Patent Application
20230322827
The present disclosure relates to an organometallic compound, an organic light-emitting device including the organometallic compound, and a diagnostic composition that includes the organometallic compound.
Organic light-emitting devices (OLEDs) are self-emission devices which produce full-color images. In addition, OLEDs have wide viewing angles and exhibit excellent driving voltage and response speed characteristics.
OLEDs include an anode, a cathode, and an organic layer between the anode and the cathode and including 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.
Further, light-emitting compounds, e.g., phosphorescence-emitting compounds, can also be used to monitor, sense, or detect biological materials, including a variety of cells and proteins.
Provided are an organometallic compound, an organic light-emitting device including the organometallic compound, and a diagnostic composition including the organometallic compound.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments.
According an aspect of an embodiment, an organometallic compound may be represented by Formula 1:
Another aspect provides 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 compounds represented by Formula 1.
In the organic layer, the organometallic compound included in the emission layer may serve as a dopant.
According to another aspect, a diagnostic composition may include at least one organometallic compound represented by Formula 1.
These and/or other aspects will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings in which:
The FIGURE is a schematic cross-sectional view of an organic light-emitting device according to an 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 clearly indicates otherwise. For example, “an element” has the same meaning as “at least one element,” unless the context clearly 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.
According to an aspect, an organometallic compound may be represented by Formula 1:
For example, the ring CY2 in Formula 1 may be i) a first ring, ii) a second ring, iii) a condensed cyclic group in which two or more first rings are condensed with each other, iv) a condensed cyclic group in which two or more second rings are condensed with each other, or v) a condensed cyclic group in which at least one first ring is condensed with at least one second ring,
In one or more embodiments, the ring CY2 in Formula 1 may be 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 thiophene group, a furan group, a pyrrole group, a cyclopentadiene group, a silole group, a 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 fluorene group, a dibenzosilole group, a dibenzoborole group, a dibenzophosphole group, a dibenzoselenophene group, a dibenzogermole group, a dibenzothiophene 5-oxide group, 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 isoxazole 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, a 5,6,7,8-tetrahydroquinoline group, an adamantane group, a norbornane group, or a norbornene group.
In one or more embodiments, the ring CY2 may be a benzene group, a naphthalene group, a 1, 2, 3, 4-tetrahydronaphthalene group, a thiophene group, a furan group, a pyrrole group, a cyclopentadiene group, a silole group, a benzothiophene group, a benzofuran group, an indole group, an indene group, a benzosilole group, a dibenzothiophene group, a dibenzofuran group, a carbazole group, a fluorene group, or a dibenzosilole group.
In Formula 1, R1 to R8, R20 and A7 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 C3-C10 cycloalkyl group, a substituted or unsubstituted C2-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 C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl 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). Q1 to Q9 may respectively be understood by referring to the descriptions of Q1 to Q9 provided herein.
In some embodiments, R20 in Formula 1 may include neither a fluoro group (—F) nor a cyano group. For example, R20 may be a group that includes neither a fluoro group (—F) nor a cyano group.
In some embodiments, in Formula 1, R1 to R8, R20 and A7 may each independently be:
In one or more embodiments, R1 to R8, R20 and A7 in Formula 1 may each independently be hydrogen, deuterium, —F, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 heterocycloalkyl group, —Si(Q3)(Q4)(Q5), or —Ge(Q3)(Q4)(Q5). Herein, R20 may include neither a fluoro group nor a cyano group.
In one or more embodiments, R1 to R8 and A7 in Formula 1 may each independently be:
In one or more embodiments, R20 in Formula 1 may be:
The designation d2 in Formula 1 indicates the number of R20(s), and may be an integer from 0 to 10. When d2 is 2 or more, two or more R20(s) may be identical to or different from each other. For example, d2 may be an integer from 0 to 6.
In an exemplary embodiment, at least one of R1 to R8, R20 or any combination thereof in Formula 1 may include at least one fluoro group (—F).
In an exemplary embodiment, at least one of R1 to R8 (for example, at least one of R2 to R8, or at least one of R3 to R6) of Formula 1 may include at least one fluoro group (—F).
In an exemplary embodiment, at least one of R1 to R8 (for example, at least one of R2 to R8, or at least one of R3 to R6) of Formula 1 may be a group including at least one fluoro group (—F).
In one or more embodiments, at least one of R1 to R8 in Formula 1 may each independently be:
A1 to A6 in Formula 1 may each independently be 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 C3-C10 cycloalkyl group, a substituted or unsubstituted C2-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 C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group.
For example, A1 to A6 in Formula 1 may each independently be:
In one or more embodiments, A1 to A6 in Formula 1 may each independently be a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C2-C10 heterocycloalkyl group.
In one or more embodiments, A1 to A6 in Formula 1 may each independently be a C1-C20 alkyl group, a C3-C10 cycloalkyl group, or a C2-C10 heterocycloalkyl group, each unsubstituted or substituted with deuterium, —F, C1-C20 alkyl group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, or any combination thereof.
In an exemplary embodiment, R1 to R8, R20 and A7 in Formula 1 may each independently be hydrogen, deuterium, —F, —CH3, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, 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 9-233, a group represented by one of Formulae 9-201 to 9-233 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 9-201 to 9-233 in which at least one hydrogen is substituted with —F, a group represented by one of Formulae 10-1 to 10-126, a group represented by one of Formulae 10-1 to 10-126 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 10-1 to 10-126 in which at least one hydrogen is substituted with —F, a group represented by one of Formulae 10-201 to 10-343, a group represented by one of Formulae 10-201 to 10-343 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 10-201 to 10-343 in which at least one hydrogen is substituted with —F, —Si(Q3)(Q4)(Q5), or —Ge(Q3)(Q4)(Q5) (herein Q3 to 05 are the same as described in the present specification), and at least one of R1 to R8 (for example, at least one of R2 to R8, or at least one of R3 to R6) may be —F, —CF3, —CF2H, —CFH2, 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 9-233 in which at least one hydrogen is substituted with —F, a group represented by one of Formulae 10-1 to 10-126 in which at least one hydrogen is substituted with —F, or a group represented by one of Formulae 10-201 to 10-343 in which at least one hydrogen is substituted with —F.
In one or more embodiments, R20 in Formula 1 may be hydrogen, deuterium, —CH3, —CD3, —CD2H, —CDH2, 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 9-201 to 9-233, a group represented by one of Formulae 9-201 to 9-233 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 10-1 to 10-126, a group represented by one of Formulae 10-1 to 10-126 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 10-201 to 10-343, a group represented by one of Formulae 10-201 to 10-343 in which at least one hydrogen is substituted with deuterium, —Si(Q3)(Q4)(Q5), or —Ge(Q3)(Q4)(Q5) (herein Q3 to Q5 are the same as described in the present specification).
