a carbocyclic aromatic system having 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 alkylaryl group” as used herein refers to a C6-C60 aryl group substituted with at least one C1-C60 alkyl group. The term “C7-C60 arylalkyl 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 at least one hetero atom selected from N, O, P, Si, S, Se, Ge, As, and B as a ring-forming atom and a cyclic aromatic system having 1 to 60 carbon atoms, and the term “C1-C60 heteroarylene group” as used herein refers to a divalent group having at least one hetero atom selected from N, O, P, Si, S, Se, Ge, As, and B as a ring-forming atom and a carbocyclic aromatic system having 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 C1-C60 heteroaryl group and the C1-C60 heteroarylene group each include two or more rings, the rings may be fused to each other.
The term “C2-C60 alkylheteroaryl group” used herein refers to a C1-C60 heteroaryl group substituted with at least one C1-C60 alkyl group.
The term “C6-C60 aryloxy group” as used herein indicates —OA102 (wherein A102 indicates the C6-C60 aryl group), the C6-C60 arylthio group indicates —SA103 (wherein A103 indicates the C6-C60 aryl group), and the C1-C60 alkylthio group indicates —SA104 (wherein A104 indicates the C1-C60 alkyl group).
The term “C1-C60 heteroaryloxy group” as used herein refers to —OA106 (wherein A106 is the C2-C60 heteroaryl group), the term “C1-C60 heteroarylthio group” as used herein indicates —SA107 (wherein A107 is the C1-C60 heteroaryl group), and the term “C2-C60 heteroarylalkyl group” as used herein refers to -A108A109 (A109 is a C1-C59 heteroaryl group, and A108 is a C1-C59 alkyl 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 non-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 the 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 1 to 60 carbon atoms) having two or more rings condensed to each other, a heteroatom selected from N, O, P, Si, S, Se, Ge, As, and B, other than carbon atoms, as a ring-forming atom, and non-aromaticity in its entire molecular structure. The monovalent non-aromatic condensed heteropolycyclic group includes a carbazolyl group. The term “divalent non-aromatic condensed heteropolycyclic group” as used herein refers to a divalent group having the same structure as the 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 a ring-forming atom, 5 to 30 carbon atoms only. The C5-C30 carbocyclic group may be a monocyclic group or a polycyclic group. The “C5-C30 carbocyclic group (unsubstituted or substituted with at least one R10a)” may include, for example, an adamantane group, a norbornane (bicyclo[2.2.1]heptane) group, a norbornene group, a bicyclo[1.1.1]pentane group, a bicyclo[2.1.1]hexane group, a bicyclo[2.2.2]octane group, a cyclopentane group, a cyclohexane group, a cyclohexene group, a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a 1,2,3,4-tetrahydronaphthalene group, a cyclopentadiene group, a silole group, and a fluorene group (each unsubstituted or substituted with at least one R10a).
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 hetero atom selected from N, O, P, Si, S, Se, Ge, As, and B other than 1 to 30 carbon atoms. The C1-C30 heterocyclic group may be a monocyclic group or a polycyclic group. The “C1-C30 heterocyclic group (unsubstituted or substituted with at least one R10a)” may include, for example, a thiophene group, a furan group, a pyrrole group, a silole group, borole group, a phosphole group, a selenophene group, a germole group, a benzothiophene group, a benzofuran group, an indole group, an indene group, a benzosilole group, a benzoborole group, a benzophosphole group, a benzoselenophene group, a benzogermole group, a dibenzothiophene group, a dibenzofuran group, a carbazole group, a dibenzosilole group, a dibenzoborole group, a dibenzophosphole group, a dibenzoselenophene group, a dibenzogermole group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azabenzothiophene group, an azabenzofuran group, an azaindole group, an azaindene group, an azabenzosilole group, an azabenzoborole group, an azabenzophosphole group, an azabenzoselenophene group, an azabenzogermole group, an azadibenzothiophene group, an azadibenzofuran group, an azacarbazole group, an azafluorene group, an azadibenzosilole group, an azadibenzoborole group, an azadibenzophosphole group, an azadibenzoselenophene group, an azadibenzogermole group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isooxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, or a 5,6,7,8-tetrahydroquinoline group, each unsubstituted or substituted with at least one R10a as defined herein.
