Patent Application
20200083458
This application claims priority to Korean Patent Application No. 10-2018-0100569, filed on Aug. 27, 2018, in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. § 119, the content of which is incorporated herein in its entirety by reference.
One or more embodiments relate to a heterocyclic compound and an organic light-emitting device including the same.
Organic light-emitting devices (OLEDs) are self-emission devices that produce full-color images, and that also have wide viewing angles, high contrast ratios, short response times, and excellent characteristics in terms of brightness, driving voltage, and response speed, compared to the devices in the art.
In an example, an organic light-emitting device includes an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer includes an emission layer. A hole transport region may be disposed between the anode and the emission layer, and an electron transport region may be disposed between the emission layer and the cathode. Holes provided from the anode may move toward the emission layer through the hole transport region, and electrons provided from the cathode may move toward the emission layer through the electron transport region. Carriers, such as holes and electrons, recombine in the emission layer to produce excitons. These excitons transit from an excited state to a ground state, thereby generating light.
Various types of organic light emitting devices are known. However, there still remains a need in OLEDs having low driving voltage, high efficiency, high brightness, and long lifespan.
Aspects of the present disclosure provide a novel heterocyclic compound and an organic light-emitting device including the same.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments.
An aspect of the present disclosure provides a heterocyclic compound represented by Formula 1:
In Formula 1,
X1 may be N or C(R1), X2 may be N or C(R2), and X3 may be N or C(R3), wherein i) one selected from X1 to X3 may be N, and the others thereof may not be N; or ii) each of X1 to X3 may not be N,
R1 to R3 may each independently be hydrogen, deuterium, a C1-C20 alkyl group, a C1-C20 alkyl group substituted with at least one deuterium, a C1-C20 alkoxy group, a C1-C20 alkoxy group substituted with at least one deuterium, or —Si(Q101)(Q102)(Q103),
L1 and L2 may each independently be selected from:
a single bond; and
a C5-C60 carbocyclic group, a pyridine group, and a π electron-rich C1-C10 heterocyclic group, each unsubstituted or substituted with at least one R10a,
L3 to L5 may each independently be selected from:
a single bond; and
a C5-C60 carbocyclic group and a C1-C60 heterocyclic group, each unsubstituted or substituted with at least one R10a,
a1 to a5 may each independently be an integer from 1 to 5, and
Ar1 and Ar2 may each independently be a group represented by Formula 3A, a group represented by Formula 3B, a group represented by Formula 3C, a group represented by Formula 3D, a group represented by Formula 3E, a group represented by Formula 3F, or a C6-C60 aryl group unsubstituted or substituted with at least one Z31:
In Formulae 3A to 3F,
ring A31 to ring A33 may each independently be a C5-C60 carbocyclic group or a π electron-rich C1-C60 heterocyclic group,
X51 may be a single bond, N(Z51a), C(Z51a)(Z51b), Si(Z51a)(Z51b), O, or S,
X54 may be N(Z54a), C(Z54a)(Z54b), Si(Z54a)(Z54b), O, or S,
X55 may be N or C(Z55),
X56 may be N or C(Z56),
X57 may be N or C(Z57),
Z31 to Z33, Z51a, Z51b, Z54a, Z54b, and Z55 to Z57 may each independently be selected from:
hydrogen, deuterium, a cyano group, a C1-C20 alkyl group, and a C1-C20 alkoxy group; and
a C5-C60 carbocyclic group, a pyridine group, and a π electron-rich C1-C60 heterocyclic group, each unsubstituted or substituted with at least one R10,
b31 to b33 may each independently be an integer from 0 to 10,
* indicates a binding site to a neighboring atom,
X11 to X13 may each independently be N or C(CN),
R4 and R5 may each independently be selected from hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, 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 C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C7-C60 arylalkyl group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted C2-C60 heteroarylalkyl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, and —Si(Q111)(Q112)(Q113),
R10a and R10b may each independently be deuterium, a cyano group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a (C1-C20 alkyl)phenyl group, a di(C1-C20 alkyl)phenyl group, a tri(C1-C20 alkyl)phenyl group, a (C6-C20 aryl)phenyl group, a di(C6-C20 aryl)phenyl group, a tri(C6-C20 aryl)phenyl group, a terphenyl group, a tetraphenyl group (or, a quaterphenyl group), a fluorenyl group, a (C1-C20 alkyl)fluorenyl group, a di(C1-C20 alkyl)fluorenyl group, a tri(C1-C20 alkyl)fluorenyl group, a (C6-C20 aryl)fluorenyl group, a di(C6-C20 aryl)fluorenyl group, a tri(C6-C20 aryl)fluorenyl group, a carbazolyl group, a (C1-C20 alkyl)carbazolyl group, a di(C1-C20 alkyl)carbazolyl group, a tri(C1-C20 alkyl)carbazolyl group, a (C6-C20 aryl)carbazolyl group, a di(C6-C20 aryl)carbazolyl group, a tri(C6-C20 aryl)carbazolyl group, a dibenzofuranyl group, a (C1-C20 alkyl)dibenzofuranyl group, a di(C1-C20 alkyl)dibenzofuranyl group, a tri(C1-C20 alkyl)dibenzofuranyl group, a (C6-C20 aryl)dibenzofuranyl group, a di(C6-C20 aryl)dibenzofuranyl group, a tri(C6-C20 aryl)dibenzofuranyl group, a dibenzothiophenyl group, a (C1-C20 alkyl)dibenzothiophenyl group, a di(C1-C20 alkyl)dibenzothiophenyl group, a tri(C1-C20 alkyl)dibenzothiophenyl group, a (C6-C20 aryl)dibenzothiophenyl group, a di(C6-C20 aryl)dibenzothiophenyl group, a tri(C6-C20 aryl)dibenzothiophenyl group, or —Si(Q121)(Q122)(Q123),
at least one substituent of 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-C60 cycloalkyl group, the substituted C1-C60 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C1-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C7-C60 arylalkyl group, the substituted C1-C60 heteroaryl group, the substituted C1-C60 heteroaryloxy group, the substituted C1-C60 heteroarylthio group, the substituted C2-C60 heteroarylalkyl group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may be selected from:
deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, 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, and a C1-C60 alkoxy group;
a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, and a C1-C60 alkoxy group, each substituted with at least one selected from deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, 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 C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C5-C60 aryl group, a C5-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, —N(Q11)(Q12), —Si(Q13)(Q14)(Q15), —B(Q16)(Q17), and —P(═O)(Q18)(Q19);
a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group;
a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group, each substituted with at least one selected from deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, 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 C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, —N(Q21)(Q22), —Si(Q23)(Q24)(Q25), —B(Q26)(Q27), and —P(═O)(Q28)(Q29); and
—N(Q31)(Q32), —Si(Q33)(Q34)(Q35), —B(Q38)(Q37), and —P(═O)(Q38)(Q39), and
Q101 to Q103, Q111 to Q113, Q121 to Q123, Q11 to Q19, Q21 to Q29, and Q31 to Q39 may each independently be selected from hydrogen, 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 C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a biphenyl group, a terphenyl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group.
Another aspect of the present disclosure 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,
wherein the organic layer includes an emission layer and the organic layer includes at least one heterocyclic 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 FIGURE which is a schematic diagram 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 of the present description. 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 in contact with the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
It will be understood that, although the terms first, second, third etc. may be used herein to describe various elements, components, regions, layers, and/or sections, these elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of the present embodiments.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The term “or” means “and/or.” It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this general inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
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.
“About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.
In an embodiment, a heterocyclic compound is provided. The heterocyclic compound according to an embodiment may be represented by Formula 1 below:
In Formula 1, X1 may be N or C(R1), X2 may be N or C(R2), and X3 may be N or C(R3), i) wherein one selected from X1 to X3 may be N, and the others thereof may not be N; or ii) each of X1 to X3 may not be N.
In an embodiment,
X1 may be C(R1), X2 may be C(R2), and X3 may be C(R3);
X1 may be N, X2 may be C(R2), and X3 may be C(R3); or
X1 may be C(R1), X2 may be N, and X3 may be C(R3), but embodiments of the present disclosure are not limited thereto.
R1 to R3 may each independently be hydrogen, deuterium, a C1-C20 alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), a C1-C20 alkyl group substituted with at least one deuterium, a C1-C20 alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a pentoxy group), a C1-C20 alkoxy group substituted with at least one deuterium, or —Si(Q101)(Q102)(Q103). Q101 to Q103 may each independently be the same as described herein.
In Formula 1,
L1 and L2 may each independently be selected from:
a single bond; and
a C5-C60 carbocyclic group, a pyridine group, and a π electron-rich C1-C10 heterocyclic group, each unsubstituted or substituted with at least one R10a, and
L3 to L5 may each independently be selected from:
a single bond; and
a C5-C60 carbocyclic group and a C1-C60 heterocyclic group, each unsubstituted or substituted with at least one R10a. R10a may be the same as described herein.
In an embodiment, L1 to L5 may each independently be selected from:
a single bond; and
a benzene group, a fluorene group, a pyridine group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, an acridine group, and a dihydroacridine group, each unsubstituted or substituted with least one R10a.
In one or more embodiments, L3 in Formula 1 may each independently be selected from a single bond and groups represented by Formulae 2-1 to 2-4, but embodiments of the present disclosure are not limited thereto:
In Formulae 2-1 to 2-4,
R11 to R13 may each independently be hydrogen, deuterium, or a C1-C10 alkyl group,
* indicate a binding site to a 6-membered ring on the left side in Formula 1, and
*′ indicates a binding site to a 6-membered ring on the right side in Formula 1.
a1 to a5 in Formula 1 respectively indicate the number of groups L1 to groups L5, and may each independently be an integer from 1 to 5. When a1 to a5 are two or more, two or more groups L1 to groups L5 may be identical to or different from each other, respectively. a1 to a5 may each independently be 1 or 2, but embodiments of the present disclosure are not limited thereto.