In one or more embodiments, A1 to A6 in Formula 1 may each independently be —CH3, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, 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 9-233, a group represented by one of Formulae 9-201 to 9-233 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 9-201 to 9-233 in which at least one hydrogen is substituted with —F, a group represented by one of Formulae 10-1 to 10-126, a group represented by one of Formulae 10-1 to 10-126 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 10-1 to 10-126 in which at least one hydrogen is substituted with —F, a group represented by one of Formulae 10-201 to 10-343, a group represented by one of Formulae 10-201 to 10-343 in which at least one hydrogen is substituted with deuterium, or a group represented by one of Formulae 10-201 to 10-343 in which at least one hydrogen is substituted with —F:
* in Formulae 9-1 to 9-39, 9-201 to 9-233, 10-1 to 10-126, and 10-201 to 10-343 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 9-233 in which at least one hydrogen is substituted with deuterium” may each be, for example, a group represented by one of Formulae 9-501 to 9-514 and 9-601 to 9-635:
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 9-233 in which at least one hydrogen is substituted with —F” may each 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 10-126 in which at least one hydrogen is substituted with deuterium” and the “group represented by one of Formulae 10-201 to 10-343 in which at least one hydrogen is substituted with deuterium” may each 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 10-126 in which at least one hydrogen is substituted with —F” and the “group represented by one of Formulae 10-201 to 10-343 in which at least one hydrogen is substituted with —F” may each be, for example, a group represented by one of Formulae 10-601 to 10-615:
In one or more embodiments, at least one of R2 to R8 of Formula 1 (for example, one or two of R2 to R8) may include at least one fluoro group (—F).
In one or more embodiments, in Formula 1,
In one or more embodiments, regarding Formula 1,
In one or more embodiments, R5 in Formula 1 may not be hydrogen.
In one or more embodiments, R20 in Formula 1 may be a C1-C20 alkyl group, a C3-C10 cycloalkyl group, or a C2-C10 heterocycloalkyl group, each unsubstituted or substituted with deuterium, a C1-C20 alkyl group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, or any combination thereof.
In one or more embodiments, R20 in Formula 1 may be a C1-C20 alkyl group, unsubstituted or substituted with deuterium, a C1-C20 alkyl group, or any combination thereof.
In one or more embodiments, d2 in Formula 1 may be 2.
In one or more embodiments, R20 in Formula 1 may be a C1-C20 alkyl group, unsubstituted or substituted with deuterium, a C1-C20 alkyl group, or any combination thereof, and d2 may be 2.
In one or more embodiments, the organometallic compound represented by Formula 1 may have at least one deuterium.
In one or more embodiments, at least one of R1 to R8 of Formula 1 may have at least one deuterium.
In one or more embodiments, at least one of R20 in number of d2 may have at least one deuterium.
In one or more embodiments, at least one of R20 in number of d2 may be a deuterium-containing C1-C20 alkyl group, a deuterium-containing C3-C10 cycloalkyl group, or a deuterium-containing C2-C10 heterocycloalkyl group, each unsubstituted or substituted with a C1-C20 alkyl group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, or any combination thereof.
In Formula 1, 1) two or more of R1 to R8 may be optionally linked to each other to form a C5-C30 carbocyclic group which is unsubstituted or substituted with at least one R1a or a C1-C30 heterocyclic group which is unsubstituted or substituted with at least one R1a, 2) two or more of R20(s) in the number of d2 may be optionally linked to each other to form a C5-C30 carbocyclic group which is unsubstituted or substituted with at least one R1a or a C1-C30 heterocyclic group which is unsubstituted or substituted with at least one R1a, and 3) two or more of A1 to A7 may be optionally linked to each other to form a C5-C30 carbocyclic group which is unsubstituted or substituted with at least one R1a or a C1-C30 heterocyclic group which is unsubstituted or substituted with at least one R1a. Herein, R1a may be understood by referring to the description of A7.
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 phrase “a C5-C30 carbocyclic group (which is unsubstituted or substituted with at least one R1a)” may include, for example, an adamantane group, a norbornene group, a bicyclo[1.1.1]pentane group, a bicyclo[2.1.1]hexane group, a bicyclo[2.2.1]heptane group (a norbornane 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, cyclopentadiene group, a 1,2,3,4-tetrahydronaphthalene group, a fluorene group, each being unsubstituted or substituted with at least one R1a.
The term “C1-C30 heterocyclic group” as used herein refers to a saturated or unsaturated cyclic group having, as a ring-forming atom, at least one heteroatom selected from N, O, Si, P, Se, B, Ge, or S other than 1 to 30 carbon atoms. The C1-C30 heterocyclic group may be a monocyclic group or a polycyclic group.
The phrase “a C1-C30 heterocyclic group (which is unsubstituted or substituted with at least one R1a)” may include, for example, a thiophene group, a furan group, a pyrrole group, a silole group, a 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, 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, and a 5,6,7,8-tetrahydroquinoline group, each being unsubstituted or substituted with at least one R1a.
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” used herein refers to a divalent group having the same structure as that of the C1-C60 alkyl group.
Examples of the C1-C60 alkyl group, the C1-C20 alkyl group, and/or the C1-C10 alkyl group are 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 iso-nonyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an iso-decyl group, a sec-decyl group, and a tert-decyl group, each unsubstituted or substituted with 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 iso-nonyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an iso-decyl group, a sec-decyl group, a tert-decyl group, or any combination thereof. For example, Formula 9-33 may be a branched C6 alkyl group, and may be 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 are a methoxy group, an ethoxy group, a propoxy group, isopropyloxy group, a butoxy group, or a pentoxy 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 that of the C3-C10 cycloalkyl group.
Examples of the C3-C10 cycloalkyl group are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a bicyclo[1.1.1]pentyl group (bicyclo[1.1.1]pentyl), a bicyclo[2.1.1]hexyl group (bicyclo[2.1.1]hexyl), a bicyclo[2.2.1]heptyl group (bicyclo[2.2.1]heptyl)(a norbornyl group), and a bicyclo[2.2.2]octyl group.
The term “C2-C10 heterocycloalkyl group” as used herein refers to a monovalent saturated monocyclic group having at least one heteroatom selected from N, O, P, Si Se, B, Ge, or S as a ring-forming atom and 2 to 10 carbon atoms, and non-limiting examples thereof include a tetrahydrofuranyl group, and a tetrahydrothiophenyl group. The term “C2-C10 heterocycloalkylene group” as used herein refers to a divalent group having the same structure as the C2-C10 heterocycloalkyl group.
Examples of the C2-C10 heterocycloalkyl group are a silolanyl group, a silinanyl group, a tetrahydrofuranyl group, a tetrahydro-2H-pyranyl group, and a tetrahydrothiophenyl group.
The term “deuterium-containing C1-C60 alkyl group (or, deuterium-containing C1-C20 alkyl group, a deuterium-containing C2-C20 alkyl group, or the like)” as used herein refers to a C1-C60 alkyl group substituted with at least one deuterium (or a C1-C20 alkyl group substituted with at least one deuterium, a C2-C20 alkyl substituted with at least one deuterium, or the like). For example, the term “the deuterium-containing C1 alkyl group (that is, a deuterium-containing methyl group)” as used herein includes —CD3, —CD2H, and —CDH2.
The term “deuterium-containing C3-C10 cycloalkyl group” as used herein refers to a C3-C10 cycloalkyl group substituted with at least one deuterium. Examples of the “deuterium-containing C3-C10 cycloalkyl group” are provided in connection with, for example, Formula 10-501.