The terms “fluorinated C1-C60 alkyl group (or a fluorinated C1-C20 alkyl group or the like)”, “fluorinated C3-C10 cycloalkyl group”, “fluorinated C1-C10 heterocycloalkyl group”, and “fluorinated phenyl group” respectively indicate a C1-C60 alkyl group (or a C1-C20 alkyl group or the like), a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, and a phenyl group, each substituted with at least one fluoro group (—F). For example, the term “fluorinated C1 alkyl group (that is, a fluorinated methyl group)” may include —CF3, —CF2H, and —CFH2. The term “fluorinated C1-C60 alkyl group (or a fluorinated C1-C20 alkyl group or the like)”, “fluorinated C3-C10 cycloalkyl group”, or “fluorinated C1-C10 heterocycloalkyl group” may be i) a fully fluorinated C1-C60 alkyl group (or, a fully fluorinated C1-C20 alkyl group or the like), a fully fluorinated C3-C10 cycloalkyl group, or a fully fluorinated C1-C10 heterocycloalkyl group, wherein, in each group, all hydrogen atoms included therein are substituted with a fluoro group, or ii) a partially fluorinated C1-C60 alkyl group (or a partially fluorinated C1-C20 alkyl group or the like), a partially fluorinated C3-C10 cycloalkyl group, or a partially fluorinated C1-C10 heterocycloalkyl group, wherein, in each group, some of the hydrogen atoms are substituted with a fluoro group but all of the hydrogen atoms included therein are not substituted with a fluoro group.
The terms “deuterated C1-C60 alkyl group (or a deuterated C1-C20 alkyl group or the like)”, “deuterated C3-C10 cycloalkyl group”, “deuterated C1-C10 heterocycloalkyl group”, and “deuterated phenyl group” respectively indicate a C1-C60 alkyl group (or a C1-C20alkyl group or the like), a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, and a phenyl group, each substituted with at least one deuterium. For example, the “deuterated C1 alkyl group (that is, a deuterated methyl group)” may include —CD3, —CD2H, and —CDH2, and examples of the “deuterated C3-C10 cycloalkyl group” may refer to, for example, Formula 10-501 and the like. The term “deuterated C1-C60 alkyl group (or, a deuterated C1-C20 alkyl group or the like)”, “deuterated C3-C10 cycloalkyl group”, or “deuterated C1-C10 heterocycloalkyl group” may be i) a fully deuterated C1-C60 alkyl group (or, a fully deuterated C1-C20 alkyl group or the like), a fully deuterated C3-C10 cycloalkyl group, or a fully deuterated C1-C10 heterocycloalkyl group, wherein, in each group, all hydrogen atoms included therein are substituted with deuterium, or ii) a partially deuterated C1-C60 alkyl group (or, a partially deuterated C1-C20 alkyl group or the like), a partially deuterated C3-C10 cycloalkyl group, or a partially deuterated C1-C10 heterocycloalkyl group, wherein, in each group, some of the hydrogen atoms are substituted for deuterium but all hydrogen atoms included therein are not substituted with deuterium.
The term “(C1-C20 alkyl) ‘X’ group” as used herein refers to a ‘X’ group that is substituted with at least one C1-C20 alkyl group. For example, the term “(C1-C20 alkyl)C3-C10 cycloalkyl group” as used herein refers to a C3-C10 cycloalkyl group substituted with at least one C1-C20 alkyl group, and the term “(C1-C20 alkyl)phenyl group” as used herein refers to a phenyl group substituted with at least one C1-C20 alkyl group. An example of a (C1 alkyl)phenyl group is a toluyl group.
The terms “an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene group, and a 5,5-dioxide group” respectively refer to heterocyclic groups having the same backbones as “an indole group, a benzoborole group, a benzophosphole group, an indene group, a benzosilole group, a benzogermole group, a benzothiophene group, a benzoselenophene group, a benzofuran group, a carbazole group, a dibenzoborole group, a dibenzophosphole group, a fluorene group, a dibenzosilole group, a dibenzogermole group, a dibenzothiophene group, a dibenzoselenophene group, a dibenzofuran group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene group, and a 5,5-dioxide group,” in which, in each group, at least one of carbon atoms forming rings thereof is substituted with nitrogen.