Ar1 and Ar2 may each independently be a group represented by Formula 3A, a group represented by Formula 3B, a group represented by Formula 3C, a group represented by Formula 3D, a group represented by Formula 3E, a group represented by Formula 3F, or a C6-C60 aryl group unsubstituted or substituted with at least one Z31:
In an embodiment, Ar1 and Ar2 in Formula 1 may be identical to each other.
In one or more embodiments, Ar1 and Ar2 in Formula 1 may be different from each other.
In one or more embodiments, each of at least one selected from Ar1 and Ar2 in Formula 1 may independently be selected from groups represented by Formulae 3A to 3C.
ring A31 to ring A33 in Formulae 3A to 3F may each independently be a C5-C60 carbocyclic group or a π electron-rich C1-C60 heterocyclic group.
For example, ring A31 to ring A33 may each independently be a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a chrysene group, an indene group, an indole group, a benzofuran group, a benzothiophene group, a benzosilole group, a fluorene group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, an acridine group, or a dihydroacridine group, but embodiments of the present disclosure are not limited thereto.
In Formulae 3A to 3F,
X51 may be a single bond, N(Z51a), C(Z51a)(Z51b), Si(Z51a)(Z51b), O, or S,
X54 may be N(Z54a), C(Z54a)(Z54b), Si(Z54a)(Z54b), O, or S,
X55 may be N or C(Z55),
X56 may be N or C(Z56), and
X57 may be N or C(Z57).
In an embodiment, in Formulae 3A and 3B, X51 may be a single bond, and X54 may be N(Z54a), O, or S, but embodiments of the present disclosure are not limited thereto.
In Formulae 3A to 3F, Z31 to Z33, Z51a, Z51b, Z54a, Z54b, and Z55 to Z57 may each independently be selected from:
hydrogen, deuterium, a cyano group, a C1-C20 alkyl group, and a C1-C20 alkoxy group; and
a C5-C60 carbocyclic group, a pyridine group, and a π electron-rich C1-C60 heterocyclic group, each unsubstituted or substituted with at least one R10b. R10b may be the same as described below.
For example, Z31 to Z33, Z51a, Z51b, Z54a, Z54b, and Z55 to Z57 may each independently be selected from:
hydrogen, deuterium, a cyano group, a C1-C20 alkyl group, and a C1-C20 alkoxy group; and
a phenyl group, a biphenyl group, a terphenyl group, a tetraphenyl group, a fluorenyl group, a dibenzocarbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a dibenzosilolyl group, an indenocarbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzosilolocarbazolyl group, an acridinyl group, and a dihydroacridinyl group, each unsubstituted or substituted with at least one R10b.
b31 to b33 respectively indicate the number of groups Z31 to groups Z33 and may each independently be an integer from 0 to 10 (for example, 0, 1, 2, 3, or 4). When b31 to b33 are two or more, two or more groups Z31 to groups Z33 may be identical to or different from each other, respectively. b31 to b33 are each independently 0, 1, or 2, but embodiments of the present disclosure are not limited thereto.
* in Formulae 3A to 3F indicates a binding site to a neighboring atom.
In an embodiment,
a ring represented by
in Formula 3A may be selected from groups represented by Formulae 3A-1 to 3A-49,
a ring represented by
in Formula 3B may be selected from groups represented by Formulae 3B-1 to 3B-40, and
a ring represented by
in Formula 3C may be a group represented by Formula 3C-1, but embodiments of the present disclosure are not limited thereto:
In Formulae 3A-1 to 3A-49, 3B-1 to 3B-40 and 3C-1, X51 and * may each independently be the same as described herein, X52 may be N(Z52a), C(Z52a)(Z52b), Si(Z52a)(Z52b), O, or S, X53 may be N(Z53a), C(Z53a)(Z53b), Si(Z53a)(Z53b), O, or S, and Z52a, Z52b, Z53a, and Z53b may each independently be the same as described in connection with Z51a.
In one or more embodiments, each of at least one selected from Ar1 and Ar2 may independently be selected from groups represented by Formulae 3G-1 to 3G-10:
In Formulae 3G-1 to 3G-10,
Z30a, to Z30f or may each independently be the same as described in connection with Z31, and
* indicates a binding site to a neighboring atom.
In Formula 1, X11 to X13 may each independently be N or C(CN).
In an embodiment, X11 to X13 may each independently be N.
In Formula 1, R4 and R5 may each independently be selected from hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, 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 C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C7-C60 aryl alkyl group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C10 heteroarylthio group, a substituted or unsubstituted C2-C60 heteroarylalkyl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, and —Si(Q111)(Q112)(Q113), wherein Q111 to Q113 may each independently be the same as described above.
For example, R4 and R5 may each independently be a phenyl group, a biphenyl group, a terphenyl group, a tetraphenyl group, a fluorenyl group, a dibenzocarbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a dibenzosilolyl group, an indenocarbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzosilolocarbazolyl group, an acridinyl group, and a dihydroacridinyl group, each unsubstituted or substituted with at least one R10c, wherein R10c may be the same as R10a described herein.
R10a and R10b may each independently be deuterium, a cyano group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a (C1-C20 alkyl)phenyl group, a di(C1-C20 alkyl)phenyl group, a tri(C1-C20 alkyl)phenyl group, a (C6-C20 aryl)phenyl group, a di(C6-C20 aryl)phenyl group, a tri(C6-C20 aryl)phenyl group, a terphenyl group, a tetraphenyl group, a fluorenyl group, a (C1-C20 alkyl)fluorenyl group, a di(C1-C20 alkyl)fluorenyl group, a tri(C1-C20 alkyl)fluorenyl group, a (C6-C20 aryl)fluorenyl group, a di(C6-C20 aryl)fluorenyl group, a tri(C6-C20 aryl)fluorenyl group, a carbazolyl group, a (C1-C20 alkyl)carbazolyl group, a di(C1-C20 alkyl)carbazolyl group, a tri(C1-C20 alkyl)carbazolyl group, a (C6-C20 aryl)carbazolyl group, a di(C6-C20 aryl)carbazolyl group, a tri(C6-C20 aryl)carbazolyl group, a dibenzofuranyl group, a (C1-C20 alkyl)dibenzofuranyl group, a di(C1-C20 alkyl)dibenzofuranyl group, a tri(C1-C20 alkyl)dibenzofuranyl group, a (C6-C20 aryl)dibenzofuranyl group, a di(C6-C20 aryl)dibenzofuranyl group, a tri(C6-C20 aryl)dibenzofuranyl group, a dibenzothiophenyl group, a (C1-C20 alkyl)dibenzothiophenyl group, a di(C1-C20 alkyl)dibenzothiophenyl group, a tri(C1-C20 alkyl)dibenzothiophenyl group, a (C6-C20 aryl)dibenzothiophenyl group, a di(C6-C20 aryl)dibenzothiophenyl group, a tri(C6-C20 aryl)dibenzothiophenyl group, or —Si(Q121)(Q122)(Q123), wherein Q122 to Q123 may each independently be the same as described above. The term “C1-C20 alkyl group” as used herein refers to a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group, and the term “C6-C20 aryl group” as used herein refers to a phenyl group, a naphthyl group, or a triphenylenyl group.
In an embodiment, R10a which may be included in L1 to L3 may not be a cyano group.
In one or more embodiments, in Formula 1,
Ar1 and Ar2 may each independently be a group represented by one selected from Formulae D′-1 to D′-7 and D001 to D279, and/or
a group represented by *-(L3)a3-*′ may be a single bond or a group represented by one selected from Formulae L-1 to L-5, and/or
may be represented by one selected from Formulae A1 to A38,
* in a group represented by
indicates a binding site to a neighboring atom, and
in a group represented by *-(L3)a3-*′, * indicates a binding site to a 6-membered ring on the left side in Formula 1, and *′ indicates a binding site to a 6-membered ring on the right side in Formula 1, but embodiments of the present disclosure are not limited thereto:
In the formulae above, * and *′ each indicate a binding site to a neighboring atom.
In one or more embodiments, the heterocyclic compound may be one selected from Compounds 1 to 1078:
Ar1 and Ar2 in Formula 1 are located at “para” positions each other as can be confirmed in Formula 1. Therefore, an overlap density of the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) in a molecule of the heterocyclic compound represented by Formula 1 increases, and a value of an oscillator strength (f) increases. As a result, the luminescence efficiency of an electronic device, for example, an organic light-emitting device, which includes the heterocyclic compound, may be improved.
Also, in Formula 1, X1 may be N or C(R1), X2 may be N or C(R2), X3 may be N or C(R3), R1 to R3 may each independently be hydrogen, deuterium, a C1-C20 alkyl group, a C1-C20 alkyl group substituted with at least one deuterium, a C1-C20 alkoxy group, a C1-C20 alkoxy group substituted with at least one deuterium, or —Si(Q101)(Q102)(Q103). That is, in Formula 1, R1 to R3 may each be a non-cyclic group. Therefore, since the heterocyclic compound represented by Formula 1 may have a relatively low deposition temperature, an electronic device, for example, an organic light-emitting device, which includes the heterocyclic compound, may have excellent lifespan characteristics.
Furthermore, in Formula 1, X11 to X13 may each independently be N or C(CN). Therefore, since the heterocyclic compound represented by Formula 1 has a relatively small decay time (Tau), an electronic device, for example, an organic light-emitting device, which includes the heterocyclic compound, may have excellent lifespan characteristics.
The heterocyclic compound represented by Formula 1 may have a singlet energy level (expressed in electron volts, eV) in a range of about 2.5 eV to about 3.0 eV.