The terms “fluorinated C1-C60 alkyl group (or a fluorinated C1-C20 alkyl group, or the like)”, “fluorinated C3-C10 cycloalkyl group”, or “fluorinated C2-C10 heterocycloalkyl group” as used herein refer to a C1-C60 alkyl group (or, C1-C20 alkyl group, or the like) substituted with at least one a fluoro group (—F), a C3-C10 cycloalkyl group substituted with at least one a fluoro group (—F), and a C2-C10 heterocycloalkyl group substituted with at least one a fluoro group (—F), respectively. For example, the term “the fluorinated C1 alkyl group (that is, the fluorinated methyl group)” includes —CF3, —CF2H, and —CFH2. The “fluorinated C1-C60 alkyl group (or the fluorinated C1-C20 alkyl group, or the like)”, “the fluorinated C3-C10 cycloalkyl group”, or “the fluorinated C2-C10 heterocycloalkyl group” may be i) a fully fluorinated C1-C60 alkyl group (or, fully fluorinated C1-C20 alkyl group, or the like), a fully fluorinated C3-C10 cycloalkyl group, or a fully fluorinated C2-C10 heterocycloalkyl group, each group in which all hydrogen 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 C2-C10 heterocycloalkyl group, each group in which some hydrogen are substituted with a fluoro group.
The term “(C1-C20 alkyl)‘X’ group” as used herein refers to a ‘X’ group 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.
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 that of the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethynyl group, and a propynyl group. The term “C2-C60 alkynylene group” as used herein refers to a divalent group having the same structure as that of the C2-C60 alkynyl group.
The term “C3-C10 cycloalkenyl group” as used herein refers to a monovalent monocyclic group that has 3 to 10 carbon atoms and at least one carbon-carbon double bond in the ring thereof and no aromaticity, and 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 heteroatom selected from N, O, P, Si, Se, B, Ge, or S as a ring-forming atom, 2 to 10 carbon atoms, and at least one 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. Non-limiting 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” used herein 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 heteroatom selected from N, O, P, Si, Se, B, Ge, or S 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 heteroatom selected from N, O, P, Si, Se, B, Ge, or S as a ring-forming atom, and 1 to 60 carbon atoms. Examples of the C1-C60 heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, and an isoquinolinyl group. When the C6-C60 heteroaryl group and the C6-C60 heteroarylene group each include two or more rings, the rings may be fused to each other.
The 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 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 selected from N, O, P, Si, Se, B, Ge, or S, other than carbon atoms, as a ring-forming atom, and no aromaticity in its entire molecular structure. Non-limiting 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.
A 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 C3-C10 cycloalkyl group, the substituted C2-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 monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may be:
In the present specification, Q1 to Q9, Q11 to Q19, Q21 to Q29, and Q31 to Q39 may each independently be hydrogen; deuterium; —F; —CI; —Br; —I; 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 C1-C60 alkyl group, unsubstituted or substituted with deuterium, a C1-C60 alkyl group, a C6-C60 aryl group, or any combination thereof; a C2-C60 alkenyl group; a C2-C60 alkynyl group; a C1-C60 alkoxy group; a C3-C10 cycloalkyl group; a C2-C10 heterocycloalkyl group; a C3-C10 cycloalkenyl group; a C2-C10 heterocycloalkenyl group; a C6-C60 aryl group, unsubstituted or substituted with deuterium, a C1-C60 alkyl group, a C6-C60 aryl group, or any combination thereof; 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.
For example, in the present specification, Q1 to Q9, Q11 to Q19, Q21 to Q29, and Q31 to Q39 may each independently be
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, and an azadibenzothiophene 5,5-dioxide group” respectively refer to a heterocyclic group having the same backbone 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, 9H-fluorene-9-one group, and a dibenzothiophene 5,5-dioxide group” in which at least one carbon atoms constituting the cyclic groups is substituted with a nitrogen.
In one or more embodiments, a group represented by
in Formula 1 may be a group represented by one of Formulae CY1 to CY108:
In Formulae CY1 to CY108,
For example, R2 to R8 in Formulae CY1 to CY108 may each independently be:
In one or more embodiments, the group represented by
in Formula 1 may be a group represented by one of Formulae A(1) to A(7):
In Formulae A(1) to A(7),
For example, R9 and R11 in Formula A(1) may each independently be a C1-C20 alkyl group, a C3-C10 cycloalkyl group, or a C2-C10 heterocycloalkyl group, each unsubstituted or substituted with deuterium, a C1-C20 alkyl group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, or any combination thereof.
In one or more embodiments, R9 and R11 in Formula A(1) may each independently be a C1-C20 alkyl group, unsubstituted or substituted with deuterium, a C1-C20 alkyl group, or any combination thereof.
In one or more embodiments, R10 and R12 in Formula A(1) may each independently be hydrogen or deuterium.
In one or more embodiments, R9 and R11 in Formula A(1) may be identical to each other.
In one or more embodiments, R9 and R11 in Formula A(1) may be different from each other.
In one or more embodiments, R9 and R11 in Formula A(1) may be different from each other, and the number of carbon included in R11 may be greater than the number of carbon included in R9.
In one or more embodiments, i) at least one of R9 to R12 in Formula A(1), ii) R11, R12, one of R21 to R26, or any combination thereof in Formulae A(2) and A(3), iii) R9, R12, one of R21 to R26, or any combination thereof in Formulae A(4) and A(5), and iv) R9, R10, one of R21 to R26, or any combination thereof in Formulae A(6) and A(7), may each independently be a deuterium-containing C1-C20 alkyl group, a deuterium-containing C3-C10 cycloalkyl group, or a deuterium-containing C2-C10 heterocycloalkyl group, each unsubstituted or substituted with a C1-C20 alkyl group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, or any combination thereof.
In one or more embodiments, at least one of R9 and R11 in Formula A(1) (for example, R9 and R11 in Formula A(1)) may each independently be a deuterium-containing C1-C20 alkyl group, a deuterium-containing C3-C10 cycloalkyl group, or a deuterium-containing C2-C10 heterocycloalkyl group, each unsubstituted or substituted with a C1-C20 alkyl group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, or any combination thereof.
In one or more embodiments, the group represented by
in Formula 1 may be a group represented by Formula A(1) or A(5).
In one or more embodiments, at least one of A1 to A6 in Formula 1 may each independently be a substituted or unsubstituted C2-C60 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C2-C10 heterocycloalkyl group.
In one or more embodiments, at least one of A1 to A3 and at least one of A4 to A6 in Formula 1 may each independently be a substituted or unsubstituted C2-C60 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C2-C10 heterocycloalkyl group.
In one or more embodiments, the number of carbons included in the group represented by *—C(A1)(A2)(A3) in Formula 1 may be 5 or more, and/or the number of carbons included in the group represented by *—C(A4)(A5)(A6) in Formula 1 may be 5 or more.
