Patent Grant
11832509
This application claims priority to and the benefits of Korean Patent Application Nos. 10-2019-0070074, filed on Jun. 13, 2019 and 10-2020-0050329, filed on Apr. 24, 2020, in the Korean Intellectual Property Office, the contents of which are incorporated herein in their entirety by reference.
One or more embodiments relate to organometallic compounds, organic light-emitting devices including the same, and diagnostic compositions including the same.
Organic light-emitting devices are self-emission devices, which have improved characteristics in terms of a viewing angle, a response time, brightness, a driving voltage, and a 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 between the anode and the emission layer, and an electron transport region may be 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 to thereby generate light.
Meanwhile, luminescent compounds, for example, phosphorescent compounds, may be used for monitoring, sensing, and detecting biological materials such as various cells and proteins.
One or more embodiments relate to organometallic compounds, organic light-emitting devices including the same, and diagnostic compositions including the same.
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 of an embodiment, an organometallic compound represented by Formula 1 is provided.
M1(L11)n11(L12)n12 <Formula 1>
In Formula 1,
a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C1-C60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, or a monovalent non-aromatic condensed heteropolycyclic group, each substituted with at least one of deuterium, —F, —Cl, —Br, —I, —CDs, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic add group or a salt thereof, a phosphoric add 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 C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C1-C60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, —N(Q21)(Q22), —Si(Q23)(Q24)(Q25), —B(Q26)(Q27), —P(═O)(Q28)(Q29), or any combination thereof; or
Another aspect provides an organic light-emitting device including a first electrode; a second electrode; and an organic layer including an emission layer between the first electrode and the second electrode, wherein the organic layer includes at least one organometallic compound represented by Formula 1.
Another aspect provides a diagnostic composition including at least one organometallic compound represented by Formula 1.
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 FIGURE which shows a schematic cross-sectional view of an organic light-emitting device according to an exemplary embodiment.
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. 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 understood that when an element is referred to as being “on” another element, it can be directly on 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 herein.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, “a,” “an,” “the,” and “at least one” do not denote a limitation of quantity, and are intended to cover both the singular and plural, unless the context dearly indicates otherwise. For example, “an element” has the same meaning as “at least one element,” unless the context dearly indicates otherwise.
“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 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.
Furthermore, relative terms, such as “lower” or “bottom” and “upper” or “top,” may be used herein to describe one element's relationship to another element as illustrated in the Figures It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the Figures For example, if the device in one of the figures is turned over, elements described as being on the “lower” side of other elements would then be oriented on “upper” sides of the other elements The exemplary term “lower,” can therefore, encompasses both an orientation of “lower” and “upper,” depending on the particular orientation of the FIGURE Similarly, if the device in one of the figures is turned over, elements described as “below” or “beneath” other elements would then be oriented “above” the other elements The exemplary terms “below” or “beneath” can, therefore, encompass both an orientation of above and below.
“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% or 5% of the stated value.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure 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.
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.
An aspect of the present disclosure provides an organometallic compound represented by Formula 1 below:
M1(L11)n11(L12)n12. <Formula 1>
M1 in Formula 1 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 one or more embodiments, M1 in Formula 1 may be beryllium (Be), magnesium (Mg), aluminum (Al), calcium (Ca), titanium (Ti), manganese (Mn), cobalt (Co), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), zirconium (Zr), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), rhenium (Re), platinum (Pt), or gold (Au).
In one or more embodiments, M1 may be Pd, Pt, or Au.
In one or more embodiments, M1 in Formula 1 may be Pt or Pd.
In one or more embodiments, M1 in Formula 1 may be Pt.
L11 in Formula 1 may be a ligand represented by Formula 1-1:
*1 to *4 in Formula 1-1 may each independently be a binding site to M1.
A10 in Formula 1-1 may be an N-containing heterocyclic group. In one or more embodiments, A10 in Formula 1-1 may include a 5-membered N-containing heterocyclic group.
In one or more embodiments, A10 may be one of Formulae A10-1 to A10-4:
In Formulae A10-1 to A10-4,
A20, A30, and A40 in Formula 1-1 may each independently be a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
In one or more embodiments, A20, A30, and A40 may each independently be 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, a furan group, a thiophene group, a silole group, an indene group, a fluorene group, an indole group, a carbazole group, a benzofuran group, a dibenzofuran group, a benzothiophene group, a dibenzothiophene group, a benzosilole group, a dibenzosilole group, an azafluorene group, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, a tetrazole 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, an indazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a benzotriazole group, a diazaindene group, a triazaindene group, a 5,6,7,8-tetrahydroisoquinoline group, or a 5,6,7,8-tetrahydroquinoline group.