Also, a difference (being an absolute value) between a singlet energy level (eV) of the heterocyclic compound and a triplet energy level (eV) of the heterocyclic compound may be in a range of about 0 eV to about 0.5 eV. Therefore, the heterocyclic compound represented by Formula 1 may emit delayed fluorescence having high efficiency and/or high luminance.
When a difference between a singlet energy level (eV) of the heterocyclic compound represented by Formula 1 and a triplet energy level (eV) of the heterocyclic compound represented by Formula 1 is within this range, up-conversion from a triplet state to a singlet state is effectively performed, and the heterocyclic compound may emit delayed fluorescence having high efficiency.
The singlet energy level and the triplet energy level are evaluated by using a density functional theory (DFT) method (for example, a DFT method of Gaussian program) structurally optimized at a level of B3LYP/6-31G(d,p).
Synthesis methods of the heterocyclic compound represented by Formula 1 may be recognized by those of ordinary skill in the art by referring to Synthesis Examples.
Another aspect of the present disclosure may provide 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, wherein the organic layer includes an emission layer, and wherein the organic layer includes at least one heterocyclic compound represented by Formula 1.
For example, the emission layer may include the heterocyclic compound represented by Formula 1. The emission layer including the heterocyclic compound may be an emission layer according to a first embodiment or a second embodiment.
The heterocyclic compound represented by Formula 1, which is included in the emission layer, may emit fluorescence (for example, thermally activated delayed fluorescence).
For example, the emission layer may consist of the heterocyclic compound represented by Formula 1.
In an embodiment, the emission layer may include a host and a dopant. The dopant may include the heterocyclic compound represented by Formula 1. An amount of the host may be larger than an amount of the dopant. The host and the dopant may be different from each other.
The heterocyclic compound included in the emission layer may act as an emitter (for example, a thermally activated delayed fluorescence emitter).
The emission layer may not include a phosphorescent dopant. That is, the emission layer may not include a compound capable of emitting light in accordance to a phosphorescence emission mechanism. Therefore, the emission layer may not include a phosphorescence emitter and does not substantially emit phosphorescence. Instead, the emission layer may be a “delayed fluorescence” emission layer that emits delayed fluorescence by transiting a triplet exciton of the heterocyclic compound represented by Formula 1 from a triplet state to a singlet state by reverse intersystem crossing (RISC), followed by transiting to a ground state.
As described above, the “delayed fluorescence” emission layer used herein is distinctly different from a “phosphorescence” emission layer that includes a phosphorescence emitter (for example, a transition metal (for example, an iridium or a platinum) complex) as a dopant and causes an energy transfer from a host to a phosphorescence emitter, without a process of emitting delayed fluorescence by transiting a triplet exciton of the heterocyclic compound represented by Formula 1 from a triplet state to a singlet state by reverse intersystem crossing (RISC), followed by transiting to a ground state.
The emission layer may include a host and a dopant. The host may include the heterocyclic compound represented by Formula 1. An amount of the host may be larger than an amount of the dopant. The host and the dopant may be different from each other. The heterocyclic compound included in the emission layer may serve to transfer energy to the dopant, instead of being an emitter.
The emission layer (for example, the emission layer according to the first embodiment or the second embodiment) may emit red light, green light, or blue light. For example, the emission layer may emit blue light, but embodiments of the present disclosure are not limited thereto.
A ratio of a delayed fluorescence component emitted from the heterocyclic compound represented by Formula 1 to a total emission component emitted from the emission layer may be 90% or more, 92% or more, 94% or more, 96% or more, or 98% or more, but embodiments of the present disclosure are not limited thereto.
The host in the emission layer in the first embodiment may include at least one selected from a first material and a second material, in addition to the heterocyclic compound represented by Formula 1, and the host in the emission layer in the second embodiment may further include at least one selected from a first material and a second material.
the first material may include at least one π electron-rich cyclic group, and may not include an electron transport moiety,
the second material may include at least one π electron-rich cyclic group and at least one electron transport moiety, and
the electron transport moiety may be selected from a cyano group, a π electron-depleted nitrogen-containing cyclic group, and a group represented by one selected from the following formulae:
In the formulae, *, *′, and *″ each indicate a binding site to a neighboring atom.
For example, i) the host may consist of at least one compound of the first material, ii) the host may consist of two different compounds of the first material, iii) the host may consist of one compound of the second material, iv) the host may consist of two different compounds of the second material, or v) the host may consist of at least one compound of the first material and at least one compound of the second material. In this manner, the host may be variously modified.
The term “π electron-depleted nitrogen-containing cyclic group” as used herein refers to a cyclic group having at least one *—N=*′ moiety. For example, the π electron-depleted nitrogen-containing cyclic group may be an imidazole group, a pyrazole group, a thiazole group, an isothiazole group, an oxazole group, an isoxazole group, a pyridine group, a pyrazine group, a pyridazine group, a pyrimidine group, an indazole group, a purine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a benzoisoquinoline group, a phthalazine group, a naphthyridine group, a quinoxaline group, a benzoquinoxaline group, a quinazoline group, a cinnoline group, a phenanthridine group, a phenanthroline group, a phenazine group, a benzimidazole group, an isobenzothiazole group, a benzoxazole group, an isobenzoxazole group, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, a thiadiazole group, an imidazopyridine group, an imidazopyrimidine group, an azaindene group, an azaindole group, an azabenzofuran group, an azabenzothiophene group, an azabenzosilole group, an azafluorene group, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, or a cyclic group condensed with any one of the foregoing groups.
The π electron-rich cyclic group may be, for example, a benzene group, a heptalene group, an indene group, a naphthalene group, an azulene group, a heptalene group, an indacene group, acenaphthylene group, a fluorene group, a spiro-bifluorene group, a benzofluorene group, a dibenzofluorene group, a phenalene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a naphthacene group, a picene group, a perylene group, a pentacene group, a hexacene group, a pentaphene group, a rubicene group, a coronene group, an ovalene group, a pyrrole group, an isoindole group, an indole group, a furan group, a thiophene group, a benzofuran group, a benzothiophene group, a benzosilole group, a benzocarbazole group, a dibenzocarbazole group, a dibenzofuran group, a dibenzothiophene group, a dibenzothiophene sulfone group, a carbazole group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, a triindolobenzene group, an acridine group, or a dihydroacridine group, but embodiments of the present disclosure are not limited thereto.
The first material and the second material may be different from each other.
In an embodiment, the first material and the second material may each independently include at least one carbazole group.
In one or more embodiments, the first material and the second material may each independently include at least two carbazole groups, but embodiments of the present disclosure are not limited thereto.
In one or more embodiments, the second material may include at least one cyano group (for example, one, two, three, or four cyano groups).
In one or more embodiments, the first material may include a cyano group-free benzene group and a cyano group-free carbazole group.
In one or more embodiments, the second material may include at least one cyano group and at least one carbazole ring.
In one or more embodiments, the second material may include at least one of a cyano group-containing benzene group and a cyano group-containing carbazole group.
In one or more embodiments,
an absolute value of a lowest unoccupied molecular orbital (LUMO) energy level of the first material may be in a range of about 0.90 eV to about 1.20 eV,
an absolute value of a HOMO energy level of the first material may be in a range of about 5.20 eV to about 5.60 eV,
an absolute value of a LUMO energy level of the second material may be in a range of about 1.80 eV to about 2.20 eV,
an absolute value of a HOMO energy level of the second material may be in a range of about 5.40 eV to about 6.00 eV, but embodiments of the present disclosure are not limited thereto.
When the HOMO and LUMO energy level ranges of the first material and the second material are within these ranges, charge and/or exciton movement and energy flow in the emission layer are smooth, and an organic light-emitting device having high luminescence efficiency and long lifespan may be implemented.
In one or more embodiments, the first material may include at least one selected from a compound represented by Formula H-1(1), a compound represented by Formula H-1(2), and a compound represented by Formula H-1(3):
In Formulae H-1(1) to H-1(3), ring A41 to ring A44 may each independently be a benzene group, a naphthalene group, an indene group, an indole group, a benzofuran group, a benzothiophene group, a benzosilole group, a fluorene group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, or a dibenzosilole group.
For example, ring A41 to ring A44 may each independently be a benzene group, a fluorene group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, or a dibenzosilole group, wherein at least one of ring A41 and ring A42 may be a benzene group, and at least one of ring A43 and ring A44 may be a benzene group.
In Formulae H-1(1) to H-1(3),
X41 may be N-[(L411)c411-Z411], C(Z415)(Z416), O, or S,
X42 may be a single bond, N-[(L412)c412-Z412], C(Z417)(Z418), O, or S,
X43 may be N-[(L413)c413-Z413], C(Z419)(Z420), O, or S, and
X44 may be a single bond, N-[(L414)c414-Z414], C(Z421)(Z422), O, or S.
L401 and L411 to L414 may each independently be selected from:
a single bond; and
a π electron-rich cyclic group unsubstituted or substituted with at least one R10d (for example, a benzene group, a heptalene group, an indene group, a naphthalene group, an azulene group, a heptalene group, an indacene group, acenaphthylene group, a fluorene group, a spiro-bifluorene group, a benzofluorene group, a dibenzofluorene group, a phenalene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a naphthacene group, a picene group, a perylene group, a pentacene group, a hexacene group, a pentaphene group, a rubicene group, a coronene group, an ovalene group, a pyrrole group, an isoindole group, an indole group, a furan group, a thiophene group, a benzofuran group, a benzothiophene group, a benzosilole group, a benzocarbazole group, a dibenzocarbazole group, a dibenzofuran group, a dibenzothiophene group, a dibenzothiophene sulfone group, a carbazole group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, a triindolobenzene group, an acridine group, or a dihydroacridine group, each unsubstituted or substituted with at least one R10d).