In one or more embodiments, A1, A2, and A3 of the group represented by *—C(A1)(A2)(A3) in Formula 1 may be linked to each other to form a C5-C30 carbocyclic group which is unsubstituted or substituted with at least one R1a or a C1-C30 heterocyclic group which is unsubstituted or substituted with at least one R1a. That is, the group represented by *—C(A1)(A2)(A3) in Formula 1 may be a C5-C30 carbocyclic group which is unsubstituted or substituted with at least one R1a or a C1-C30 heterocyclic group which is unsubstituted or substituted with at least one R1a (for example, an adamantane group, a norbornene group, a bicyclo[1.1.1]pentane group, a bicyclo[2.1.1]hexane group, a bicyclo[2.2.1]heptane group (a norbornane group), a bicyclo[2.2.2]octane group, a cyclopentane group, a cyclohexane group, or a cyclohexene group, each unsubstituted or substituted with at least one R1a).
In one or more embodiments, A4, A5, and A6 of the group represented by *—C(A4)(A5)(A6) in Formula 1 may be linked to each other to form a C5-C30 carbocyclic group which is unsubstituted or substituted with at least one Ria or a C1-C30 heterocyclic group which is unsubstituted or substituted with at least one R1a. That is, the group represented by *—C(A4)(As)(A6) in Formula 1 may be a C5-C30 carbocyclic group which is unsubstituted or substituted with at least one R1a or a C1-C30 heterocyclic group which is unsubstituted or substituted with at least one R1a (for example, an adamantane group, a norbornene group, a bicyclo[1.1.1]pentane group, a bicyclo[2.1.1]hexane group, a bicyclo[2.2.1]heptane group (a norbornane group), a bicyclo[2.2.2]octane group, a cyclopentane group, a cyclohexane group, or a cyclohexene group, each unsubstituted or substituted with at least one R1a).
In one or more embodiments, A1, A2, and A3 in Formula 1 may each independently be a substituted or unsubstituted C1 alkyl group (a substituted or unsubstituted methyl group).
In one or more embodiments, A1, A2, and A3 in Formula 1 may each independently be a C1 alkyl group unsubstituted or substituted with deuterium, —F, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, or any combination thereof.
For example, the organometallic compound may be at least one of Compounds 1 to 16 below, but embodiments of the present disclosure are not limited thereto.
In an organometallic compound represented by Formula 1, 1) ring CY1 (see Formula 1′) is, as illustrated in Formula 1, a condensed cyclic group in which two benzene groups are condensed with one pyridine group, and 2) at least one of R1 to R8, R20, or any combination thereof includes at least one a fluoro group (—F). Accordingly, the transition dipole moment of the organometallic compounds may be increased, and the conjugation length of the organometallic compounds is relatively increased and structural rigidity thereof is increased, leading to a decrease in non-radiative transition. Thus, an electronic device, for example, an organic light-emitting device, including the organometallic compound represented by Formula 1 may have high quantum efficiency (FOE), and thus, may have high luminescence efficiency.
In one or more embodiments, A1 to A6 in Formula 1 may each independently be 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 C3-C10 cycloalkyl group, a substituted or unsubstituted C2-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 C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group. That is, A1 to A6 in Formula 1 may each have one or more carbons.
Although not wishing to be bound to a particular theory, an α-proton has chemical reactivity that is about 105 greater than that of a β-proton. That is, the α-proton may cause a side reaction due to production of intermediates in various forms during synthesis and/or storage of a compound. However, carbons bound to each A1 to A6 in Formula 1 as described above may not include the α-proton, and in this regard, the organometallic compound represented by Formula 1 may have a stable chemical structure with minimal occurrence of a side reaction before/after synthesis, and at the same time, an intermolecular interaction of the organometallic compound may be minimized during the operation of an electronic device (for example, an organic light-emitting device) including the organometallic compound.
Furthermore, Formula 1 has Ligand 2 being bulky and having a strong electron donating capability and thus, an interaction between Ligand 1 and Ligand 2 in Formula 1 may be enhanced. Thus, the organometallic compound represented by Formula 1 may have improved structural rigidity, a full width at half maximum (FWHM) in the photoluminescent spectrum or electroluminescent spectrum of the organometallic compound represented by Formula 1 may be reduced, and a vibronic state of the organometallic compound represented by Formula 1 may be reduced. Accordingly a non-radiative decay of the organometallic compound represented by Formula 1 can be reduced and thus an electronic device, for example, an organic light-emitting device, including the organometallic compound represented by Formula 1 may have high luminescence efficiency and long lifespan.
The highest occupied molecular orbital (HOMO) energy level, lowest unoccupied molecular orbital (LUMO) energy level, and T1 energy level of Compounds 1 to 16, which are encompassed by the organometallic compound represented by Formula 1, were evaluated by using Gaussian 09 that performs molecular structure optimizations according to density functional theory (DFT) at a degree of B3LYP. The results thereof are shown in Table 1.
In one or more embodiments, when R20 in the organometallic compound represented by Formula 1 includes neither a fluoro group (—F) nor a cyano group, the organometallic compound represented by Formula 1 may emit light having high color purity (for example, light having a relatively narrow full width at half maximum (FWHM) in the photoluminescent spectrum or electroluminescent spectrum).
In one or more embodiments, the FWHM of the emission peak of the photoluminescent spectrum or electroluminescent spectrum of the organometallic compound may be 64 nm or less. For example, the FWHM of the emission peak of the photoluminescent spectrum or electroluminescent spectrum of the organometallic compound may be from about 45 nm to about 64 nm, about 45 nm to about 59 nm, about 49 nm to about 55 nm or about 50 nm to about 55 nm.
In one or more embodiments, the maximum emission wavelength (emission peak wavelength, λmax) of the emission peak of the photoluminescent spectrum or electroluminescent spectrum of the organometallic compound may be from about 615 nm to about 640 nm. In one or more embodiments, the maximum emission wavelength (emission peak wavelength, λmax) of the emission peak of the photoluminescent spectrum or electroluminescent spectrum of the organometallic compound may be from about 615 nm to about 630 nm or about 620 nm to about 630 nm.
In one or more embodiments, the highest occupied molecular orbital (HOMO) energy level of the organometallic compound represented by Formula 1 may be in the range of −5.300 eV to −5.050 eV, for example, −5.200 eV to −5.100 eV. The HOMO energy level may be evaluated by a cyclic voltammetry. For example, the HOMO energy level may be evaluated in accordance to a method described in Table 2 described hereinafter.
In one or more embodiments, the lowest unoccupied molecular orbital (LUMO) energy level of the organometallic compound represented by Formula 1 may be in the range of −2.900 eV to −2.300 eV, for example, −2.700 eV to −2.300 eV. The LUMO energy level may be evaluated by using an UV absorption spectrum. For example, the LUMO energy level may be evaluated in accordance to a method described in Table 2 described hereinafter.
In one or more embodiments, the photoluminescence quantum yield of the organometallic compound represented by Formula 1 in film may be from about 91% to about 100%. For example, the PLQY of the organometallic compound in a film may be from about 92% to about 100%, from about 93% to about 100%, from about 94% to about 100%, from about 95% to about 100%, from about 96% to about 100%, from about 97% to about 100%, from about 98% to about 100%, or from about 99% to about 100%, or about 100%. For example, the PLQY in film may be evaluated in accordance with Evaluation 2 described hereinafter.
In one or more embodiments, a decay time of the organometallic compound represented by Formula 1 may be 0.9 μs and less, for example, in the range of 0.6 μs to 0.8 μs. The decay time may be evaluated from Time-resolved photoluminescence (TRPL) of the organometallic compound represented by Formula 1. For example, the decay time may be evaluated in accordance with Evaluation 3 described hereinafter.