T1 in Formula 1-1 may be a single bond, *—N[(L1)a1-(R1)b1]—*′, *—B(R1)—*′, *—P(R1)—*′, *—C(R1)(R2)—*′, *—Si(R1)(R2)—*′, *—Ge(R1)(R2)—*′, *—S—*′, *—Se—*′, *—O—*′, *—C(═O)—*′, *—S(═O)—*′, *—S(═O)2—*′, *—C(R1)═C(R2)—*′, *—C(═S)—*′, or *—CC—*′, and
In one or more embodiments, T1 may be a single bond, *—N[(L1)a1-(R1)b1]—*′, *—B(R1)—*′, *—C(R1)(R2)—*′, *—Si(R1)(R2)—*′, *—O—*′, or *—S—*′.
According to one or more embodiments, T1 may be *—N[(L1)a1-(R1)b1]—*′, *—B(R1)—*′, *—C(R1)(R2)—*′, *—Si(R1)(R2)—*′, *—O—′, or *—S—*′.
In one or more embodiments, T2 may be a single bond, *—N[(L2)a2-(R3)b3]—*′, *—C(R3)(R4)—*′, *—Si(R3)(R4)—*′, *—O—*′, or *—S—*′.
L1 and L2 in Formula 1-1 may each independently be a single bond, a substituted or unsubstituted C5-C30 carbocyclic group, or a substituted or unsubstituted C1-C30 heterocyclic group, and
In one or more embodiments, L1 and L2 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; or
X11 in Formula 1-1 may be C(R11) or N. For example, X11 may be C(R11). In one or more embodiments, X11 may be N.
X12 in Formula 1-1 may be C(R12) or N. For example, X12 may be C(R12). In one or more embodiments, X12 may be N.
In one or more embodiments, X11 may be C(R11), X12 may be C(R12), and as described later, R11 and R12 may optionally be linked together to form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group.
In one or more embodiments, X11 may be C(R11), X12 may be C(R12), and R11 and R12 may optionally be linked together to form a benzene group, a pyridine group, a pyrimidine group, a pyrazine group, or a pyridazine group.
X20 in Formula 1-1 may be C or N.
X30 in Formula 1-1 may be C or N.
X40 in Formula 1-1 may be C or N.
X21, X22, X31, X32 and X41 in Formula 1-1 may each independently be C or N.
According to one or more embodiments, a bond between M1 and A10, a bond between M1 and A20, a bond between M1 and A30, and a bond between M1 and A40 may each independently be a coordination bond or a covalent bond.
According to one or more embodiments, a bond between M1 and A10 may be a coordination bond.
In Formula 1, two bonds of a bond between M1 and A20, a bond between M1 and A30, and a bond between M1 and A40 may each be a covalent bond, and the other bond may be a coordination bond.
Thus, the organometallic compound represented by Formula 1 may be electrically neutral.
According to one or more embodiments, a bond between M1 and A20 may be a covalent bond, a bond between M1 and A30 may be a covalent bond, and a bond between M1 and A40 may be a coordination bond.
Ar1 in Formula 1-1 is a substituted or unsubstituted C5-C30 carbocyclic group, and when Ar1 is a benzene group (for example, a substituted benzene group), Ar1 may be represented by one of Formulae Ar1-1 to Ar1-18:
E11 to E15 in Formulae Ar1-1 to Ar1-18 may each independently be a substituted or unsubstituted C1-C60 alkyl 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 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 C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group.
E16 and E17 in Formulae Ar1-1 to Ar1-18 may each independently be a substituted or unsubstituted C6-C60 alkyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted C3-C10 cycloalkyl group, an unsubstituted C7-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 C6-C60 aryl group, an unsubstituted CT-COO aryl group, a substituted or unsubstituted C7-C60 alkyl aryl 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 C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group.
According to one or more embodiments, Ar1 may be a substituted benzene group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted anthracene group, a substituted or unsubstituted phenanthrene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted pyrene group, or a substituted or unsubstituted chrysene group,
In one or more embodiments, Ar1 may be a group represented by one of Formulae Ar1-1 to Ar1-18.
In one or more embodiments, E11 to E15 may each independently be: 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 sec-pentyl group, a tert-pentyl 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;
In one or more embodiments, E16 and E17 may each independently bean 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;
According to one or more embodiments, E11 to E15 may each independently be: 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 sec-pentyl group, a tert-pentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, or a tert-hexyl group;
In one or more embodiments, E16 and E17 may each independently bean n-hexyl group, an isohexyl group, a sec-hexyl group, or a tert-hexyl group;
E11 to E15 may each independently be:
an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a phenyl group, a naphthyl group, a pyridinyl group, or a pyrimidinyl group;
According to one or more embodiments, E16 and E17 may each independently be; an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a pyridinyl group, or a pyrimidinyl group;
In one or more embodiments, E11 to E17 may each independently bean n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a naphthyl group, a pyridinyl group, or a pyrimidinyl group;
In one or more embodiments, Ar1 may be represented by one of Formulae Ar1-1 to Ar1-8, Ar1-10 to Ar1-13, and Ar1-15 to Ar1-18.