Each of a401 and c411 to c414 indicates the number of each of L401 and L411 to L414, respectively, and may independently be an integer from 1 to 10 (for example, an integer from 1 to 5). When a401 is two or more, two or more of groups L401 may be identical to or different from each other, when c411 is two or more, two or more of groups L411 may be identical to or different from each other, when c412 is two or more, two or more of groups L412 may be identical to or different from each other, when c413 is two or more, two or more of groups L413 may be identical to or different from each other, and when c414 is two or more, two or more of groups L414 may be identical to or different from each other.
Z41 to Z44 and Z411 to Z422 may each independently be selected from:
hydrogen, deuterium, a C1-C20 alkyl group, and a C1-C20 alkoxy group; and
a π electron-rich cyclic group unsubstituted or substituted with at least one R10d (for example, a phenyl group, a biphenyl group, a terphenyl group, a tetraphenyl group, a naphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthrenyl group, an anthracenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a pyrrolyl group, an isoindolyl group, an indolyl group, a furanyl group, a thiophenyl group, a benzofuranyl group, a benzothiophenyl group, a benzosilolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a dibenzosilolyl group, an indenocarbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzosilolocarbazolyl group, an acridinyl group, or a dihydroacridinyl group, each unsubstituted or substituted with at least one R10d).
Each of b41 to b44 indicates the number of each of Z41 to Z44, respectively, and may independently be 1, 2, 3, or 4.
R10d may be defined the same as R10a, but R10d is not a cyano group.
In an embodiment, in Formulae H-1(1) to H-1(3),
L401 and L411 to L414 may each independently be selected from:
a single bond; and
a benzene group, a fluorene group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, an acridine group, or a dihydroacridine group, each unsubstituted or substituted with at least one R10d,
Z41 to Z44 and Z411 to Z422 may each independently be selected from:
hydrogen, deuterium, a C1-C10 alkyl group, and a C1-C10 alkoxy group; and
a phenyl group, a biphenyl group, a terphenyl group, a tetraphenyl group, a fluorenyl group, a dibenzocarbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a dibenzosilolyl group, an indenocarbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzosilolocarbazolyl group, an acridinyl group, or a dihydroacridinyl group, each unsubstituted or substituted with at least one R10d,
but embodiments of the present disclosure are not limited thereto.
In an embodiment, the first material may include at least one compound selected from Compounds H1 to H32, but embodiments of the present disclosure are not limited thereto:
In an embodiment, the first material may not be an amine-based compound.
In one or more embodiments, the first material may not be 1,3-bis(9-carbazolyl)benzene (mCP), tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP), 3,3-bis(carbazo-9-yl)biphenyl (mCBP), N,N′-di(1-naphthyl)-N, N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB), 4,4′,4″-tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), or N, N′-bis(3-methylphenyl)-N, N′-diphenylbenzidine (TPD).
In one or more embodiments, the second material may include a compound represented by Formula E-1:
[Ar301]xb11-[(L301)xb1-R301]xb21. Formula E-1
In Formula E-1,
Ar301 may be selected from a substituted or unsubstituted C5-C60 carbocyclic group and a substituted or unsubstituted C1-C60 heterocyclic group,
xb11 may be 1, 2, or 3,
L301 may be selected from a single bond, a group represented by one selected from the following formulae, a substituted or unsubstituted C5-C60 carbocyclic group, and a substituted or unsubstituted C1-C60 heterocyclic group, wherein *, *′, and *″ in the following formulae each indicate a binding site to a neighboring atom,
xb1 may be an integer from 1 to 5,
R301 may be selected from hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, 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 C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C7-C60 arylalkyl group, a substituted or unsubstituted C1-C10 heteroaryl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C10 heteroarylthio group, a substituted or unsubstituted C2-C60 heteroarylalkyl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —Si(Q301)(Q302)(Q303), —N(Q301)(Q302), —B(Q301)(Q302), —C(═O)(Q301), —S(═O)2(Q301), —S(═O)(Q301), —P(═O)(Q301)(Q302), and —P(═S)(Q301)(Q302),
xb21 may be an integer from 1 to 5, and
Q301 to Q303 may each independently be selected from a C1-C10 alkyl group, a C1-C10 alkoxy group, a phenyl group, a biphenyl group, a terphenyl group, and a naphthyl group, and satisfies one of Condition 1 to Condition 3:
Condition 1
Each of at least one selected from Ar301, L301, and R301 in Formula E-1 may independently include a π electron-depleted nitrogen-containing cyclic group
Condition 2
At least one L301 in Formula E-1 may include a group represented by one selected from the following formulae:
Condition 3
At least one R301 in Formula E-1 may be selected from a cyano group, —S(═O)2(Q301), —S(═O)(Q301), —P(═O)(Q301)(Q302), and —P(═S)(Q301)(Q302).
In one or more embodiments, the second material may include at least one selected from a compound represented by Formula E-1(1), a compound represented by Formula E-1(2), and a compound represented by Formula E-1(3):
In Formulae E-1(1) to E-1(3),
ring A1, ring A2, ring A5, and ring A6 may each independently be selected from a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a cyclopentadiene group, a thiophene group, a furan group, 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, a dibenzothiophene 5,5-dioxide group, an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, and a phenanthroline group.
For example, ring A1, ring A2, ring A5, and ring A6 may each independently be selected from a benzene group, a carbazole group, a fluorene group, a dibenzothiophene group, and a dibenzofuran group.
In Formulae E-1(1) to E-1(3), Z1 to Z6 may each independently be selected from:
hydrogen, deuterium, and a cyano group; or
a C1-C20 alkyl group, a phenyl group, a biphenyl group, a terphenyl group, a dibenzofuranyl group, and a dibenzothiophenyl group, each unsubstituted or substituted with at least one selected from deuterium, a cyano group, a C1-C20 alkyl group, a phenyl group, and a biphenyl group.
For example, in Formulae E-1(1) to E-1(3), Z1 to Z6 may each independently be selected from:
hydrogen, deuterium, and a cyano group; or
a C3-C10 alkyl group, a phenyl group, a biphenyl group, a terphenyl group, a dibenzofuranyl group, and a dibenzothiophenyl group, each unsubstituted or substituted with at least one selected from deuterium, a cyano group, a C3-C10 alkyl group, a phenyl group, and a biphenyl group.
In an embodiment, in Formulae E-1(1) to E-1(3), Z1 to Z6 may each independently be selected from:
hydrogen, deuterium, and a cyano group; or
an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, a sec-pentyl group, a tert-pentyl group, a phenyl group, a biphenyl group, and a terphenyl group, each unsubstituted or substituted with at least one selected from deuterium, a cyano group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, a sec-pentyl group, a tert-pentyl group, a phenyl group, and a biphenyl group.
In Formulae E-1(1) to E-1(3), b1 to b6 respectively indicate the number of groups Z1 to groups Z6, and may each independently be 1, 2, or 3. When b1 to b6 are two or more, two or more groups Z1 to groups Z6 may be identical to or different from each other.
In an embodiment, in Formulae E-1(1) to E-1(3), at least one selected from groups Z1 in the number of b1, groups Z2 in the number of b2, groups Z3 in the number of b3, groups Z4 in the number of b4, groups Z5 in the number of b5, and groups Re in the number of b6 may be a cyano group.
For example, the number of cyano groups included in the compound represented by Formula E-1(1), the number of cyano groups included in the compound represented by Formula E-1(2), and the number of cyano groups included in the compound represented by Formula E-1(3) may each independently be 1, 2, or 3, but embodiments of the present disclosure are not limited thereto.
In an embodiment, in Formulae E-1(1) to E-1(3),
at least one selected from groups Z1 in the number of b1 and groups Z2 in the number of b2 may be a cyano group,
at least one selected from groups Z3 in the number of b3 and groups Z4 in the number of b4 may be a cyano group,
at least one selected from groups Z5 in the number of b5 and groups Z6 in the number of b6 may be a cyano group,
at least one selected from groups Z1 in the number of b1 and groups Z2 in the number of b2 may be a cyano group, and at least one selected from groups Z3 in the number of b3 and groups Z4 in the number of b4 may be a cyano group,
at least one selected from groups Z1 in the number of b1 and groups Z2 in the number of b2 may be a cyano group, and at least one selected from groups Z5 in the number of b5 and groups Z6 in the number of b6 may be a cyano group,
at least one selected from groups Z3 in the number of b3 and groups Z4 in the number of b4 may be a cyano group, and at least one selected from groups Z5 in the number of b5 and groups Z6 in the number of b6 may be a cyano group, or
at least one selected from groups Z1 in the number of b1 and groups Z2 in the number of b2 may be a cyano group, at least one selected from groups Z3 in the number of b3 and groups Z4 in the number of b4 may be a cyano group, and at least one selected from groups Z5 in the number of b5 and groups Z6 in the number of b6 may be a cyano group.
In Formulae E-1(1) to E-1(3), X21 and X22 may each independently be O or S, and m may be 0 or 1.
In an embodiment, a group represented by
in Formulae E-1(1) to E-1(3) may be one selected from groups represented by Formulae PO1 to PO25, PM1 to PM25, PP1 to PP18, MO1 to MO37, MM1 to MM37, MP1 to MP25, OO1 to OO37, OM1 to OM37, OP1 to OP25, O1 to O16, M1 to M16, and P1 to P9:
In Formulae PO1 to PO25, PM1 to PM25, PP1 to PP18, MO1 to MO37, MM1 to MM37, MP1 to MP25, OO1 to OO37, OM1 to OM37, OP1 to OP25, O1 to O16, M1 to M16, and P1 to P9, Z10 to Z10 may each independently be the same as described in connection with Z3 and Z4, and * and * each indicate a binding site to a neighboring atom.