In one or more embodiments, the horizontal orientation ratio of the transition dipole moment of the organometallic compound represented by Formula 1 may be from about 90% to about 100%.
For example, the horizontal orientation ratio of the transition dipole moment of the organometallic compound may be, for example, from about 90% to about 100%, from about 91% to about 100%, from about 92% to about 100%, from about 93% to about 100%, from about 94% to about 100%, from about 95% to about 100%, from about 96% to about 100%, from about 97% to about 100%, from about 98% to about 100%, from about 99% to about 100%, or about 100%.
The horizontal orientation ratio of the transition dipole moment may be evaluated by using an angle-dependent photoluminescence (PL) measurement apparatus. The angle-dependent PL measurement apparatus may be understood by referring to, for example, the description of the angle-dependent PL measurement apparatus disclosed in Korean application No. 2013-0150834. Korean application No. 2013-0150834 is incorporated herein.
As described above, since the horizontal orientation ratio of the transition dipole moment of the organometallic compound is high, when an organic light-emitting device including the organometallic compound is driven, an electric field may be emitted in a substantially parallel to a film including the organometallic compound, and thus, optical loss caused by a waveguide mode and/or a surface plasmon polariton mode may be reduced. An external extraction efficiency of the electronic device emitting light (that is, an efficiency of light extracted to the outside from the electronic device (for example, an organic light-emitting device) including a film including the organometallic compound (for example, an emission layer to be described)) by such a mechanism may be present. Accordingly, an electronic device, for example, an organic light-emitting device, including the organometallic compound may have high luminescence efficiency.
Synthesis methods of the organometallic compound represented by Formula 1 may be understood 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 in an organic layer of an organic light-emitting device, for example, for use as a dopant in an emission layer of the organic layer. Thus, another aspect provides an organic light-emitting device that includes: a first electrode; a second electrode; and an organic layer disposed between the first electrode and the second electrode and including an emission layer, and the organic layer includes at least one organometallic compounds represented by Formula 1.
Since the organic light-emitting device includes an organic layer including the organometallic compound represented by Formula 1 described above, excellent characteristics may be obtained in terms of the driving voltage, the external quantum efficiency, a roll-off ratio, a lifespan and a relatively narrow FWHM of an electroluminescence (EL) spectrum emission peak.
The organometallic compound of Formula 1 may be used 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 of the organometallic compound represented by Formula 1 in the emission layer is smaller than an amount of the host).
In one or more embodiments, the emission layer may emit red light.
The expression “(an organic layer) includes at least one organometallic compounds” used herein may include a case in which “(an organic layer) includes identical organometallic compounds represented by Formula 1” and a case in which “(an organic layer) includes two or more different organometallic compounds represented by Formula 1.”
For example, the organic layer may include, as the organometallic compound, only Compound 1. In this regard, Compound 1 may exist in an 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 first electrode may be an anode, which is a hole injection electrode, and the second electrode may be a cathode, which is an electron injection electrode, or the first electrode may be a cathode, which is an electron injection electrode, and the second electrode may be an anode, which is a hole injection electrode.
In one or more embodiments, in the organic light-emitting device, the first electrode 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.
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.
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 general organic light-emitting devices 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 a material 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.
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, which are 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 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 m-MTDATA, TDATA, 2-TNATA, NPB, 3-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated-NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (PANI/CSA), polyaniline/poly(4-styrenesulfonate) (PANI/PSS), a compound represented by Formula 201 below, a compound represented by Formula 202 below, or any combination thereof:
Ar101 and Ar102 in Formula 201 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 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 C2-C10 heterocycloalkyl 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, or any combination thereof.
The designations 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 a phenyl group, a naphthyl group, an anthracenyl group, or a pyridinyl group, each unsubstituted or substituted with 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, a pyridinyl group, or any combination thereof.
In one or more embodiments, the compound represented by Formula 201 may be represented by Formula 201A:
For example, the hole transport region may include one of Compounds HT1 to HT21 or any combination thereof:
The 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 a hole injection layer, a hole transport layer, an electron blocking layer, or any combination thereof, the thickness of the hole injection layer may be in a range of about 100 Å to about 10,000 Å, for example, about 100 Å to about 1,000 Å, and a thickness of the hole transport layer may be in a range of about 50 Å to about 2,000 Å, for example, about 100 Å to about 1,500 Å. When the thicknesses of the hole transport region, the hole injection layer and the hole transport layer are within these ranges, satisfactory hole transporting characteristics may be obtained without a substantial increase in driving voltage.
The hole transport region may further include, in addition to these materials, a charge-generation material for the improvement of conductive properties. The charge-generation material may be homogeneously or non-homogeneously dispersed in the hole transport region.
The charge-generation material may be, for example, a p-dopant. The p-dopant may be a quinone derivative, a metal oxide, a cyano group-containing compound, or any combination thereof, but embodiments of the present disclosure are not limited thereto. Examples of the p-dopant are a quinone derivative, such as tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinone dimethane (F4-TCNQ), or F6-TCNNQ; a metal oxide, such as a tungsten oxide or a molybdenum oxide; a cyano group-containing compound, such as Compound HT-D1 below; or any combination thereof.
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 a material for the hole transport region described above, a material for a host to be explained later, or any combination thereof. 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, Compound H21, or any combination thereof.
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 hole transport layer.
The emission layer may include a host and a dopant, and the dopant may include an organometallic compound represented by Formula 1 described herein.
The host may include TPBi, TBADN, ADN (also referred to as “DNA”), CBP, CDBP, TCP, mCP, Compound H50, Compound H51, Compound 52, or any 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 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, but 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 BCP, Bphen, and BAlq.
In one or more embodiments, the hole blocking layer may include the host, a material for forming an electron transport layer to be described later, a material for forming an electron injection layer to be described later, or any combination thereof.
The 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. 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 BCP, Bphen, TPBi, Alq3, Balq, TAZ, NTAZ, or any combination thereof:
In one or more embodiments, the electron transport layer may include one of Compounds ET1 to ET25 or any combination thereof:
The 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, ET-D2, or a combination thereof.
The electron transport region may include an electron injection layer (EIL) that promotes flow of electrons from the second electrode 19 thereinto.
The electron injection layer may include LiF, NaCl, CsF, Li2O, BaO, or any combination thereof.
The 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 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 metal, an alloy, an electrically conductive compound, or any 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 formed as the material for forming the second electrode 19. 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.
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 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.
4-chloro-8-methyl-9-(trifluoromethyl)benzo[f]isoquinoline (24.53 g, 82.95 mmol), (3,5-dimethyl phenyl)boronic acid (14.93 g, 99.54 mmol), Pd(PPh3)4 (4.80 g, 4.15 mmol), and K2CO3 (34.38 g, 248.85 mmol), tetrahydrofuran (THF) (200 mL), and distilled water (50 mL) were mixed together, and the mixed solution was stirred under reflux for 18 hours. Then, the reaction temperature was lowered to room temperature, and an extraction process was performed thereon by using methylene chloride (MC). An organic layer extracted therefrom was dried by adding anhydrous magnesium sulfate (MgSO4) thereto to remove moisture, and then, filtered. A solvent was removed from a filtrate under reduced pressure, and a residue was purified by using column chromatography under conditions of ethyl acetate (EA):hexane=1:5, thereby obtaining 24.37 g (80%) of Compound L1(1).