R1 to R4, R11, R12, R20, R30, and R40 in Formula 1-1 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro 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 alkylaryl 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 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(Q1)(Q2), —Si(Q3)(Q4)(Q5), —B(Q6)(Q7), or —P(═O)(Q8)(Q9), and
b1 and b3 in Formula 1-1 may each independently be an integer from 1 to 5, and
b20, b30, and b40 in Formula 1-1 may each independently be an integer from 1 to 10, and
In one or more embodiments, R1 to R4, R11, R12, R20, R30 and R40 may each independently be:
According to one or more embodiments, R1 to R4, R11, R12, R20, R30 and R40 may each independently be:
In one or more embodiments, R1 to R4, R11, R12, R20, R30, and R40 may each independently be hydrogen, deuterium, —F, a cyano group, a nitro group, —SF5, —CH3, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a group represented by one of Formulae 9-1 to 9-19, or a group represented by one of Formulae 10-1 to 10-194:
In Formulae 9-1 to 9-19 and 10-1 to 10-194, * indicates a binding site to a neighboring atom, Ph may be a phenyl group, and TMS may be a trimethylsilyl group.
According to one or more embodiments, neighboring two or more of R1 to R4, R20, R30, and R40 may be linked together to form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group.
In one or more embodiments, neighboring two or more of R1 to R4, R20, R30, and R40 in Formula 1 may optionally be linked together to form a cyclopentane 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 the same as described in connection with R1.
In one or more embodiments, neighboring two or more of R1 to R4, R20, R30, and R40 may optionally be linked together to form, via a single bond, a double bond or first linking group, 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 (for example, a fluorene group, a xanthene group, an acridine group, or the like, each unsubstituted or substituted with at least one R10a). R10a is the same as described in connection with R1.
The first linking group may be *—N(R5)—*′, *—B(R5)—*′, *—P(R6)—*′, *—C(R5)(R6)—*′, *—Si(R5)(R6)—*′, *—Ge(R5)(R6)—*′, *—S—*′, *—Se—*′, *—O—*′, *—C(═O)—*′, *—S(═O)—*′, *—S(═O)2—*′, *—C(R5)═*′, *═C(R5)—*′, *—C(R5)═C(R6)—*′, *—C(═S)—*′ or *—C≡C—*′, and R5 and R6 are the same as described in connection with R1, and * and *′ each indicate a binding site to a neighboring atom.
In one or more embodiments, the organometallic compound represented by Formula 1 may be represented by one of Formulae 2-1 or 2-2:
In Formulae 2-1 and 2-2,
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 C6-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 alkylaryl 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 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 is:
L12 in Formula 1 may be a monodentate ligand or a bidentate ligand.
For example, L12 in Formula 1 may be a ligand represented by one of Formulae 7-1 to 7-11, but embodiments are not limited thereto:
In Formulae 7-1 to 7-11,
For example, A71 and A72 in Formula 7-1 may each independently be a benzene group, a naphthalene group, an imidazole group, a benzimidazole group, a pyridine group, a pyrimidine group, a triazine group, a quinoline group, or an isoquinoline group, but embodiments of the present disclosure are not limited thereto.
In one or more embodiments, X71 and X72 in Formula 7-1 may be N, but embodiments of the present disclosure are not limited thereto. In one or more embodiments, X72 and X79 in Formula 7-11 may be N, but embodiments of the present disclosure are not limited thereto.
In one or more embodiments, in Formula 7-7, X73 may be C(Q73) X74 may be C(Q74); X75 may be C(Q75); X76 may be C(Q76); and X77 may be C(Q77), but embodiments of the present disclosure are not limited thereto.
In one or more embodiments, in Formula 7-8, X78 may be N(Q78); and X79 may be N(Q79), but embodiments of the present disclosure are not limited thereto.
In one or more embodiments, Y71 and Y72 in Formulae 7-2, 7-3 and 7-8 may each independently be a substituted or unsubstituted methylene group, or a substituted or unsubstituted phenylene group, but embodiments of the present disclosure are not limited thereto.
In one or more embodiments, Z71 and Z72 in Formulae 7-1 and 7-2 may each be O, but embodiments of the present disclosure are not limited thereto.
In one or more embodiments, Z73 in Formula 7-4 may be P, but embodiments of the present disclosure are not limited thereto.