In an embodiment, in Formulae PO1 to PO25, PM1 to PM25, PP1 to PP18, MO1 to MO37, MM1 to MM37, MP1 to MP25, OO1 to OO37, OM1 to OM37, OP1 to OP25, O1 to O16, M1 to M16 and P1 to P9, Z10 to Z19 may not be a cyano group.
In one or more embodiments, in Formulae PO1 to PO25, PM1 to PM25, PP1 to PP18, MO1 to MO37, MM1 to MM37, MP1 to MP25, OO1 to OO37, OM1 to OM37, OP1 to OP25, O1 to O16, M1 to M16, and P1 to P9, Z10 to Z19 may each independently be selected from:
hydrogen, deuterium, or a cyano group; or
a C1-C20 alkyl group, a phenyl group, a biphenyl group, a terphenyl group, a dibenzofuranyl group, or a dibenzothiophenyl group, each unsubstituted or substituted with at least one selected from deuterium, a cyano group, a C1-C20 alkyl group, a phenyl group, and a biphenyl group.
In an embodiment, the second material may include at least one compound selected from Compounds E1 to E8, but embodiments of the present disclosure are not limited thereto:
A difference between a triplet energy level (eV) of the host and a triplet energy level (eV) of the heterocyclic compound represented by Formula 1 may be in a range of about 0.2 eV to about 0.5 eV. While not wishing to be bound by theory, it is understood that when the difference between the triplet energy level (eV) of the host and the triplet energy level (eV) of the heterocyclic compound represented by Formula 1 is within this range, it is possible to prevent energy of the triplet exciton generated in the heterocyclic compound represented by Formula 1 from leaking toward the host in the emission layer, thereby implementing efficient light emission. An activated excitation energy level of the host is suppressed, thereby implementing long lifespan driving of the organic light-emitting device.
The triplet energy level is evaluated by using a DFT method (for example, a DFT method of Gaussian program) structurally optimized at a level of B3LYP/6-31G(d,p).
In the first embodiment, an amount of the heterocyclic compound represented by Formula 1 in the emission layer may be in a range of about 0.01 parts by weight to about 30 parts by weight based on 100 pars by weight of the host, but embodiments of the present disclosure are not limited thereto. While not wishing to be bound by theory, it is understood that when the amount of the heterocyclic compound represented by Formula 1 is within this range, a high-quality organic light-emitting device may be implemented without concentration quenching.
The FIGURE a schematic view of an organic light-emitting device 10 according to an embodiment. Hereinafter, the structure of an organic light-emitting device according to an embodiment and a method of manufacturing an organic light-emitting device according to an embodiment will be described in connection with the FIGURE. The organic light-emitting device 10 includes a first electrode 11, an organic layer 15, and a second electrode 19, which are sequentially stacked.
A substrate may be additionally disposed 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.
The first electrode 11 may be formed by depositing or sputtering a material for forming the first electrode 11 on the substrate. The first electrode 11 may be an anode. The material for forming the first electrode 11 may be selected from materials with a high work function to facilitate hole injection. The first electrode 11 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. The material for forming the first electrode may be, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), and zinc oxide (ZnO). In one or more embodiments, magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), or magnesium-silver (Mg—Ag) may be used as the material for forming the first electrode.
The first electrode 11 may have a single-layered structure or a multi-layered structure including two or more layers. For example, the first electrode 11 may have a three-layered structure of ITO/Ag/ITO, but the structure of the first electrode 110 is not limited thereto.
The organic layer 15 may be disposed on the first electrode 11.
The organic layer 15 may include a hole transport region, an emission layer, and an electron transport region.
The hole transport region may be disposed between the first electrode 11 and the emission layer.
The hole transport region may include at least one selected from a hole injection layer, a hole transport layer, an electron blocking layer, and a buffer layer.
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, the hole injection layer may be disposed on the first electrode 11 by using one or more suitable methods selected from vacuum deposition, spin coating, casting, or Langmuir-Blodgett (LB) deposition.
When the hole injection layer is formed by vacuum deposition, the deposition conditions may vary according to a compound that is used to form the hole injection layer, and the structure and thermal characteristics of the hole injection layer. For example, the deposition conditions may include a deposition temperature of about 100° C. to about 500° C., a vacuum pressure of about 10−8 torr to about 10−3 torr, and a deposition rate of about 0.01 Angstroms per second (Å/sec) to about 100 Å/sec. However, the deposition conditions are not limited thereto.
When the hole injection layer is formed using spin coating, coating conditions may vary according to the material used to form the hole injection layer, and the structure and thermal properties of the hole injection layer. For example, a coating speed may be from about 2,000 revolutions per minute (rpm) to about 5,000 rpm, and a temperature at which a heat treatment is performed to remove a solvent after coating may be from about 80° C. to about 200° C. However, the coating conditions are not limited thereto.
Conditions for forming a hole transport layer and an electron blocking layer may be understood by referring to conditions for forming the hole injection layer.
The hole transport region may include at least one selected from m-MTDATA, TDATA, 2-TNATA, NPB, 13-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated-NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzene sulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrene sulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (PANI/CSA), polyaniline/poly(4-styrene sulfonate) (PANI/PSS), a compound represented by Formula 201 below, and a compound represented by Formula 202:
Ar101 and Ar102 in Formula 201 may each independently be selected from:
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 chrysenylene group, a naphthacenylene group, a picenylene group, a perylenylene group, and a pentacenylene group; and
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 chrysenylene group, a naphthacenylene group, a picenylene group, a perylenylene group, and a pentacenylene group, each substituted with at least one selected from deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C10 cycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkyl group, a C1-C10 heterocycloalkenyl group, a C5-C60 aryl group, a C5-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group.
In Formula 201, xa and xb may each independently be an integer from 0 to 5, or may be 0, 1, or 2. For example, xa may be 1 and xb may be 0, but embodiments of the present disclosure are not limited thereto.
R101 to R108, R111 to R119, and R121 to R124 in Formulae 201 and 202 may each independently be selected from:
hydrogen, 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-C10 alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and so on), and a C1-C10 alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and so on);
a C1-C10 alkyl group or a C1-C10 alkoxy group, each substituted with at least one selected from 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, and a phosphoric acid group or a salt thereof;
a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, and a pyrenyl group; and
a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, and a pyrenyl group, each substituted with at least one selected from 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-C10 alkyl group, or a C1-C10 alkoxy group,
but embodiments of the present disclosure are not limited thereto.
R109 in Formula 201 may be selected from:
a phenyl group, a naphthyl group, an anthracenyl group, and a pyridinyl group; and
a phenyl group, a naphthyl group, an anthracenyl group, and a pyridinyl group, each substituted with at least one selected from 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, and a pyridinyl group.
In an embodiment, the compound represented by Formula 201 may be represented by Formula 201A, but embodiments of the present disclosure are not limited thereto:
R10l, R111, R112, and R109 in Formula 201A are the same as described above.
For example, the compound represented by Formula 201, and the compound represented by Formula 202 may include Compounds HT1 to HT20, but embodiments of the present disclosure are not limited thereto:
A thickness of the hole transport region may be in a range of about 100 Angstroms (Å) to about 10,000 Å, for example, about 100 Å to about 1,000 Å. When the hole transport region includes a hole injection layer and a hole transport layer, the thickness of the hole injection layer may be in a range of about 100 Å to about 10,000 Å, and for example, about 100 Å to about 1,000 Å, and the thickness of the hole transport layer may be in a range of about 50 Å to about 2,000 Å, and for example, about 100 Å to about 1,500 Å. While not wishing to be bound by theory, it is understood that when the thicknesses of the hole transport region, the hole injection layer, and the hole transport layer are within these ranges, satisfactory hole transporting characteristics may be obtained without a substantial increase in driving voltage.
The hole transport region may further include, in addition to these materials, a charge-generation material for the improvement of conductive properties. The charge-generation material may be homogeneously or non-homogeneously dispersed in the hole transport region.
The charge-generation material may be, for example, a p-dopant. The p-dopant may be one selected from a quinone derivative, a metal oxide, and a cyano group-containing compound, but embodiments of the present disclosure are not limited thereto. Non-limiting examples of the p-dopant are a quinone derivative, such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4-TCNQ); a metal oxide, such as a tungsten oxide or a molybdenium oxide; and a cyano group-containing compound, such as Compound HT-D1 or Compound HT-D2 below, but are not limited thereto.
The hole transport region may include a buffer layer.
Also, the buffer layer may compensate for an optical resonance distance according to a wavelength of light emitted from the emission layer, and thus, efficiency of a formed organic light-emitting device may be improved.
The hole transport region may further include an electron blocking layer. The electron blocking layer may include, for example, mCP, but embodiments of the present disclosure are not limited thereto:
Then, an emission layer may be formed on the hole transport region by vacuum deposition, spin coating, casting, LB deposition, or the like. When the emission layer is formed by vacuum deposition or spin coating, the deposition or coating conditions may be similar to those applied in forming the hole injection layer although the deposition or coating conditions may vary according to a compound that is used to form the emission layer.
When the organic light-emitting device is a full-color organic light-emitting device, the emission layer may be patterned into a red emission layer, a green emission layer, and a blue emission layer. In one or more embodiments, due to a stacked structure including a red emission layer, a green emission layer, and/or a blue emission layer, the emission layer may emit white light.
The emission layer may include a host and a thermally activated delayed fluorescent dopant, and the host and the fluorescent dopant may be the same as described above.
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. While not wishing to be bound by theory, it is understood that 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 disposed on the emission layer.
The electron transport region may include at least one selected from a hole blocking layer, an electron transport layer, and an electron injection layer.