MALDI-TOFMS (m/z): C23H18F3N (M+) 365.37.
Compound L1(1) (24.37 g, 66.70 mmol), iridium chloride (11.75 g, 33.32 mmol), ethoxyethanol (300 mL), and distilled water (100 mL) were mixed together, and the mixed solution was stirred under reflux for 24 hours. The reaction temperature was lowered to room temperature, and a solid produced therefrom was separated by filtration. A filtrate was sufficiently washed by using water, methanol, and hexane in the stated order, and a solid obtained therefrom was dried in a vacuum oven, thereby obtaining Compound L1(2) (19.00 g, 69%).
Compound L1(2) (19.00 g, 11.48 mmol), 3,7-diethyl-3,7-dimethylnonane-4,6-dione) (13.80 g, 57.40 mmol), Na2CO3 (12.17 g, 114.80 mmol), and ethoxyethanol (300 mL) were mixed together, and the mixed solution was stirred for 24 hours. A mixture obtained therefrom was filtered, and a filtered solid was sufficiently washed by using methanol and hexane, and purified by using column chromatography under conditions of dichloromethane:n-hexane=1:1 (v/v), thereby obtaining Compound 1 (13.00 g, 55%). Compound 1 was identified by mass spectrometry and high performance liquid chromatography (HPLC).
HRMS(MALDI) calcd for C61H60F6IrN2O2: m/z 1159.42, Found: 1159.37.
Compound 2 (11 g, 60%) was obtained in the same manner as in the synthesis of Compound 1 of Synthesis Example 1, except that 3,3,7,7-tetramethylnonane-4,6-dione was used instead of 3,7-diethyl-3,7-dimethylnonane-4,6-dione. Compound 2 was identified by mass spectrometry and HPLC.
HRMS(MALDI) calcd for C59H56F6IrN2O2: m/z 1131.39, Found: 1131.32.
Compound 3 (5 g, 50%) was obtained in the same manner as in the synthesis of Compound 1 of Synthesis Example 1, except that 2,2,6,6-tetramethylheptane-3,5-dione was used instead of 3,7-diethyl-3,7-dimethylnonane-4,6-dione. Compound 3 was identified by mass spectrometry and HPLC.
(HRMS(MALDI) calcd for C57H52F6IrN2O2: m/z 1160.35, Found: 1160.37.
4-chloro-8-fluorobenzo[f]isoquinoline (19.22 g, 82.95 mmol) (3,5-dimethylphenyl)boronic acid (14.93 g, 99.54 mmol), Pd(PPh3)4 (4.80 g, 4.15 mmol), K2CO3 (34.38 g, 248.85 mmol), THF (200 mL), and distilled water (50 mL) were mixed together, and the mixed solution was stirred under reflux for 18 hours. Then, the reaction temperature was lowered to room temperature, and an extraction process was performed thereon by using MC. An organic layer extracted therefrom was dried by adding MgSO4 thereto to remove moisture, and then, filtered. A solvent was removed from a filtrate under reduced pressure, and a residue was purified by using column chromatography under conditions of EA:hexane=1:5, thereby obtaining 20.1 g (80%) of Compound L4(1).
MALDI-TOFMS (m/z): C21H16FN (M+) 301.36.
Compound L4(1) (20.10 g, 66.70 mmol), iridium chloride (11.75 g, 33.32 mmol), ethoxyethanol (300 mL), and distilled water (100 mL) were mixed together, and the mixed solution was stirred under reflux for 24 hours. The reaction temperature was lowered to room temperature, and a solid produced therefrom was separated by filtration. A filtrate was sufficiently washed by using water, methanol, hexane in the stated order, and a solid obtained therefrom was dried in a vacuum oven, thereby obtaining Compound L4(2) (19.00 g, 69%).
Compound L4(2) (19.00 g, 11.48 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (10.56 g, 57.40 mmol), Na2CO3 (12.17 g, 114.80 mmol), and ethoxyethanol (300 mL) were mixed together, and the mixed solution was stirred for 24 hours to proceed a reaction. A mixture obtained therefrom was filtered, and a filtered solid was sufficiently washed by using methanol and hexane, and purified by using column chromatography under conditions of dichloromethane:n-hexane=1:1 (v/v), thereby obtaining Compound 4 (13.00 g, 55%). Compound 4 was identified by mass spectrometry and HPLC.
HRMS(MALDI) calcd for C53H48F2IrN2O2: m/z 975.19, Found: 975.20 Synthesis Example 5 (Compound 5)
4-chloro-7,9-difluorobenzo[f]isoquinoline (20.71 g, 82.95 mmol), (3,5-dimethylphenyl)boronic acid (14.93 g, 99.54 mmol), Pd(PPh3)4 (4.80 g, 4.15 mmol), K2CO3 (34.38 g, 248.85 mmol), THF (200 mL), and distilled water (50 mL) were mixed together, and the mixed solution was stirred under reflux for 18 hours. Then, the reaction temperature was lowered to room temperature, and an extraction process was performed thereon by using MC. An organic layer extracted therefrom was dried by adding MgSO4 thereto to remove moisture, and then, filtered. A solvent was removed from a filtrate under reduced pressure, and a residue was purified by using column chromatography under conditions of EA:hexane=1:5, thereby obtaining 21.30 g (80%) of Compound L5(1).
MALDI-TOFMS (m/z): C21H15F2N (M+) 319.35.
Compound L5(1) (21.30 g, 66.70 mmol), iridium chloride (11.75 g, 33.32 mmol), ethoxyethanol (300 mL), and distilled water (100 mL) were mixed together, and the mixed solution was stirred under reflux for 24 hours. The reaction temperature was lowered to room temperature, and a solid produced therefrom was separated by filtration. A filtrate was sufficiently washed by using water, methanol, hexane in the stated order, and a solid obtained therefrom was dried in a vacuum oven, thereby obtaining Compound L5(2) (19.00 g, 69%).
Compound L5(2) (19.00 g, 11.48 mmol), 3,7-diethyl-3,7-dimethylnonane-4,6-dione (13.80 g, 57.40 mmol), Na2CO3 (12.17 g, 114.80 mmol), and ethoxyethanol (300 mL) were mixed together, and the mixed solution was stirred for 24 hours. A mixture obtained therefrom was filtered, and a filtered solid was sufficiently washed by using methanol and hexane, and purified by using column chromatography under conditions of dichloromethane:n-hexane=1:1 (v/v), thereby obtaining Compound 5 (13.00 g, 55%). Compound 5 was identified by mass spectrometry and HPLC.
HRMS(MALDI) calcd for C57H54F4IrN2O2: m/z 1067.38, Found: 1067.28.
