Patent Application
20240010636
This application claims priority to and the benefit of Korean Patent Application Nos. 10-2022-0055745, filed on May 4, 2022, and 10-2023-0057772, filed on May 3, 2023, in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. § 119, the entire contents of which are incorporated by reference herein.
The present subject matter relates to a heterocyclic compound, an organic light-emitting device including the same, and an electronic apparatus including the organic light-emitting device.
Organic light-emitting devices (OLEDs) are self-emissive devices, which have improved characteristics in terms of viewing angles, response time, brightness, driving voltage, and response speed. In addition, OLEDs produce full-color images.
In an example, an organic light-emitting device includes an anode, a cathode, and an organic layer that is arranged between the anode and the cathode and includes an emission layer. A hole transport region may be provided between the anode and the emission layer, and an electron transport region may be provided between the emission layer and the cathode. Holes provided from the anode may move toward the emission layer through the hole transport region, and electrons provided from the cathode may move toward the emission layer through the electron transport region. The holes and the electrons may recombine in the emission layer to produce excitons. The excitons may transition from an excited state to a ground state, thereby generating light.
Provided are a heterocyclic compound, an organic light-emitting device including the same, and an electronic apparatus including the organic light-emitting device.
Additional aspects will be set forth in part in the detailed description that follows and, in part, will be apparent from the detailed description, or may be learned by practice of the presented exemplary embodiments provided herein.
According to an aspect, there is provided a heterocyclic compound represented by Formula 1:
wherein, in Formulae 1 and A, E1 is a group represented by Formula A,
According to another aspect, an organic light-emitting device includes a first electrode, a second electrode, and an organic layer arranged between the first electrode and the second electrode, wherein the organic layer includes an emission layer, and wherein the organic layer further includes at least one of the heterocyclic compounds represented by Formula 1.
According to another aspect, an electronic apparatus includes the organic light-emitting device.
The above and other aspects, features, and advantages of certain exemplary embodiments will be more apparent from the following detailed description taken in conjunction with the FIGURE, which is a schematic cross-sectional view of an organic light-emitting device 10 according to one or more embodiments.
Reference will now be made in further detail to exemplary embodiments, examples of which are illustrated in the accompanying drawing, wherein like reference numerals refer to like elements throughout. In this regard, the present exemplary embodiments may have different forms and should not be construed as being limited to the detailed descriptions set forth herein. Accordingly, the exemplary embodiments are merely described in further detail below, and by referring to the FIGURE, to explain certain aspects. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
The terminology used herein is for the purpose of describing one or more exemplary embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. The term “or” means “and/or.” It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
It will be understood that, although the terms first, second, third etc. may be used herein to describe various elements, components, regions, layers, and/or sections, these elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of the present embodiments.
Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
It will be understood that when an element is referred to as being “on” another element, it can be directly in contact with the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this general inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
“About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.
As used herein, when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (for example, phenyl, naphthyl, or the like) or as if it were the whole molecule (for example, benzene, naphthalene, or the like). It is to be understood that the nomenclature may be used interchangeably herein.
As used herein, an “energy level” (e.g., a highest occupied molecular orbital (HOMO) energy level or a triplet (Ti) energy level) is expressed as an absolute value from a vacuum level. In addition, when the energy level is referred to as being “deep,” “high,” or “large,” the energy level has a large absolute value based on “0 electron Volts (eV)” of the vacuum level, and when the energy level is referred to as being “shallow,” “low,” or “small,” the energy level has a small absolute value based on “0 eV” of the vacuum level.
A heterocyclic compound according to an aspect is represented by Formula 1:
wherein, in Formulae 1,
In one or more embodiments, k1 may be an integer from 1 to 3.
In Formulae 1 and A,
In one or more embodiments, n1 may be 2 or 3.
n2 is an integer from 0 to 3.
In one or more embodiments, n2 may be 0 or 1.
In Formulae 1 and A, R1 to R6 are each independently hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C7-C60 alkyl aryl group, a substituted or unsubstituted C7-C60 aryl alkyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C2-C60 alkyl heteroaryl group, a substituted or unsubstituted C2-C60 heteroaryl alkyl group, a substituted or unsubstituted C1-C6 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —Ge(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q9), or —P(Q8)(Q9).
In Formula A, R7 is hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —Ge(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q9), or —P(Q8)(Q9).