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 and BPhen, but may also include other materials:
A thickness of the hole blocking layer may be in a range of about 20 Å to about 1,000 Å, for example, about 30 Å to about 300 Å. While not wishing to be bound by theory, it is understood that when the thickness of the hole blocking layer is within these ranges, the hole blocking layer may have excellent hole blocking characteristics without a substantial increase in driving voltage.
The electron transport layer may include at least one selected from BCP, BPhen, Alq3, BAlq, TAZ, and NTAZ:
In one or more embodiments, the electron transport layer may include at least one of Compounds ET1 to ET25, but are not limited thereto:
A thickness of the electron transport layer may be in a range of about 100 Å to about 2,000 Å, for example, about 150 Å to about 1,500 Å. While not wishing to be bound by theory, it is understood that when the thickness of the electron transport layer is within the range described above, the electron transport layer may have satisfactory electron transport characteristics without a substantial increase in driving voltage.
Also, the electron transport layer may further include, in addition to the materials described above, a metal-containing material.
The metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 (lithium 8-hydroxyquinolate, LiQ) or ET-D2.
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 at least one selected from LiF, NaCl, CsF, Li2O, and BaO.
A thickness of the electron injection layer may be in a range of about 1 Å to about 100 Å, for example, about 3 Å to about 90 Å. While not wishing to be bound by theory, it is understood that 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 formed on the organic layer 150. The second electrode 19 may be a cathode. A material for forming the second electrode 19 may be selected from metal, an alloy, an electrically conductive compound, and a combination thereof, which have a relatively low work function. For example, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), or magnesium-silver (Mg—Ag) may be used as a material for forming the second electrode 19. In one or more embodiments, to manufacture a top-emission type light-emitting device, a transmissive electrode formed using ITO or IZO may be used as the second electrode 19.
Hereinbefore, the organic light-emitting device has been described with reference to
The 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 iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an iso-amyl group, and a hexyl group. The term “C1-C60 alkylene group” as used herein refers to a divalent group having the same structure as the C1-C60 alkyl group.
The term “C1-C60 alkoxy group” as used herein refers to a monovalent group represented by —OA101 (wherein A101 is the C1-C60 alkyl group), and examples thereof include a methoxy group, an ethoxy group, and an iso-propyloxy group.
The term “C2-C60 alkenyl group” as used herein refers to a hydrocarbon group having at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethenyl group, a propenyl group, and a butenyl group. The term “C2-C60 alkenylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein refers to a hydrocarbon group having at least one carbon-carbon triple bond in the middle or at the terminus of the C2-Coo alkyl group, and examples thereof include an ethynyl group, and a propynyl group. The term “C2-C60 alkynylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkynyl group.
The term “C3-C10 cycloalkyl group” as used herein refers to a monovalent saturated hydrocarbon monocyclic group having 3 to 10 carbon atoms, and non-limiting examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. The term “C3-C10 cycloalkylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkyl group.
The term “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 and 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.
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, and S as a ring-forming atom, 2 to 10 carbon atoms, and at least one double bond in its ring. Non-limiting examples of the C2-C10 heterocycloalkenyl group include a 2,3-dihydrofuranyl group, and a 2,3-dihydrothiophenyl group. The term “C2-C10 heterocycloalkenylene group” as used herein refers to a divalent group having the same structure as the C2-C60 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 C5-C60 arylene group each include two or more rings, the rings may be fused to each other.
The term “C2-C60 heteroaryl group” as used herein refers to a monovalent group having a heterocyclic aromatic system that has at least one heteroatom selected from N, O, P, Si, and S as a ring-forming atom, and 2 to 60 carbon atoms. The term “C2-C60 heteroarylene group,” as used herein refers to a divalent group having a heterocyclic aromatic system that has at least one heteroatom selected from N, O, P, Si, and S as a ring-forming atom, and 2 to 60 carbon atoms. Non-limiting examples of the C2-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 C2-C60 heteroaryl group and the C2-C60 heteroarylene group each include two or more rings, the rings may be fused to each other.
The term “C6-C60 aryloxy group” as used herein refers to —OA102 (wherein A102 is the C6-C60 aryl group), a C6-C60 arylthio group as used herein indicates —SA103 (wherein A103 is the C6-C60 aryl group), and the term “C7-C60 arylalkyl group” as used herein indicates -A104A105 (wherein A105 is the C6-C59 aryl group and A104 is the C1-C53 alkylene group).
The term “C1-C60 heteroaryloxy group” as used herein refers to —OA106 (wherein A106 is the C2-C60 heteroaryl group), the term “C1-C60 heteroarylthio group” as used herein indicates —SA107 (wherein A107 is the C1-C60 heteroaryl group), and the term “C2-C60 heteroarylalkyl group” as used herein refers to -A108A109 (A109 is a C1-C59 heteroaryl group, and A108 is a C1-C59 alkylene group).
The term “monovalent non-aromatic condensed polycyclic group” as used herein refers to a monovalent group having two or more rings condensed to each other, only carbon atoms (for example, the number of carbon atoms may be in a range of 8 to 60) as a ring-forming atom, and no aromaticity in its entire molecular structure. Non-limiting 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 having two or more rings condensed to each other, a heteroatom selected from N, O, P, Si, and S, other than carbon atoms (for example, the number of carbon atoms may be in a range of 2 to 60), 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.
At least one substituent of 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 C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C1-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C7-C60 arylalkyl group, the substituted C1-C60 heteroaryl group, the substituted C1-C60 heteroaryloxy group, the substituted C1-C60 heteroarylthio group, the substituted C2-C60 heteroarylalkyl group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may be selected from:
deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, 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, and a C1-C60 alkoxy group;
a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, and a C1-C60 alkoxy group, each substituted with at least one selected from deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, 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 C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, —N(Q11)(Q12), —Si(Q13)(Q14)(Q15), —B(Q16)(Q17), and —P(═O)(Q18)(Q19);
a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group;
a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group, each substituted with at least one selected from deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, 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 C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, —N(Q21)(Q22), —Si(Q23)(Q24)(Q25), —B(Q26)(Q27) and —P(═O)(Q28)(Q29); and
—N(Q31)(Q32), —Si(Q33)(Q34)(Q35), —B(Q36)(Q37) and —P(═O)(Q38)(Q30), and
Q101 to Q103, Q111 to Q113, Q121 to Q123, Q11 to Q19, Q21 to Q29, and Q31 to Q39 may each independently be selected from hydrogen, 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 C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a biphenyl group, a terphenyl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group, a C1-C60 heteroaryl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group.
For example, Q101 to Q103, Q111 to Q113, Q121 to Q123, Q11 to Q19, Q21 to Q29, and Q31 to Q39 may each independently be hydrogen, deuterium, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a naphthyl group, a fluorenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a triphenylenyl group, a biphenyl group, a terphenyl group, or a tetraphenyl group, but embodiments of the present disclosure are not limited thereto.
The term “room temperature” as used herein refers to about 25° C.
The terms “biphenyl group”, “terphenyl group”, and “tetraphenyl group” as used herein each refer to a monovalent group in which two, three, or four benzene groups are linked to each other via a single bond, respectively.
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.
Synthesis of Intermediate 2(1)
2-chloro-4,6-diphenyl-1,3,5-triazine (3.0 grams (g), 11.21 millimoles, mmol), (2,5-difluorophenyl)boronic acid (2.12 g, 13.45 mmol), palladium tetrakis(triphenylphosphine) (Pd(PPh3)4) (0.65 g, 0.56 mmol), and potassium carbonate (K2CO3) (4.65 g, 33.62 mmol) were added to a mixture of 20 milliliters (mL) of tetrahydrofuran and 20 mL of distilled water, and the reaction mixture was heated under reflux. After the reaction was completed, the reaction product was cooled to room temperature, and methanol was added thereto. The reaction solution was filtered through silica gel. An organic layer obtained therefrom was concentrated and precipitated by adding methanol thereto to synthesize Intermediate 2(1) (white solid, 3.23 g, yield of 83%).
Synthesis of Compound 2
Intermediate 2(1) (5.18 g, 15 mmol), 3,6-di-tert-butyl-9H-carbazole (12.57 g, 45 mmol), and potassium-tert-butoxide (t-BuOK) (4.21 g, 37.5 mmol) were added to 30 mL of N,N-dimethylformamide and stirred at a temperature of 120° C. for 12 hours. After the reaction was completed, the reaction product was cooled to room temperature, and methanol was added thereto. The reaction solution was filtered through silica gel. The organic layer obtained therefrom was concentrated, redissolved in toluene, filtered through silica gel, and then concentrated. The resultant obtained therefrom was recrystallized by using toluene to synthesize Compound 2 (yellow solid, 9.39 g, yield of 48%).
LC-MS (Calcd.: 864.19 g/mol, Found: 864.27 g/mol (M+1)).
Synthesis of Intermediate 1074(1)
2,4-bis(4-(tert-butyl)phenyl)-6-chloro-1,3,5-triazine (5.0 g, 13.16 mmol), (2,5-difluorophenyl)boronic acid (2.49 g, 15.79 mmol), palladium tetrakis(triphenylphosphine (Pd(PPh3)4) (0.76 g, 0.66 mmol), and potassium carbonate (K2CO3) (5.46 g, 39.48 mmol) were added to a mixture of 22 mL of tetrahydrofuran and 22 mL of distilled water, and the reaction mixture was heated under reflux. After the reaction was completed, the reaction product was cooled to room temperature, and the organic layer was extracted therefrom by using dichloromethane and water and filtered through silica gel. The obtained organic layer was concentrated and precipitated by adding methanol thereto to synthesize Intermediate 1074(1) (white solid, 5.0 g, yield of 83%).