Substituents of the substituted C5-C30 carbocyclic group, the substituted C2-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 C1-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C7-C60 alkylaryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C7-C60 arylalkyl group, the substituted C1-C60 heteroaryl group, the substituted C1-C60 heteroaryloxy group, the substituted C1-C60 heteroarylthio group, the substituted C2-C60 heteroarylalkyl group, the substituted C2-C60 alkylheteroaryl group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may each independently be:
Hereinafter, compounds and organic light-emitting devices according to one or more exemplary embodiments are described in further detail with reference to Synthesis Examples and Examples, but the present disclosure is not limited thereto. The wording “B was used instead of A” used in describing Synthesis Examples means that an amount of A that was used was identical to an amount of B that was used, in terms of a molar equivalent.
Scheme 1 shows the synthesis of Compound 24.
Synthesis of Compound L24-dimer
Compound L24 (4-(3,5-dimethylphenyl)-8,10-diisopropyl-2-methylbenzo[h]quinazoline) (1.86 grams (g), 4.86 millimoles (mmol)) and iridium chloride hydrate (0.76 g, 2.16 mmol) were mixed with 24 milliliters (mL) of 2-ethoxyethanol and 8 mL of deionized water, and the mixture was stirred at reflux for 24 hours at 120° C. and after the reaction, cooled to room temperature (ca. 25° C.). A solid material formed therefrom was separated by filtration and washed thoroughly with water, methanol, and hexane in the stated order to obtain a solid which was then dried in a vacuum oven to obtain Compound L24-dimer (1.50 g, 70%). The obtained compound was used in the synthesis of compound 24 without further purification.
Synthesis of Compound 24
Compound L24-dimer (0.96 g, 0.5 mmol), 3,7-diethyl-3,7-dimethylnonane-4,6-dione (0.72 g, 3.01 mmol), and Na2CO3 (0.32 g, 3.01 mmol) were mixed with 30 mL of 2-ethoxyethanol, and then stirred for 24 hours to proceed reaction. An organic layer was extracted from the resultant obtained therefrom by using ethyl acetate, anhydrous magnesium sulfate (MgSO4) was added thereto to remove water, and followed by filtration to obtain a filtrate which was then decompressed to obtain residue, which was then purified by performing column chromatography using a mixture of dichloromethane and hexane (1:1 vol/vol), to thereby obtain Compound 24 (0.64 g, 53%). The obtained compound was identified by high resolution mass spectrometry (HRMS) and high performance liquid chromatography (HPLC) analysis.
HRMS (matrix assisted laser desorption ionization-time of flight, MALDI-TOF) calcd. for C69H85IrN4O2: m/z 1194.6302, Found: 1194.6300.
Scheme 2 shows the synthesis of Compound 485.
Synthesis of Compound L485-Dimer
Compound L485 (4-(3-(tert-butyl)-5-methylphenyl)-10-isopropylbenzo[h]quinazoline) (1.84 g, 5.00 mmol) and iridium chloride hydrate (0.78 g, 2.22 mmol) were mixed with 21 mL of 2-ethoxyethanol and 7 mL of deionized water, and the mixture was stirred at reflux for 24 hours at 120° C. and after the reaction, cooled to room temperature. A solid material formed therefrom was separated by filtration and washed thoroughly with water, methanol, and hexane in the stated order to obtain a solid which was then dried in a vacuum oven to obtain Compound L485-dimer (1.80 g, 84%). The obtained compound was used in the synthesis of compound 485 without further purification.
Synthesis of Compound 485
Compound L485-dimer (1.01 g, 0.53 mmol), 3,3,7,7-tetramethylnonane-4,6-dione (0.67 g, 3.16 mmol), and Na2CO3 (0.34 g, 3.16 mmol) were mixed with 30 mL of 2-ethoxyethanol, and then stirred for 24 hours to proceed reaction. An organic layer was extracted from the resultant obtained therefrom by using ethyl acetate, anhydrous magnesium sulfate (MgSO4) was added thereto to remove water, and followed by filtration to obtain a filtrate which was then decompressed to obtain residue, which was then purified by performing column chromatography using a mixture of dichloromethane and hexane (1:1 vol/vol), to thereby obtain Compound 485 (0.72 g, 60%). The obtained compound was identified by HRMS and HPLC analysis.