In one or more embodiments, R5 to R7 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —Ge(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q9), or —P(Q8)(Q9).
In one or more embodiments, R1 to R4 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —Ge(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q9), or —P(Q8)(Q9).
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 C1-C60 alkylthio group, the substituted C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C1-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C7-C60 alkyl aryl group, the substituted C7-C60 aryl alkyl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl group, the substituted C2-C60 alkyl heteroaryl group, the substituted C2-C60 heteroaryl alkyl group, the substituted C1-C60 heteroaryloxy group, the substituted C1-C60 heteroarylthio group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group is:
Q1 to Q9, Q11 to Q19, Q21 to Q29, and Q31 to Q39 are each independently hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C7-C60 alkyl aryl group, a substituted or unsubstituted C7-C60 aryl alkyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C2-C60 alkyl heteroaryl group, a substituted or unsubstituted C2-C60 heteroaryl alkyl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group.
In Formula 1, d1, d2, d3, d5, and d6 indicate the number of R1(s), R2(s), R3(s), R5(s), and R6(s), respectively, and are each independently a number of 0 to 4 (e.g., 0, 1, 2, 3, or 4). When d1 is 2 or greater, two or more of R1 may be identical to or different from each other, when d2 is 2 or greater, two or more of R2 may be identical to or different from each other, when d3 is 2 or greater, two or more of R3 may be identical to or different from each other, when d5 is 2 or greater, two or more of R5 may be identical to or different from each other, and when d6 is 2 or greater, two or more of R6 may be identical to or different from each other.
In Formula 1, d4 indicates the number of R3(s), and is an integer from 0 to 3 (e.g., 0, 1, 2, or 3). When d4 is 2 or greater, two or more of R4 may be identical to or different from each other.
In Formula 1, d7 indicates the number of R7(s), and is an integer from 0 to 5 (e.g., 0, 1, 2, 3, 4, or 5). When d7 is 2 or greater, two or more of R7 may be identical to or different from each other.
In one or more embodiments, at least one of d2 and d1 may be an integer of 1 or greater. In one or more embodiments, at least one of d2 and d1 may be 4.
In one or more embodiments, R1 to R6 may each independently be:
In one or more embodiments, R1 to R7 may each independently be:
In one or more embodiments, R1 to R6 may each independently be:
wherein, in Formulae 9-1 to 9-61, 9-201 to 9-240, 10-1 to 10-129, and 10-201 to 10-355, * indicates a binding site to a neighboring atom, “Ph” represents a phenyl group, “TMS” represents a trimethylsilyl group, “TMG” represents a trimethylgermyl group, and “t-Bu” represents a t-butyl group.
In one or more embodiments, R1 to R6 may each independently be:
wherein, in Formulae 9-1 to 9-61 and 9-201 to 9-240, * indicates a binding site to a neighboring atom.
The heterocyclic compound represented by Formula 1 includes at least one deuterium.
In one or more embodiments, the heterocyclic compound may include deuterium as a substituent or may include deuterium as a part of a substituent group (i.e., a group that is substituted with at least one deuterium). For example, one or more of R1 to R7 may be deuterium, and/or one or more of R1 to R7 may be a group that is substituted with at least one deuterium (for example, —CH2D, —CHD2, —CD3, or the like).
In one or more embodiments, the heterocyclic compound represented by Formula 1 may satisfy at least one of Conditions 1 to 7:
For example, the heterocyclic compound may satisfy at least one of Conditions 1 and 2.
In one or more embodiments, the heterocyclic compound may satisfy at least two of Conditions 1 to 7.
In one or more embodiments, the heterocyclic compound may satisfy at least three of Conditions 1 to 7.
In one or more embodiments, the heterocyclic compound may satisfy at least four of Conditions 1 to 7.
In one or more embodiments, the heterocyclic compound may satisfy at least five of Conditions 1 to 7.
In one or more embodiments, the heterocyclic compound may satisfy at least six of Conditions 1 to 7.
In one or more embodiments, the heterocyclic compound may satisfy all of Conditions 1 to 7.
In one or more embodiments, the heterocyclic compound represented by Formula 1 may satisfy at least one of Conditions 1′ to 7′:
In one or more embodiments, the heterocyclic compound may satisfy at least two of Conditions 1′ to 7′.
In one or more embodiments, the heterocyclic compound may satisfy at least three of Conditions 1′ to 7′.