Synthesis of Compound 1074
Intermediate 1074(1) (2.62 g, 5.73 mmol), 3,6-di-tert-butyl-9H-carbazole (4.0 g, 14.31 mmol), and cesium carbonate (Cs2CO3) (9.33 g, 28.63 mmol) were added to 30 mL of N,N-dimethylformamide, and the reaction mixture was stirred at a temperature of 165° C. for 12 hours. After the reaction was completed, the reaction product was cooled to room temperature, and methanol was added thereto. The reaction solution was filtered through silica gel. The organic layer obtained therefrom was concentrated, redissolved in toluene, filtered through silica gel, and then concentrated. The resultant obtained therefrom was recrystallized by using dichloromethane and methanol to synthesize Compound 1074 (yellow solid, 4.34 g, yield of 78%).
LC-MS (Calcd.: 976.41 g/mol, Found: 976.5 g/mol (M+1)).
Synthesis of Intermediate 1075(1)
2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (8.12 g, 18.65 mmol), 2-bromo-1,4-difluorobenzene (3.0 g, 15.54 mmol), palladium tetrakis(triphenylphosphine) (Pd(PPh3)4) (0.89 g, 0.78 mmol), and potassium carbonate (K2CO3) (6.44 g, 46.63 mmol) were added to a mixture of 20 mL of tetrahydrofuran and 25 mL of distilled water, and the reaction mixture was heated under reflux. After the reaction was completed, the reaction product was cooled to room temperature, and the organic layer was extracted therefrom by using dichloromethane and water and filtered through silica gel. The obtained organic layer was concentrated and recrystallized by using a mixture of dichloromethane and ethyl acetate to synthesize Intermediate 1075(1) (white solid, 4.8 g, yield of 73%).
Synthesis of Compound 1075
Intermediate 1075(1) (1.81 g, 4.29 mmol), 3,6-di-tert-butyl-9H-carbazole (3.0 g, 10.74 mmol), and cesium carbonate (Cs2CO3) (7.0 g, 21.47 mmol) were added to 43 mL of N,N-dimethylformamide, and the reaction mixture was stirred at a temperature of 165° C. for 12 hours. After the reaction was completed, the reaction product was cooled to room temperature, and methanol was added thereto. The reaction solution was filtered through silica gel. The organic layer obtained therefrom was concentrated, redissolved in toluene, filtered through silica gel, and then concentrated. The resultant obtained therefrom was recrystallized by using a mixture of dichloromethane and hexane to synthesize Compound 1075 (yellow solid, 2.83 g, yield of 70%).
LC-MS (Calcd.: 940.29 g/mol, Found: 976.39 g/mol (M+1)).
Synthesis of Intermediate 1076(1)
Magnesium (7.76 g, 319.2 mmol) was added to a flask in a nitrogen atmosphere, and 1-bromo-3,5-di-tert-butylbenzene (90.03 g, 334.4 mmol) was dissolved in 300 mL of tetrahydrofuran, slowly added to the flask containing magnesium, and the reaction mixture was stirred at a temperature of 70° C. for 2 hours. After the reaction was completed, the reaction product was cooled to room temperature to obtain (3,5-di-tert-butylphenyl)magnesium bromide Grignard reagent. The Grignard reagent was directly used in a subsequent reaction without any purification. The Grignard reagent was slowly added dropwise to a reaction container in which 2,4,6-trichloro-1,3,5-triazine was dissolved in 300 mL of tetrahydrofuran at a temperature of −40° C. for 20 minutes, and the reaction mixture was stirred at the same temperature for 30 minutes. Then, the reaction container was heated to room temperature and stirred for 16 hours, and was further heated to a temperature of 60° C. and additionally stirred for 4 hours. After the reaction was completed, the reaction product was cooled to room temperature, and the organic layer extracted therefrom by using 1 L of dichloromethane, hydrochloric acid (1 normal (N), 500 mL), and distilled water was concentrated and then recrystallized by using dichloromethane and acetonitrile to synthesize Intermediate 1076(1) (white solid, 53.56 g, yield of 72%).
Synthesis of Intermediate 1076(2)
Intermediate 1076(1) (7.38 g, 15 mmol), (2,5-difluorophenyl)boronic acid (3.55 g, 22.5 mmol), potassium phosphate tribasic (K3PO4) (4.78 g, 22.5 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba3)) (275 mg, 0.3 mmol), and tri-tert-butylphosphine (P(tBu)3) (242 mg, 12 mmol) were added to 30 mL of dioxane, and the reaction mixture was heated under reflux. After the reaction was completed, the reaction product was cooled to room temperature, the organic layer was extracted therefrom by using toluene and water, filtered through silica gel, concentrated, and then precipitated by using methanol to synthesize Intermediate 1076(2) (white solid, 6.17 g, yield of 72%).
Synthesis of Compound 1076
Compound 1076 (6.8 g, yield of 58%) was synthesized in the same manner as Compound 2 of Synthesis Example 1, except that Intermediate 1076(2) was used instead of Intermediate 2(1).
LC-MS (Calcd.: 1088.63 g/mol, Found: 1088.73 g/mol (M+1)).
Compound 1 (2.4 g, yield of 63%) was synthesized in the same manner as Compound 1074 of Synthesis Example 2, except that carbazole (9H-carbazole) was used instead of 3,6-di-tert-butyl-9H-carbazole, and Intermediate 2(1) was used instead of Intermediate 1074(1).
LC-MS (Calcd.: 716.26 g/mol, Found: 717.26 g/mol (M+1)).
Compound 1077 (2.4 g, yield of 50%) was synthesized in the same manner as in Synthesis Example 5, except that 6-(tert-butyl)-9H-carbazole-3-carbonitrile was used instead of carbazole.
LC-MS (Calcd.: 802.00 g/mol, Found: 802.10 g/mol (M+1)).
Synthesis of Intermediate 14(1)
Intermediate 14(1) (15.30 g, yield of 87%) was synthesized in the same manner as Intermediate 2(1) of Synthesis Example 1, except that (5-chloro-2-fluorophenyl)boronic acid was used instead of (2,5-difluorophenyl)boronic acid.
LC-MS (Calcd.: 361.80 g/mol, Found: 361.90 g/mol (M+1)).
Synthesis of Intermediate 14(2)
Intermediate 14(1) (28.1 g, 77.67 mmol), bis(pinacolato)diboron (39.45 g, 155.33 mmol), potassium acetate (AcOK) (22.87 g, 233.00 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) (7.11 g, 7.77 mmol), and tricyclohexylphosphine (P(Cy)3) (2.178 g, 7.77 mmol) were added to a reaction container, dissolved in 155 mL of dioxane, and the reaction mixture was stirred at a temperature of 120° C. After the reaction was completed, the reaction product was cooled to room temperature, and the organic layer was extracted therefrom by using ethyl acetate and water, filtered through silica gel, and then concentrated. The solid compound (Intermediate 14(2)) (32.40 g, yield of 92%) obtained therefrom was directly used in a subsequent reaction without any purification.
Synthesis of Intermediate 14(3)
Intermediate 14(3) (6 g, yield of 83%) was synthesized in the same manner as Intermediate 2(1) of Synthesis Example 1, except that bromobenzene was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine.
LC-MS (Calcd.: 403.46 g/mol, Found: 400.56 g/mol (M+1)).
Synthesis of Compound 14
Compound 14 (0.66 g, yield of 30%) was synthesized in the same manner as Compound 1074 of Synthesis Example 2, except that 3,6-diphenyl-9H-carbazole was used instead of 3,6-di-tert-butyl-9H-carbazole, and Intermediate 14(3) was used instead of Intermediate 1074(1).
LC-MS (Calcd.: 702.86 g/mol, Found: 702.96 g/mol (M+1)).
Compound 13 (0.70 g, yield of 33%) was synthesized in the same manner as Compound 14 of Synthesis Example 7, except that 3,6-di-tert-butyl-9H-carbazole was used instead of 3,6-diphenyl-9H-carbazole.
LC-MS (Calcd.: 662.88 g/mol, Found: 662.98 g/mol (M+1)).
Synthesis of Intermediate 71(1)
Compound 71(1) (6 g, yield of 83%) was synthesized in the same manner as Intermediate 2(1) of Synthesis Example 1, except that 2′-bromo-1,1′: 3′,1″-terphenyl was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and a starting material 71(A) was used instead of (2,5-difluorophenyl)boronic acid.
LC-MS (Calcd.: 555.66 g/mol, Found: 555.76 g/mol (M+1)).
Synthesis of Compound 71
Compound 71 (4.7 g, yield of 70%) was synthesized in the same manner as Compound 14 of Synthesis Example 7, except that Intermediate 71(1) was used instead of Intermediate 14(3).
LC-MS (Calcd.: 855.03 g/mol, Found: 855.13 g/mol (M+1)).
Compound 70 (3.8 g, yield of 72%) was synthesized in the same manner as Compound 71 of Synthesis Example 9, except that 3,6-di-tert-butyl-9H-carbazole was used instead of 3,6-diphenyl-9H-carbazole.
LC-MS (Calcd.: 815.06 g/mol, Found: 815.16 g/mol (M+1)).
Synthesis of Intermediate 37(1)
Intermediate 37(1) (6 g, yield of 83%) was synthesized in the same manner as Intermediate 2(1) of Synthesis Example 1, except that 5′-bromo-1,1′:3′,1″-terphenyl was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and a starting material 71(A) was used instead of (2,5-difluorophenyl)boronic acid.
LC-MS (Calcd.: 555.66 g/mol, Found: 555.76 g/mol (M+1)).
Synthesis of Compound 37
Compound 37 (4.9 g, yield of 82%) was synthesized in the same manner as Compound 14 of Synthesis Example 7, except that Intermediate 37(1) was used instead of Intermediate 14(3).
LC-MS (Calcd.: 855.03 g/mol, Found: 855.13 g/mol (M+1)).