For example, R71 to R80 and Q73 to Q79 in Formulae 7-1 to 7-11 may each independently be:
L12 in Formula 1 may be a ligand represented by one of Formulae 5-1 to 5-116 and 8-1 to 8-23, but embodiments of the present disclosure are not limited thereto:
In Formulae 5-1 to 5-116 and 8-1 to 8-23, R51 to R53 may each independently be:
In Formula 1, n11 may be 1, and n12 may be 0, 1, or 2.
In one or more embodiments, M1 in Formula 1 may be Pt, n11 may be 1, and n12 may be 0, but embodiments of the present disclosure are not limited thereto.
In one or more embodiments, the organometallic compound may be one of Compounds 1 to 428:
The organometallic compound represented by Formula 1 may satisfy the structure of Formula 1 described above, and due to the structure in which A10 ring in L11 ligand is N-substituted with Ar1 group, the organometallic compound may have improved photochemical stability, and may be suitable for deep blue light emission. An electronic device, for example, an organic light-emitting device, using the organometallic compound represented by Formula 1 may be excellent in luminescence efficiency, lifespan, and color purity.
In addition, the organometallic compound has the structure in which A10 is a 5-membered N-containing heterocyclic ring and to which other rings are not condensed. Accordingly, the conjugation length is short, and thus, the luminescence quantum yield is increased and deep blue light may be emitted. Therefore, the lifespan of the organic light-emitting device using the organometallic compound may be increased.
In one or more embodiments, the highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), triplet (T1) energy level, and spin density of compound 125 and comparative compound A are evaluated by using DFT method of Gaussian program (structurally optimized at the level of B3LYP, 6-31G(d,p)). Results thereof are shown in Table 1.
From Table 1, it is confirmed that the organometallic compound represented by Formula 1 has such electric characteristics that are suitable for use as a material for an emission layer for an electronic device, for example, an organic light-emitting device.
In addition, the organometallic compound represented by Formula 1 exhibits a higher spin density compared to comparative compound A, and thus metal-ligand charge transfer (MLCT) occurs efficiently, resulting in an increase in the efficiency and lifetime of the 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.
Accordingly, the organometallic compound represented by Formula 1 is suitable for use as a material for an organic layer of organic light-emitting device, for example, an emission layer. Thus, another aspect provides an organic light-emitting device including: a first electrode; a second electrode; and an organic layer placed between the first electrode and the second electrode and including an emission layer, and the organic layer includes at least one organometallic compound represented by Formula 1.
The organic light-emitting device may have, due to the inclusion of an organic layer including the organometallic compound represented by Formula 1, a low driving voltage, high efficiency, high power efficiency, high quantum efficiency, a long lifespan, a low roll-off ratio, and excellent color purity.
In one or more embodiments, in the organic light-emitting device, the first electrode is an anode, and the second electrode is a cathode, and the organic layer further includes a hole transport region between the first electrode and the emission layer and an electron transport region between the emission layer and the second electrode, and the hole transport region includes a hole injection layer, a hole transport layer, an electron blocking layer, or any combination thereof, and the electron transport region includes a hole blocking layer, an electron transport layer, an electron injection layer, or any combination thereof.
In one or more embodiments, the organometallic compound represented by Formula 1 may be included in the emission layer.
The organometallic compound included in the emission layer may act as an emitter. For example, an emission layer including the organometallic compound represented by Formula 1 may emit phosphorescent light generated by the transfer of the triplet excitons of the organometallic compound into the ground state.
In one or more embodiments, the emission layer including the organometallic compound represented by Formula 1 may further include a host. The host may be any host, and details of the host may be the same as described herein. The amount of the host in the emission layer may be greater than the amount of the organometallic compound represented by Formula 1.
In one or more embodiments, the emission layer may include a host and a dopant, the host may be any host, and the dopant may include the organometallic compound represented by Formula 1. The emission layer may emit phosphorescent light generated by the transfer of triplet excitons of the organometallic compound, which acts as a dopant, to the ground state.
According to one or more embodiments, when the emission layer further includes a host, the amount of the host may be greater than the amount of the organometallic compound.
In one or more embodiments, the emission layer may include a host and a dopant, the host may be any host, and the dopant may include the organometallic compound represented by Formula 1, and the emission layer may further include a fluorescent dopant. The emission layer may emit fluorescent light that is generated by the transfer of the triplet excitons of the organometallic compound to the fluorescent dopant and then transition thereof.
According to one or more embodiments, the emission layer may emit blue light having the maximum luminescence wavelength of about 410 nm to about 490 nm.
The expression “(an organic layer) includes at least one organometallic compound represented by Formula 1” 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, the organic layer may include, as the organometallic compound, only Compound 1. In this embodiment, Compound 1 may be included 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. In this regard, Compound 1 and Compound 2 may exist in an identical layer (for example, Compound 1 and Compound 2 all may exist in an emission layer).