HRMS (MALDI-TOF) calcd for C65H77IrN4O2: m/z 1138.5676, Found: 1138.5676.
Scheme 3 shows the synthesis of Compound 507.
Synthesis of Compound L507-Dimer
Compound L507 (4-(3,5-dimethylphenyl)-2,8,10-trimethylbenzo[h]quinazoline) (1.67 g, 5.12 mmol) and iridium chloride hydrate (0.803 g, 2.28 mmol) were mixed with 18 mL of 2-ethoxyethanol and 6 mL of deionized water, and the mixture was stirred at reflux for 24 hours at 120° C. and after the reaction, cooled to room temperature. A solid material formed therefrom was separated by filtration and washed thoroughly with water, methanol, and hexane in the stated order to obtain a solid which was then dried in a vacuum oven to obtain Compound L507-dimer (1.61 g, 80%). The obtained compound was used in the synthesis of compound 507 without further purification.
Synthesis of Compound 507
Compound L507-dimer (1.11 g, 0.63 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (0.70 g, 3.80 mmol), and Na2CO3 (0.40 g, 3.80 mmol) were mixed with 20 mL of 2-ethoxyethanol, and then stirred for 24 hours to proceed reaction. An organic layer was extracted from the resultant obtained therefrom by using ethyl acetate, anhydrous magnesium sulfate (MgSO4) was added thereto to remove water, and followed by filtration to obtain a filtrate which was then decompressed to obtain residue, which was then purified by performing column chromatography using a mixture of dichloromethane and hexane (1:1 vol/vol), to thereby obtain Compound 507 (0.65 g, 50%). The obtained compound was identified by HRMS and HPLC analysis.
HRMS (MALDI-TOF) calcd for C57H61IrN4O2: m/z 1026.4424, Found: 1026.4422.
Scheme 4 shows the synthesis of Compound 531.
Synthesis of Compound L531-Dimer
Compound L531 (4-(dibenzo[b,d]furan-4-yl)-8,10-diisobutyl-2-isopropylbenzo[h]quinazoline) (1.84 g, 3.67 mmol) and iridium chloride hydrate (0.57 g, 1.63 mmol) were mixed with 18 mL of 2-ethoxyethanol and 6 mL of deionized water, and the mixture was stirred at reflux for 24 hours at 120° C. and after the reaction, cooled to room temperature. A solid material formed therefrom was separated by filtration and washed thoroughly with water, methanol, and hexane in the stated order to obtain a solid which was then dried in a vacuum oven to obtain Compound L531-dimer (1.72 g, 80%). The obtained compound was used in the synthesis of compound 531 without further purification.
Synthesis of Compound 531
Compound L531-dimer (1.21 g, 0.49 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (0.55 g, 2.96 mmol), and Na2CO3 (0.32 g, 2.96 mmol) were mixed with 20 mL of 2-ethoxyethanol, and then stirred for 24 hours to proceed reaction. An organic layer was extracted from the resultant obtained therefrom by using ethyl acetate, anhydrous magnesium sulfate (MgSO4) was added thereto to remove water, and followed by filtration to obtain a filtrate which was then decompressed to obtain residue, which was then purified by performing column chromatography using a mixture of dichloromethane and hexane (1:1 vol/vol), to thereby obtain Compound 531 (0.55 g, 42%). The obtained compound was identified by HRMS and HPLC analysis.
HRMS (MALDI-TOF) calcd for C77H81IrN4O2: m/z 1318.5887, Found: 1318.5886.
Synthesis of Compound B
Scheme 5 shows the synthesis of Compound B.