In one or more embodiments, the heterocyclic compound may satisfy at least four of Conditions 1′ to 7′.
In one or more embodiments, the heterocyclic compound may satisfy at least five of Conditions 1′ to 7′.
In one or more embodiments, the heterocyclic compound may satisfy at least six of Conditions 1′ to 7′.
In one or more embodiments, the heterocyclic compound may satisfy all of Conditions 1′ to 7′.
In one or more embodiments, the substitution ratio of deuterium of the heterocyclic compound represented by Formula 1 may be greater than about 0% and less than or equal to about 100%.
In one or more embodiments, the substitution ratio of deuterium of the heterocyclic compound represented by Formula 1 may be greater than or equal to about 10% and less than or equal to about 100%. For example, the substitution ratio of deuterium may be greater than or equal to about 10% and less than or equal to about 100%, greater than or equal to about 10% and less than or equal to about 90%, greater than or equal to about 15% and less than or equal to about 100%, greater than or equal to about 15% and less than or equal to about 90%, greater than or equal to about 20% and less than or equal to about 100%, greater than or equal to about 20% and less than or equal to about 90%, greater than or equal to about 40% and less than or equal to about 100%, or greater than or equal to about 40% and less than or equal to about 90%.
In one or more embodiments, the substitution ratio of deuterium of heterocyclic compound may be greater than or equal to about 40% and less than or equal to about 90%.
The term “substitution ratio of deuterium of the heterocyclic compound represented by Formula 1” as used herein refers to the ratio of a number of substituents substituted with deuterium to the number of substituents that can be substituted in the core of the heterocyclic compound represented by Formula 1. That is, the substitution rate of deuterium refers to, in Formulae 1 and A, the ratio of the number of deuterium in R1 to R7 to the total number of R1 to R7.
In one or more embodiments, among R1, R2, R3, R4, R5, R6, and R7, at least about 10% of the substituents may be deuterium.
In one or more embodiments, among R1, R2, R3, R4, R5, R6, and R7, at least about 20% of the substituents may be deuterium.
In one or more embodiments, among R1, R2, R3, R4, R5, R6, and R7, at least about 30% of the substituents may be deuterium.
In one or more embodiments, among R1, R2, R3, R4, R5, R6, and R7, at least about 40% of the substituents may be deuterium.
In one or more embodiments, among R1, R2, R3, R4, R5, R6, and R7, at least about 80% of the substituents may be deuterium.
In one or more embodiments, among R1, R2, R3, R4, R5, R6, and R7, at least about 90% of the substituents may be deuterium.
In one or more embodiments, the heterocyclic compound represented by Formula 1 may be represented by Formula 1A:
wherein, in Formula 1A,
In one or more embodiments, a moiety represented by
in Formula 1 may be a group represented by one of Formulae 2-1 to 2-4:
wherein, in Formulae 2-1 to 2-4,
In one or more embodiments, a moiety represented by
in Formula 1 may be a group represented by one of Formulae 3-1 to 3-16:
wherein, in Formulae 3-1 to 3-16
In one or more embodiments, in Formulae 3-1 to 3-4, at least one of R11 to R14, R21 to R24, R31 to R34, and R41 to R44 may be deuterium.
In one or more embodiments, in Formulae 3-1 to 3-4, some or all of R11 to R14, R21 to R24, R31 to R34, and R41 to R44 may be deuterium.
In one or more embodiments, in Formulae 3-5 to 3-16, at least one of R11 to R14, R21 to R24, R31 to R38, and R41 to R48 may be deuterium.
In one or more embodiments, in Formulae 3-5 to 3-16, some or all of R11 to R14, R21 to R24, R31 to R38, and R41 to R48 may be deuterium.
In one or more embodiments, the group represented by Formula A may be a group represented by one of Formulae A-1 to A-13:
wherein, in Formulae A-1 to A-13,
In one or more embodiments, in Formulae A-1 to A-4, at least one of R61 to R65 and R71 to R75 may be deuterium.
In one or more embodiments, in Formulae A-1 to A-4, some or all of R61 to R65 and R71 to R7 s may be deuterium.
In one or more embodiments, in Formulae A-5 to A-13, at least one of R61 to R70 and R71 to R75 may be deuterium.
In one or more embodiments, in Formulae A-5 to A-13, some or all of R61 to R65 and R71 to R75 may be deuterium.