4-chloro-9-fluorobenzo[f]isoquinoline (19.21 g, 82.95 mmol), (3,5-dimethylphenyl)boronic acid (14.93 g, 99.54 mmol), Pd(PPh3)4 (4.80 g, 4.15 mmol), K2CO3 (34.38 g, 248.85 mmol), THF (200 mL), and distilled water (50 mL) were mixed together, and the mixed solution was stirred under reflux for 18 hours. Then, the reaction temperature was lowered to room temperature, and an extraction process was performed thereon by using MC. An organic layer extracted therefrom was dried by adding MgSO4 thereto to remove moisture, and then, filtered. A solvent was removed from a filtrate under reduced pressure, and a residue was purified by using column chromatography under conditions of EA:hexane=1:5, thereby obtaining 20.10 g (80%) of Compound L6(1).
MALDI-TOFMS (m/z): C21H16FN (M+) 301.36.
Compound L6(1) (20.10 g, 66.70 mmol), iridium chloride (11.75 g, 33.32 mmol), ethoxyethanol (300 mL), and distilled water (100 mL) were mixed together, and the mixed solution was stirred under reflux for 24 hours. The reaction temperature was lowered to room temperature, and a solid produced therefrom was separated by filtration. A filtrate was sufficiently washed by using water, methanol, hexane in the stated order, and a solid obtained therefrom was dried in a vacuum oven, thereby obtaining Compound L6(2) (19.00 g, 69%).
Compound L6(2) (19.00 g, 11.48 mmol), 3,3,7,7-tetramethylnonane-4,6-dione (13.80 g, 57.40 mmol), Na2CO3 (12.17 g, 114.80 mmol), and ethoxyethanol (300 mL) were mixed together, and the mixed solution was stirred for 24 hours. A mixture obtained therefrom was filtered, and a filtered solid was sufficiently washed by using methanol and hexane, and purified by using column chromatography under conditions of dichloromethane:n-hexane=1:1 (v/v), thereby obtaining Compound 6 (13.00 g, 55%). Compound 6 was identified by mass spectrometry and HPLC.
HRMS(MALDI) calcd for C55H52F2IrN2O2: m/z 1003.36, Found: 1003.25.
4-chloro-9-(trifluoromethyl)benzo[f]isoquinoline (23.36 g, 82.95 mmol), (3,5-dimethylphenyl)boronic acid (14.93 g, 99.54 mmol), Pd(PPh3)4 (4.80 g, 4.15 mmol), K2CO3 (34.38 g, 248.85 mmol), THF (200 mL), and distilled water (50 mL) were mixed together, and the mixed solution was stirred under reflux for 18 hours. Then, the reaction temperature was lowered to room temperature, and an extraction process was performed thereon by using MC. An organic layer extracted therefrom was dried by adding MgSO4 thereto to remove moisture, and then, filtered. A solvent was removed from a filtrate under reduced pressure, and a residue was purified by using column chromatography under conditions of EA:hexane=1:5, thereby obtaining 23.43 g (80%) of Compound L10(1).
MALDI-TOFMS (m/z): C22H16FN (M+) 351.36.
Compound L10(1) (23.43 g, 66.70 mmol), iridium chloride (11.75 g, 33.32 mmol), ethoxyethanol (300 mL), and distilled water (100 mL) were mixed together, and the mixed solution was stirred under reflux for 24 hours. The reaction temperature was lowered to room temperature, and a solid produced therefrom was separated by filtration. A filtrate was sufficiently washed by using water, methanol, hexane in the stated order, and a solid obtained therefrom was dried in a vacuum oven, thereby obtaining Compound L10(2) (19.00 g, 69%).
Compound L10(2) (19.00 g, 11.48 mmol), 1-((3R,5R,7R)-adamantan-1-yl)-4,4-dimethylpentane-1,3-dione (15.06 g, 57.40 mmol), Na2CO3 (12.17 g, 114.80 mmol), and ethoxyethanol (300 mL) were mixed together, and the mixed solution was stirred for 24 hours. A mixture obtained therefrom was filtered, and a filtered solid was sufficiently washed by using methanol and hexane, and purified by using column chromatography under conditions of dichloromethane:n-hexane=1:1 (v/v), thereby obtaining Compound 10 (13.00 g, 55%). Compound 10 was identified by mass spectrometry and HPLC.
HRMS(MALDI) calcd for C61H54F6IrN2O2: m/z 1153.37, Found: 1153.32.
4-chloro-6-fluorobenzo[f]isoquinoline (19.21 g, 82.95 mmol), (3,5-dimethylphenyl)boronic acid (14.93 g, 99.54 mmol), Pd(PPh3)4 (4.80 g, 4.15 mmol), K2CO3 (34.38 g, 248.85 mmol), THF (200 mL), and distilled water (50 mL) were mixed together, and the mixed solution was stirred under reflux for 18 hours. Then, the reaction temperature was lowered to room temperature, and an extraction process was performed thereon by using MC. An organic layer extracted therefrom was dried by adding MgSO4 thereto to remove moisture, and then, filtered. A solvent was removed from a filtrate under reduced pressure, and a residue was purified by using column chromatography under conditions of EA:hexane=1:5, thereby obtaining 20.10 g (80%) of Compound L13(1).
MALDI-TOFMS (m/z): C21H16FN (M+) 301.36.
Compound L13(1) (20.10 g, 66.70 mmol), iridium chloride (11.75 g, 33.32 mmol), ethoxyethanol (300 mL), and distilled water (100 mL) were mixed together, and the mixed solution was stirred under reflux for 24 hours. The reaction temperature was lowered to room temperature, and a solid produced therefrom was separated by filtration. A filtrate was sufficiently washed by using water, methanol, and hexane in the stated order, and a solid obtained therefrom was dried in a vacuum oven, thereby obtaining Compound L13(2) (19.00 g, 69%).
Compound L13(2) (19.00 g, 11.48 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (10.56 g, 57.40 mmol), Na2CO3 (12.17 g, 114.80 mmol), and ethoxyethanol (300 mL) were mixed together, and the mixed solution was stirred for 24 hours. A mixture obtained therefrom was filtered, and a filtered solid was sufficiently washed by using methanol and hexane, and purified by using column chromatography under conditions of dichloromethane:n-hexane=1:1 (v/v), thereby obtaining Compound 13 (13.00 g, 55%). Compound 13 was identified by mass spectrometry and HPLC.
HRMS(MALDI) calcd for C53H48F2IrN2O2: m/z 975.19, Found: 975.20.
4-chloro-7-fluorobenzo[f]isoquinoline (19.21 g, 82.95 mmol), (3,5-dimethylphenyl)boronic acid (14.93 g, 99.54 mmol), Pd(PPh3)4 (4.80 g, 4.15 mmol), K2CO3 (34.38 g, 248.85 mmol), THF (200 mL), and distilled water (50 mL) were mixed together, and the mixed solution was stirred under reflux for 18 hours. Then, the reaction temperature was lowered to room temperature, and an extraction process was performed thereon by using MC. An organic layer extracted therefrom was dried by adding MgSO4 thereto to remove moisture, and then, filtered. A solvent was reduced from a filtrate under reduced pressure, and a residue was purified by using column chromatography under conditions of EA:hexane=1:5, thereby obtaining 20.10 g (80%) of Compound L16(1).
MALDI-TOFMS (m/z): C21H16FN (M+) 301.36.