The term “organic layer” used herein refers to a single layer and/or a plurality of layers 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.
FIGURE is a schematic cross-sectional view of an organic light-emitting device 10 according to an exemplary 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 be 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), 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 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 any 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.
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 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 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 at least one of m-MTDATA, TDATA, 2-TNATA, NPB, β-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated-NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonicacid (PANI/CSA), polyaniline/poly(4-styrenesulfonate) (PANI/PSS), a compound represented by Formula 201 below, a compound represented by Formula 202 below, or any combination thereof:
Ar101 to Ar102 in Formula 201 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:
According to an embodiment, the compound represented by Formula 201 may be represented by Formula 201A below, but embodiments of the present disclosure are not limited thereto:
R101, R111, R112, and R109 in Formula 201A may be understood by referring to the description provided herein.
For example, the compound represented by Formula 201, and the compound represented by Formula 202 may include compounds HT1 to HT20 illustrated below, but are not limited thereto:
A thickness of the hole transport region may be in a range of about 100 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, a hole transport layer, or any combination thereof, a thickness of the hole injection layer may be in a range of about 100 Å to about 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 one a quinone derivative, a metal oxide, or a cyano group-containing compound, but embodiments of the present disclosure are not limited thereto. Examples of the p-dopant are: a quinone derivative, such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4-TCNQ); a metal oxide, such as a tungsten oxide or a molybdenum oxide; and a cyano group-containing compound, such as Compound HT-D1 below, but are not limited thereto.
The hole transport region may include a buffer layer.
Also, 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.
Meanwhile, when the hole transport region includes an electron blocking layer, a material for the electron blocking layer may be 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. Then, an emission layer (EML) 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.
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 TPBi, TBADN, ADN (also referred to as “DNA”), CBP, CDBP, TCP, mCP, Compound H50, Compound H51, or any combination thereof:
In one or more embodiments, the host may further include a compound represented by Formula 301 below.
A111 and Ar112 in Formula 301 may each independently be:
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:
Ar122 to Ar125 in Formula 302 are the same as described in detail 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 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.
In one or more embodiments, the organic layer of the organic light-emitting device may further include a fluorescent dopant in addition to the organometallic compound represented by Formula 1.
For example, the fluorescent dopant may be a condensation polycyclic compound or a styryl compound.
For example, the fluorescent dopant may include one of a naphthalene-containing core, a fluorene-containing core, a spiro-bifluorene-containing core, a benzofluorene-containing core, a dibenzofluorene-containing core, a phenanthrene-containing core, an anthracene-containing core, a fluoranthene-containing core, a triphenylene-containing core, a pyrene-containing core, a chrysene-containing core, a naphthacene-containing core, a picene-containing core, a perylene-containing core, a pentaphene-containing core, an indenoanthracene-containing core, a tetracene-containing core, a bisanthracene-containing core, and cores represented by Formulae 501-1 to 501-18, but embodiments of the present disclosure are not limited thereto:
In one or more embodiments, the fluorescent dopant may be a styryl-amide-based compound and a styryl-carbazole-based compound, but embodiments of the present disclosure are not limited thereto.
In one or more embodiments, the fluorescent dopant may be compounds represented by Formula 501:
In Formula 501,
Ar501 may be:
For example, in Formula 501,
Ar501 may be:
In one or more embodiments, the fluorescent dopant may include a compound represented by one of Formulae 502-1 to 502-5:
In Formulae 502-1 to 502-5,
L501 to L508 are each the same as described in connection with L501 in Formula 501,
The fluorescent dopant may include at least one compound of the following compounds FD(1) to FD(16) and FD1 to FD13:
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 any 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 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 BCR, Bphen, BAlq, or any combination thereof 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 these ranges, the hole blocking layer may have excellent hole blocking characteristics without a substantial increase in driving voltage.
The electron transport layer may include at least one of BCP, Bphen, Alq3, BAlq, TAZ, NTAZ, or any combination thereof.
In one or more embodiments, the electron transport layer may include at least one of ET1 to ET25, but 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, the electron transport layer may have satisfactory electron transport characteristics without a substantial increase in driving voltage.
Also, 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 (lithium quinolate, LiQ) or ET-D2:
The electron transport region may include an electron injection layer (EIL) that promotes the flow of electrons from the second electrode 19 thereinto.
The electron injection layer may include at least one of LiF, NaCl, CsF, Li2O, BaO, or any 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. 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 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 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), 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 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, and non-limiting 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” 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” used herein refers to a monovalent group represented by —SA102 (wherein A102 is the C1-C60 alkyl group), and examples thereof include a methylthio group, an ethylthio group, and an isopropylthio 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 C3-C60 alkyl group, and examples thereof include an ethynyl group, and a propynyl group. The term “C3-C60 alkynylene group” as used herein refers to a divalent group having the same structure as the C3-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 N, O, P, Si, B, Se, Ge, Te, S, or any combination thereof 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.