Synthesis of Compound LB-Dimer
Compound LB (4-(3,5-dimethylphenyl)-7-isopropylquinazoline) (2.01 g, 7.30 mmol) and iridium chloride hydrate (1.14 g, 3.24 mmol) were mixed with 30 mL of 2-ethoxyethanol and 10 mL of deionized water, and the mixture was stirred at reflux for 24 hours at 120° C. and after the reaction, cooled to room temperature. A solid material formed therefrom was separated by filtration and washed thoroughly with water, methanol, and hexane in the stated order to obtain a solid which was then dried in a vacuum oven to obtain Compound LB-dimer (1.51 g, 60%). The obtained compound was used in the synthesis of Compound B without further purification.
Synthesis of Compound B
Compound LB-dimer (1.05 g, 0.68 mmol), 3,7-diethylnonane-4,6-dione (0.86 g, 4.09 mmol), and Na2CO3 (0.43 g, 4.09 mmol) were mixed with 20 mL of 2-ethoxyethanol, and then stirred for 24 hours to proceed reaction. An organic layer was extracted from the resultant obtained therefrom by using ethyl acetate, anhydrous magnesium sulfate (MgSO4) was added thereto to remove water, and followed by filtration to obtain a filtrate which was then decompressed to obtain residue, which was then purified by performing column chromatography using a mixture of dichloromethane and hexane (1:1 vol/vol), to thereby obtain Compound B (0.57 g, 42%). The obtained compound was identified by HRMS and HPLC analysis.
HRMS (MALDI-TOF) calcd for C51H61IrN4O2: m/z 954.4424, Found: 954.4422.
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 deionized 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.
HT3 and F6-TCNNQ were vacuum-codeposited at the weight ratio of 98:2 on the ITO anode to form a hole injection layer having a thickness of 100 Angstrom (A), HT3 was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 1,350 Å, and then, HT21 was vacuum-deposited on the hole transport layer to form an electron blocking layer having a thickness of 300 Å.
Subsequently, H52 (host) and Compound 24 (dopant) were co-deposited at a weight ratio of 98:2 on the electron blocking layer to form an emission layer having a thickness of 400 Å.
Afterward, ET3 and ET-D1 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, ET-D1 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 having a structure of ITO (1,500 Å)/HT3+F6-TCNNQ (2 wt %) (100 Å)/HT3 (1,350 Å)/HT21 (300 Å)/H52+Compound 24(2 wt %) (400 Å)/ET3+ET-D1 (50%) (350 Å)/ET-D1 (10 Å)/Al (1,000 Å).
Organic light-emitting devices were manufactured in the same manner as in Example 1, except that in forming an emission layer, for use as a dopant, corresponding compounds shown in Table 2 were used instead of Compound 24.
For each organic light-emitting device manufactured according to Examples 1 to 4 and Comparative Examples A to B, driving voltage (voltage, V), a maximum value of external quantum efficiency (Max EQE, %), a roll-off ratio (%), a full width at half maximum (FWHM) of an emission peak in an electroluminescence (EL) spectrum, and lifespan LT97 were evaluated, and results thereof are shown in Table 2. As evaluation devices, a current-voltmeter (Keithley 2400) and luminance meter (Minolta Cs-1000A) were used, and the lifespan (LT97) (at 3500 candela per square meter, cd/m2) was evaluated as the time (hours, hr) taken for luminance to reduce to 97% of 100% of the initial luminance. In Table 2, listed data of Max EQE and lifespan are in relative values (%). The roll-off ratio was calculated according to Equation 20 below.
Roll off ratio=[1−(efficiency (at 3,500 cd/m2)/maximum emission efficiency)]×100% Equation 20
Referring to Table 2, it is confirmed that the organic light-emitting devices manufactured according to Examples 1 to 4 have improved driving voltage, improved external quantum efficiency, improved roll-off ratios, and improved lifespan and may emit light having relatively narrow (or, small) FWHM, compared to the organic light-emitting devices manufactured according to Comparative Examples A and B.
Since the organometallic compound have excellent thermal stability and electrical characteristics, an electronic device, for example, an organic light-emitting device, including the organometallic compound, may have improved characteristics in terms of driving voltage, external quantum efficiency, roll-off ratio, and lifespan and may emit light having relatively narrow (or, small) FWHM, and thus high-quality electronic apparatus may be provided by using the organic light-emitting device.
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.
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| Number | Date | Country | |
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| 20220013734 A1 | Jan 2022 | US |