Compound L16(1) (20.10 g, 66.70 mmol), iridium chloride (11.75 g, 33.32 mmol), ethoxyethanol (300 mL), and distilled water (100 mL) were mixed together, and the mixed solution was stirred under reflux for 24 hours. The reaction temperature was lowered to room temperature, and a solid produced therefrom was separated by filtration. A filtrate was sufficiently washed by using water, methanol, and hexane in the stated order, and a solid obtained therefrom was dried in a vacuum oven, thereby obtaining Compound L16(2) (19.00 g, 69%).
Compound L16(2) (19.00 g, 11.48 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (10.56 g, 57.40 mmol), Na2CO3 (12.17 g, 114.80 mmol), and ethoxyethanol (300 mL) were mixed together, and the mixed solution was stirred for 24 hours. A mixture obtained therefrom was filtered, and a filtered solid was sufficiently washed by using methanol and hexane, and purified by using column chromatography under conditions of dichloromethane:n-hexane=1:1 (v/v), thereby obtaining 16 (13.00 g, 55%). Compound 16 was identified by mass spectrometry and HPLC.
HRMS(MALDI) calcd for C53H48F2IrN2O2: m/z 975.19, Found: 975.20.
HOMO and LUMO energy levels of Compounds 1 to 6, 10, 13, 16, A to D and E1 to E3 were evaluated according to the method in Table 2. Results thereof are shown in Table 3.
Compound H52 and Compound 1 were co-deposited at a vacuum pressure of 10−7 torr and at a weight ratio of 98:2 to produce a 40 nm-thick film.
The PLQY of Compound 1 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). The results thereof are shown in Table 4.
The PLQY of each of Compounds 2 to 6, 10, 13, 16, A to D and E1 to E3 were performed, and the results thereof are shown in Table 4.
As shown in Table 4, Compounds 1 to 6, 10, 13 and 16 were found to have excellent PLQY (in film) compared with Compounds A to D and E1 to E3.
A quartz substrate washed with chloroform and pure water was prepared, and then, the materials that are shown in Table 5 were vacuum (co)-deposited under a vacuum pressure of 10−7 torr to prepare Films 1 to 6, 10, 13, 16, A to D and E1 to E3 each having a thickness of 50 nanometers (nm).
Each of PL spectra of the prepared Films 1 to 6, 10, 13, 16, A to D and E1 to E3 was evaluated at room temperature by using a time-resolved photoluminescence (TRPL) measurement system, FluoTime 300 (available from PicoQuant), and a pumping source, PLS340 (available from PicoQuant, excitation wavelength=340 nm, spectral width=20 nm). Then, a wavelength of the main peak in each PL spectrum was determined, and upon photon pulses (pulse width=500 picoseconds, ps) applied to the film by PLS340, the number of photons emitted at the wavelength of the main peak for each film was repeatedly measured over time by time-correlated single photon counting (TCSPC), thereby obtaining TRPL curves available for the sufficient fitting. Based on the results obtained therefrom, two or more exponential decay functions were set forth for the fitting, thereby obtaining Tdecay(Ex), i.e., a decay time, for Films 1 to 6, 10, 13, 16, A to D and E1 to E3. The results thereof are shown in Table 5. The functions used for the fitting are as described in Equation 1, and a decay time Tdecay having the largest value among values for each of the exponential decay functions used for the fitting was taken as Tdecay(Ex), i.e., a decay time. Here, during the same measurement time as the measurement time for obtaining TRPL curves, the same measurement was repeated once more in a dark state (i.e., a state where a pumping signal incident on each of the films was blocked), thereby obtaining a baseline or a background signal curve available as a baseline for the fitting:
As shown in Table 5, Compounds 1 to 6, 10, 13 and 16 were found to have excellent decay time compared with Compounds A to D and E1 to E3.
The ITO-patterned glass substrate as an anode was cut into a size of 50 mm×50 mm×0.5 mm, ultrasonically cleaned with isopropyl alcohol and pure water, each for 5 minutes, and then irradiated with ultraviolet light for 30 minutes and cleaned by exposure to ozone. Then, the resultant substrate was mounted on a vacuum deposition apparatus.
HT3 and F6TCNNQ were vacuum co-deposited on the ITO anode at the weight ratio of 98:2 to form a hole injection layer having a thickness of 100 Å, HT3 was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 1350 Å, and then, HT21 was vacuum-deposited on the hole transport layer to form an electron blocking layer having a thickness of 300 Å.
Then, H52 (host) and Compound 1 (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.
Then, 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, and 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 1000 Å, thereby completing the manufacture of an organic light-emitting device having the structure of ITO (1500 Å) /HT3+F6TCNNQ (2 wt %) (100 Å)/HT3 (1350 Å)/HT21 (300 Å)/H52+Compound 1 (2 wt %) (400 Å)/ET3+ET-D1 (50%) (350 Å)/ET-D1 (10 Å)/Al(1000 Å).
Organic light-emitting devices were manufactured in substantially the same manner as in Example 1, except that the compounds shown in Table 6 were used instead of Compound 1 as a dopant in the formation of an emission layer. Evaluation Example 4: Evaluation of characteristics of organic light-emitting device
The driving voltage, current density, maximum of external quantum efficiency (Max EQE), roll-off ratio, FWHM of the emission peak in the EL spectrum, color-coordinate, and/or lifespan (LT97) of the organic light-emitting devices manufactured in Examples 1 to 9 and Comparative Examples A to D and E1 to E3 were evaluated. The results thereof are shown in Tables 6 and 7. A Keithley 2400 current voltmeter and a luminance meter (Minolta Cs-1000A) were used in the evaluation. The lifespan (LT97) refers to time required for the initial luminance of 3,500 nit of the organic light-emitting device to reduce by 97% and expressed as a relative value (%). The roll-off ratio was calculated by Equation 20:
Roll-off ratio={1−(efficiency (at 3,500 nit)/maximum luminescence efficiency)}×100% Equation 20
Referring to Tables 6 and 7, the organic light-emitting device of Examples 1 to 9 were found to have excellent driving voltage, excellent external quantum efficiency, excellent roll-off ratio, and excellent lifespan characteristics compared with Comparative Examples A to D and E1 to E3, with emitting a red light having a relatively narrow FWHM.
As apparent from the foregoing description, the organometallic compound may have excellent electrical characteristics and stability. Thus, an electronic device, e.g., an organic light-emitting device, including the organometallic compound may have improved driving voltage, improved external quantum emission efficiency, improved roll-off ratio, improved lifespan and relatively narrow FWHM of an emission peak of an EL spectrum. Further, a diagnostic composition that includes the organometallic compound may have a high diagnostic efficiency, because the organometallic compound is excellent in phosphorescent emission characteristics.
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 |
|---|---|---|---|
| 10-2019-0037212 | Mar 2019 | KR | national |
| 10-2019-0136671 | Oct 2019 | KR | national |
This is a continuation application of U.S. application Ser. No. 16/669,772, filed Oct. 31, 2019, which claims priority to and the benefit of Korean Patent Applications Nos. 10-2019-0037212, filed on Mar. 29, 2019, and 10-2019-0136671, filed on Oct. 30, 2019, in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. § 119, the contents of which are incorporated herein in their entirety by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16669772 | Oct 2019 | US |
| Child | 18210212 | US |