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 cartoon-carbon double bond in the ring thereof and no aromatidty, and non-limiting 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 N, O, P, Si, B, Se, Ge, Te S, or any combination thereof as a ring-forming atom, 2 to 10 carbon atoms, and at least one carbon-carbon double bond in its ring. Examples of the C2-C10 heterocycloalkenyl group are 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 C7-C60 alkylaryl group refers to a C6-C60 aryl group substituted with at least one C1-C60 alkyl group.
The term “C1-C60 heteroaryl group” as used herein refers to a monovalent group having a cyclic aromatic system that has at least one N, O, P, Si, B, Se, Ge, Te, S, or any combination thereof 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 cyclic aromatic system that has at least one N, O, P, Si, B, Se, Ge, Te, S, or any combination thereof as a ring-forming atom, and 1 to 60 cartoon 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 C3-C60 alkylheteroaryl group 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 is the C6-C60 aryl group), and the term “C6-C60 arylthio group” as used herein indicates —SA103 (wherein A103 is the C6-C60 aryl group).
The term “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 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 2 to 60 carbon atoms) having two or more rings condensed to each other, a heteroatom N, O, P, Si, B, Se, Ge, Te, S, or any combination thereof 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 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 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 N, O, Si, P, B, Se, Ge, Te, S, or any combination thereof other than 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 C2-C60 alkylaryl 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 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, a compound and an organic light-emitting device according to embodiments are described in detail with reference to Synthesis Example and Examples. However, the compound and 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.
102.8 mmol (7 g) 1H-imidazole, 133.7 mmol (39 g) 1,3-dibromo-5-(tert-butyl)benzene, 25.7 mmol (4.9 g) CuI, 30.9 mmol (5.6 g) 1,10-phenanthroline, and 205.7 mmol (67 g) Cs2CO3 were added to 200 mL of dimethylformamide (DMF), and then, the resultant mixture was refluxed at a temperature of 130° C. for 12 hours. The reaction product obtained therefrom was cooled, and combined with ethyl acetate and water. The organic layer was separated, washed three times with water and dried using magnesium sulfate, and then, a solvent was removed therefrom under reduced pressure, thereby obtaining a crude product. The crude product was subjected to silica gel column chromatography (eluent: ethyl acetate:hexane) to obtain Intermediate 125(1) (yield of 60%).
MALDI-TOF (m/z): 278.05 [M]+
101.4 mmol (20.0 g) 2-methoxy-9H-carbazole and 152.1 mmol (32.6 g) 2-bromo-4-(tert-butyl)pyridine were dissolved in 340 ml of dioxane, and then, 50.7 mmol (9.7 g) CuI, 152.1 mmol (32.3 g) K3PO4, and 72.4 mmol (12.2 ml) trans-1,2-cyclohexanediamine were added thereto, followed by refluxing at a temperature of 120° C. for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, and mixed with ethyl acetate and water. The organic layer was separated, washed three times with water and dried using magnesium sulfate, and then, a solvent was removed therefrom under reduced pressure, thereby obtaining a crude product. The crude product was subjected to silica gel column chromatography (eluent: ethyl acetate:hexane) to obtain Intermediate 125(2) (yield of 85%).
MALDI-TOF (m/z): 331.16 [M]+
95.3 mmol (31.5 g) Intermediate 125(2) and 1.4 mol (165.3 g) pyridine hydrochloride were added and refluxed in a neat condition at a temperature of 180° C. for 20 hours. After completion of the reaction, the mixture was cooled to room temperature, and mixed with dichloromethane and water. The organic layer was separated, washed three times with water and dried using magnesium sulfate, and then, a solvent was removed therefrom under reduced pressure, thereby obtaining a crude product. The crude product was subjected to silica gel column chromatography (eluent: ethyl acetate:dichloromethane:hexane) to obtain Intermediate 125(3) (yield of 65%).
MALDI-TOF (m/z): 317.15 [M]+
17.9 mmol (5 g) Intermediate 125(1) and 15.0 mmol (4.7 g) Intermediate 125(3) were dissolved in 300 ml of dimethyl sulfoxide (DMSO), and then, 4.9 mmol (0.8 g) CuI, 59.9 mmol (12.7 g) K3PO4, and 22.5 mmol (2.7 g) picolinic add were added thereto, and the resultant mixture was refluxed at a temperature of 100° C. for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, and mixed with ethyl acetate and water. The organic layer was separated, washed three times with water and dried using magnesium sulfate, and then, a solvent was removed therefrom under reduced pressure, thereby obtaining a crude product. The crude product was subjected to silica gel column chromatography (eluent: ethyl acetate:hexane) to obtain Intermediate 125(4) (yield of 71%).