Compound 46 (0.7 g, yield of 34%) was synthesized in the same manner as Compound 14 of Synthesis Example 7, except that 12H-benzofuro[2,3-a]carbazole was used instead of 3,6-diphenyl-9H-carbazole.
LC-MS (Calcd.: 640.75 g/mol, Found: 640.85 g/mol (M+1)).
Compound 21 (0.7 g, yield of 10%) was synthesized in the same manner as in Synthesis Example 5, except that 12H-benzofuro[2,3-a]carbazole was used instead of carbazole.
LC-MS (Calcd.: 819.92 g/mol, Found: 820.02 g/mol (M+1)).
Synthesis of Intermediate 346(1)
4-chloro-2,6-diphenyltriazine (10 g, 37.35 mmol), (2,5-difluoropyridin-3-yl)boronic acid (7.122 g, 44.82 mmol), potassium phosphate tribasic (K3PO4) (15.86 g, 74.70 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba3)) (0.68 g, 0.75 mmol), and a phosphine ligand (SPhos) (1.533 g, 3.74 mmol) were added to a mixture of 60 mL of dioxane and 60 mL of distilled water, and the reaction mixture was heated under reflux. After the reaction was completed, the reaction product was cooled to room temperature, and the organic layer was extracted therefrom by using toluene and water and filtered through silica gel. The obtained organic layer was concentrated and precipitated by using methanol to synthesize Intermediate 346(1) (white solid, 2.32 g, yield of 18%).
LC-MS (Calcd.: 346.34 g/mol, Found: 346.3 g/mol (M+1)).
Synthesis of Compound 346
Compound 346 (3.2 g, yield of 55%) was synthesized in the same manner as Compound 1074 of Synthesis Example 2, except that Intermediate 346(1) was used instead of Intermediate 1074(1).
LC-MS (Calcd.: 865.18 g/mol, Found: 866.2 g/mol (M+1)).
Compound 25 (2.9 g, yield of 34%) was synthesized in the same manner as Compound 14 of Synthesis Example 7, except that 5H-benzofuro[3,2-c]carbazole was used instead of 3,6-diphenyl-9H-carbazole.
LC-MS (Calcd.: 640.75 g/mol, Found: 640.85 g/mol (M+1)).
Synthesis of Intermediate 1078(1)
2,4,6-trichloro-1,3,5-triazine (6.0 g, 32.54 mmol), (4-fluorophenyl)boronic acid (9.56 g, 68.33 mmol), potassium carbonate (K2CO3) (17.98 g, 130.15 mmol), and bis(triphenylphosphine)palladium(II), dichloride PdCl2(PPh3)4) (1.14 g, 1.63 mmol) were added to 70 mL of toluene, and the reaction mixture was heated under reflux at a temperature of 60° C. After the reaction was completed, the reaction product was cooled to room temperature, and the organic layer was extracted by using toluene and water and filtered through silica gel. The obtained organic layer was concentrated and precipitated by using methanol to synthesize Intermediate 1078(1) (white solid, 4.01 g, yield of 40%).
LC-MS (Calcd.: 303.54 g/mol, Found: 303.64 g/mol (M+1)).
Synthesis of Intermediate 1078(2)
Intermediate 1078(1) (i.e., 2-chloro-4,6-bis(4-fluorophenyl)-1,3,5-triazine) (3.8 g, 12.51 mmol), (2,5-difluorophenyl)boronic acid (2.37 g, 15.01 mmol), palladium tetrakis(triphenylphosphine) (Pd(PPh3)4) (0.72 g, 0.63 mmol), and potassium carbonate (K2CO3) (3.46 g, 25.02 mmol) were added to a mixture of 20 mL of toluene and 7 mL of distilled water, and the reaction mixture was heated under reflux at a temperature of 100° C. After the reaction was completed, the reaction product was cooled to room temperature, and the organic layer was extracted therefrom by using toluene and water and filtered through silica gel. The obtained organic layer was concentrated and precipitated by using methanol to synthesize Intermediate 1078(2) (white solid, 4.2 g, yield of 88%).
Synthesis of Compound 1078
Compound 1078 (2.6 g, yield of 27%) was synthesized in the same manner as Compound 1 of Synthesis Example 5, except that Intermediate 1078(2) was used instead of Intermediate 2(1).
LC-MS (Calcd.: 970.15 g/mol, Found: 970.25 g/mol (M+1)).
HOMO, LUMO, T1, and S1 energy levels of Compounds shown in Table 2 were measured by using methods described in Table 1, and results thereof are shown in Table 2.
Referring to Table 2, it is confirmed that Compounds shown in Table 2 have excellent electric characteristics.
PL spectra of Compounds shown in Table 4 were measured by using methods described in Table 3, and FWHM of each Compound was evaluated. The results thereof are shown in Table 4.
Referring to Table 4, it is confirmed that Compounds shown in Table 4 have excellent luminescence characteristics.
(1) Preparation of Thin Film
A quartz substrate washed with chloroform and pure water was prepared, and Compound 2 and Compound E4 were co-deposited at a weight ratio of 5:5 at a vacuum degree of 10−7 torr to manufacture a thin film having a thickness of 50 nanometers (nm).
(2) Evaluation of PLQY
A PLQY of the thin film was evaluated by using Hamamatsu a Photonics absolute PL quantum yield measurement system including a xenon light source, a monochromator, a photonic multichannel analyzer, and an integrating sphere and employing a PLQY measurement software (Hamamatsu Photonics, Ltd., Shizuoka, Japan), and a PLQY of Compound 2 in film was evaluated.
(3) Evaluation of Decay Time
A PL spectrum of the thin film was evaluated at room temperature by using a PicoQuant TRPL measurement system FluoTime 300 and a PicoQuant pumping source PLS340 (excitation wavelength=340 nm, spectral width=20 nm), a wavelength of a main peak of the spectrum was determined, PLS340 repeatedly measured the number of photons emitted from the thin film at the wavelength of the main peak due to a photon pulse (pulse width=500 picoseconds, ps) applied to the thin film according to time based on time-correlated single photon counting (TCSPC), thereby obtaining a sufficiently fittable TRPL curve. Tdecay(Ex) (decay time) of Compound 2 of the thin film was obtained by fitting two or more exponential decay function to the result obtained therefrom. The function used for fitting is expressed by Equation 1, and the greatest value of Tdecay obtained from each exponential decay function used for fitting was taken as Tdecay(Ex) and shown in Table 5. The remaining values of Tdecay may be used to determine a lifetime of a decay of a general fluorescence. At this time, a baseline or background signal curve was obtained by repeating the same measurement once more for the same measurement time as the measurement time for obtaining the TRPL curve in a dark state (a state in which a pumping signal applied to the predetermined film was blocked), and the baseline or background signal curve was fitted and used as a baseline.
(4) Table 5
The procedures of the above (1) to (3) were repeated with respect to the remaining Compounds of Table 5, and results thereof are shown in Table 5.
Referring to Table 5, it is confirmed that Compounds shown in Table 5 have excellent PLQY (in film) and decay time characteristics.
A glass substrate, on which a 1,500 Å-thick ITO electrode (first electrode, anode) was formed, was sonicated with distilled water. After the washing with distilled water was completed, ultrasonic wave washing was performed by using a solvent such as iso-propyl alcohol, acetone, and methanol, and the glass substrate was dried and then transferred to a plasma cleaner. The glass substrate was cleaned for 5 minutes by using oxygen plasma and provided to a vacuum deposition apparatus.
Compound HT3 and Compound HT-D2 were co-deposited on the ITO electrode of the glass substrate to form a hole injection layer having a thickness of 100 Å, Compound HT3 was deposited on the hole injection layer to form a hole transport layer having a thickness of 1,350 Å, and mCP was deposited on the hole transport layer to form an electron blocking layer having a thickness of 100 Å, thereby forming a hole transport region.
A host and a dopant were co-deposited on the hole transport region at a weight ratio of 85:15 to form an emission layer having a thickness of 300 Å. Compound E4 was used as the host, and Compound 2 was used as the dopant.
Compound BCP was vacuum-deposited on the emission layer to form a hole blocking layer having a thickness of 100 Å, Compound ET3 and LiQ were vacuum-deposited on the hole blocking layer to form an electron transport layer having a thickness of 300 Å, LiQ was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and Al was deposited on the electron injection layer to form a second electrode (cathode) having a thickness of 1,000 Å, thereby completing the manufacture of an organic light-emitting device.
Organic light-emitting devices were manufactured in the same manner as in Example 1, except that the dopant in the emission layer was changed as shown in Table 6.
The driving voltage, luminescence efficiency, and lifespan (T95) of each of Examples 1 to 8 and Comparative Examples A-1 to D were measured by using a current-voltage meter (Keithley 2400) and a luminance meter (Minolta Cs-1000A), and the results thereof are shown in Table 6. The lifespan (T95) data (at 500 candelas per square meter, cd/m2) in Table 6 indicates an amount of time (hours, hr) that lapsed when luminance was 95% of initial luminance (100%). The luminescence efficiency and the lifespan are relative values with respect to the luminescence efficiency and the lifespan of Example 2.
Referring to Table 6, it is confirmed that the organic light-emitting devices of Examples 1 to 8 have excellent driving voltage, luminescence efficiency and lifespan “at the same time”, as compared with those of the organic light-emitting devices of Comparative Examples A-1 to A-5, B-1 to B-6, C-1 to C-3, and D.
Since the heterocyclic compound has excellent electric characteristics and thermal stability, the organic light-emitting device including the heterocyclic compound may have low driving voltage, low driving voltage, high luminescence efficiency, and long lifespan 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 of the present disclosure as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2018-0100569 | Aug 2018 | KR | national |