MALDI-TOF (m/z): 514.26 [M]+
19.0 mmol (6.0 g) 1,3-di-tert-butyl-5-iodobenzene, 28.8 mmol (3.5 g) mesitylene compound, and 24.0 mmol (4.1 g) 3-chloroperoxybenzoic acid (m-CBPA) were dissolved in 50 ml of dichloromethane, and then, cooled in an ice bath at a temperature of 0° C. 48.0 mmol (4.2 ml) triflic add was added dropwise thereto. After the temperature was raised to room temperature, the resultant mixture was stirred for 2 hours and then a solvent was completely removed therefrom. A small amount of diethyl ether was added thereto, followed by stirring and filtration. The obtained crude product 125(5) was used for the next reaction.
8.6 mmol (5.0 g) Intermediate 125(5), 5.7 mmol (3.3 g) Intermediate 125(4), and 0.4 mmol (0.1 g) copper acetate (Cu(OAc)2) were added to 30 mL of dimethylformamide (DMF), and then, the resultant mixture was refluxed at a temperature of 130° C. for 12 hours. The crude product obtained by removing the solvent therefrom under reduced pressure was subjected to silica gel column chromatography (eluent: dichloromethane:acetone) to obtain Intermediate 125(6) (yield of 82%).
MALDI-TOF (m/z): 702.42 [M]+
4.0 mmol (1.5 g) Pt(COD)Cl2, 4.0 mmol (3.4 g) Intermediate 125(6), and 12.0 mmol (1.0 g) sodium acetate (NaOAc) were added to 200 mL of benzonitrile, and then, refluxed at a temperature of 180° C. for 12 hours. After completion of the reaction, the resultant mixture was cooled to room temperature and the solvent was removed therefrom under reduced pressure to obtain a crude product, which was then subjected to silica gel column chromatography (eluent dichloromethane and hexane) to obtain compound 125 (yield of 53%).
MALDI-TOF (m/z): 895.36 [M]+
PMMA in CH2Cl2 solution, 5 wt % of CBP, and Compound 125 were mixed, and then, the result was coated on a quartz substrate by using a spin coater, and then, heat-treated in an oven at a temperature of 80° C., and cooled to room temperature to obtain a film.
The PLQY of Compound 125 in film was evaluated by using a Hamamatsu Photonics absolute PL quantum yield measurement system equipped with a xenon light source, a monochromator, a photonic multichannel analyzer, and an integrating sphere, and using PLQY measurement software (Hamamatsu Photonics, Ltd., Shizuoka, Japan), and the same experiment was performed on Compound A. Results thereof are shown in Table 2.
From Table 2, it can be confirmed that Compound 125 has substantially the same maximum luminescence wavelength as Compound A, and has high luminescence quantum efficiency and thus has excellent luminescence characteristics.
An ITO glass substrate was cut to a size of 50 mm×50 mm×0.5 mm and then, sonicated in acetone, isopropyl alcohol and pure water, each for 15 minutes, and then, washed by exposure to UV ozone for 30 minutes.
Then, m-MTDATA was deposited on an ITO electrode (anode) of the glass substrate at a deposition rate of 1 Å/sec to form a hole injection layer having a thickness of 600 Å, and then, α-NPD was deposited on the hole injection layer at a deposition rate of 1 Å/sec to form a hole transport layer having a thickness of 250 Å.
Compound 125 (dopant) and CBP (host) were co-deposited on the hole transport layer at a deposition rate of 0.1 Å/sec and a deposition rate of 1 Å/sec, respectively, to form an emission layer having a thickness of 400 Å.
BAlq was deposited on the emission layer at a deposition rate of 1 Å/sec to form a hole blocking layer having a thickness of 50 Å, and Alq3 was deposited on the hole blocking layer to form an electron transport layer having a thickness of 300 Å, and then, LiF was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and then, Al was vacuum deposited on the electron injection layer to form a second electrode (cathode) having a thickness of 1,200 Å, thereby completing manufacturing of an organic light-emitting device having a structure of ITO/m-MTDATA (600 Å)/α-NPD (250 Å)/CBP+Compound 125 (10%) (400 Å)/BAlq (50 Å)/Alq3 (300 Å)/LiF (10 Å)/Al (1,200 Å).
An organic light-emitting device was 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 3 were used.
The driving voltage, external quantum efficiency (EQE), and lifespan (T80) of each of the organic light-emitting devices manufactured according to Example 1 and Comparative Example 1 were evaluated as a relative value. Results thereof are shown in Table 3. This evaluation was performed using a current-voltage meter (Keithley 2400) and a luminance meter (Minolta Cs-1000A), and the lifespan (T80) was evaluated by measuring, as a relative value, the amount of time that elapsed until luminance was reduced to 80% of the initial luminance of 100%.
Referring to Table 3, it can be seen that the organic light-emitting device of Example 1 has excellent external quantum efficiency and lifespan, and, compared to the organic light-emitting device of Comparative Example 1, has higher external quantum efficiency and a longer lifespan.
An organic light-emitting device was manufactured in the same manner as in Example 1, except that, in forming the emission layer, the weight ratio of compound CBP, which was used as a host, was 88.5%, and the weight ratio of compound 125 and compound FD, which were used as dopants, was 10%:1.5%.
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, Compound FD was used instead of Compound 1.
The driving voltage, external quantum efficiency (EQE), and maximum luminescence wavelength and lifespan (T80) of each of the organic light-emitting devices manufactured according to Example 2 and Comparative Example 2 were evaluated. Results thereof are shown in Table 4. A current-voltage meter (Keithley 2400) and a luminance meter (Minolta Cs-1000A) were used as an apparatus for evaluation, and the lifespan (T80) (at 1200 nit) was evaluated by measuring the amount of time that elapsed until luminance was reduced to 80% of the initial brightness of 100%.
From Table 4, it can be seen that the organic light-emitting device of Example 2 had a lower driving voltage and significantly improved external quantum efficiency and lifespan characteristics compared to the organic light-emitting device of Comparative Example 2.
The organometallic compound has excellent photochemical stability, and an organic light-emitting device using the organometallic compound may have improved efficiency and lifespan. Such organometallic compounds have excellent phosphorescent luminescent characteristics, and thus, when used, a diagnostic composition having a high diagnostic efficiency may be provided.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the figures, 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 |
|---|---|---|---|
| 10-2019-0070074 | Jun 2019 | KR | national |
| 10-2020-0050329 | Apr 2020 | KR | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 7553560 | Lamansky et al. | Jun 2009 | B2 |
| 10199583 | Hang et al. | Feb 2019 | B1 |
| 20130168656 | Tsai et al. | Jul 2013 | A1 |
| 20150105556 | Li et al. | Apr 2015 | A1 |
| 20180182981 | Chen | Jun 2018 | A1 |
| 20180219161 | Li et al. | Aug 2018 | A1 |
| 20180375036 | Chen | Dec 2018 | A1 |
| 20190036039 | Jung | Jan 2019 | A1 |
| 20190036042 | Kim | Jan 2019 | A1 |
| 20190119312 | Chen | Apr 2019 | A1 |
| 20190280222 | Kim et al. | Sep 2019 | A1 |
| 20200199164 | Kim et al. | Jun 2020 | A1 |
| 20200216481 | Chen et al. | Jul 2020 | A1 |
| 20200266366 | Bold et al. | Aug 2020 | A1 |
| 20200392173 | Bae | Dec 2020 | A1 |
| 20200395560 | Bae | Dec 2020 | A1 |
| 20210098721 | Jung | Apr 2021 | A1 |
| 20210380620 | Kim | Dec 2021 | A1 |
| 20220081457 | Bae | Mar 2022 | A1 |
| 20230002429 | Min | Jan 2023 | A1 |
| Number | Date | Country |
|---|---|---|
| 108840886 | Nov 2018 | CN |
| 109748938 | May 2019 | CN |
| 4120381 | Jan 2023 | EP |
| 1020160012941 | Feb 2016 | KR |
| 1020180077023 | Jul 2018 | KR |
| 1020190000812 | Jan 2019 | KR |
| 1020200076583 | Jun 2020 | KR |
| 2002015645 | Feb 2002 | WO |
| 2005019373 | Mar 2005 | WO |
| Entry |
|---|
| CAS reg. No. 2567555-29-5, Jan. 5, 2021. (Year: 2021). |
| CAS reg. No. 2567560-16-9, Jan. 5, 2021. (Year: 2021). |
| English Abstract of CN 109748938. |
| Extended European search report issued by the European Patent Office dated Oct. 16, 2020 in the examination of the European Patent Application No. 20179489.8, which corresponds to the U.S. Application above. |
| Ruben Seifert, et al., Chemical degradation mechanisms of highly efficient blue phosphorescent emitters used for organic light emitting diodes, Organic Electronics,14 (2013) 115-123. |
| Xiao-Chun Hang,, et al., Highly Efficient Blue-Emitting Cyclometalated Platinum(II) Complexes by Judicious Molecular Design, Angewandte Chemie, International Edition (2013), 52(26), 6753-6756. |
| Number | Date | Country | |
|---|---|---|---|
| 20200395559 A1 | Dec 2020 | US |