In one or more embodiments, a moiety represented by
in Formula 1 may be a group represented by one of Formulae 4-1 to 4-17:
wherein, in Formulae 4-1 to 4-17,
In one or more embodiments, at least one of R51 to R55 in Formulae 4-1 and 4-17 may be deuterium.
In one or more embodiments, some or all of R51 to R55 in Formula 4-1 to 4-17 may be deuterium.
In one or more embodiments, in Formulae 4-4 to 4-12, E11 and E12 may be identical to or different from each other.
In one or more embodiments, in Formulae 4-13 to 4-17, E11 and E13 may be identical to or different from each other.
In one or more embodiments, a moiety represented by
in Formula 1A may be a group represented by one of Formulae 5-1 to 5-15:
wherein, in Formulae 5-1 to 5-15,
In one or more embodiments, when n1 in Formula 1A is 2, a moiety represented by
in Formula 1A may be a group represented by one of Formulae 5-10 to 5-15.
In one or more embodiments, when n1 in Formula 1A is 3, a moiety represented by
in Formula 1A may be a group represented by one of Formulae 5-1 to 5-15.
The heterocyclic compound represented by Formula 1 may be represented by one of Formulae 1-1 to 1-36, 1-73 to 1-111, 1-145 to 1-180, or 1-217 to 1-252:
wherein, in Formulae 1-1 to 1-36, 1-73 to 1-111, 1-145 to 1-180, and 1-217 to 1-252, at least one hydrogen is substituted with deuterium.
In one or more embodiments, in Formulae 1-1 to 1-36, 1-73 to 1-111, 1-145 to 1-180, and 1-217 to 1-252, all hydrogen atoms except for those substituted with deuterium may be substituted with a substituted Rx, wherein Rx is as described in connection with R1.
In one or more embodiments, the heterocyclic compound represented by Formula 1 may be one of Compounds 1 to 580:
In the heterocyclic compound represented by Formula 1, a first benzene group, a second benzene group, a first carbazole group, and a second carbazole group are sequentially bonded through a single bond, and moreover, a benzene group and a carbazole group may be further included, wherein “N” in the first carbazole group is bonded to the benzene group, and “N” in the second carbazole group is bonded to the first carbazole group (see, e.g., Formula 1′). Accordingly, the heterocyclic compound represented by Formula 1 may have a relatively high triplet (Ti) energy level.
In addition, the heterocyclic compound represented by Formula 1 includes at least one deuterium. A distance of the carbon-deuterium (C-D) bond is shorter than a distance of the carbon-hydrogen (C—H) bond, the bond energy is high, and the frequency is large so that the range of structural fluctuation is small, and thus the heterocyclic compound may have structural stability. In addition, due to the kinetic isotope effect, the heterocyclic compound may have hole stability in structures related to hole movement.
In one or more embodiments, the heterocyclic compound represented by Formula 1 may have a triplet (Ti) energy level of greater than or equal to about 2.8 eV, or about 2.8 eV to about 3.5 eV (e.g., see Table 1).
In one or more embodiments, the heterocyclic compound represented by Formula 1 may have an absolute value of a highest occupied molecular orbital (HOMO) energy level of less than or equal to about 5.2 eV, or about 4.8 eV to about 5.2 eV or about 5.0 eV to about 5.2 eV (e.g., see Table 1).
The triplet (Ti) energy level and the HOMO energy level may be evaluated based on the density functional theory (DFT).
For example, regarding Compounds 331, 339 and 183 belonging to the heterocyclic compound represented by Formula 1, the HOMO energy level, lowest unoccupied molecular orbital (LUMO) energy level, singlet (Si) energy level, triplet (Ti) energy level were calculated using a DFT method of the Gaussian 09 program with the molecular structure optimized at the B3LYP/6-31 G(d,p) levels, and results thereof are shown in Table 1.
The method of synthesizing the heterocyclic compound represented by Formula 1 may be recognized by those skilled in the art and with reference to the Synthesis Examples described herein.
According to another aspect, an organic light-emitting device includes a first electrode; a second electrode; and an organic layer arranged between the first electrode and the second electrode, wherein the organic layer includes an emission layer, and wherein the organic layer further includes at least one of the heterocyclic compounds represented by Formula 1.
When the organic light-emitting device includes such an organic layer including at least one of the aforementioned heterocyclic compounds represented by Formula 1, long lifespan characteristics or the like may be achieved.
The first electrode may be an anode, which is a hole injection electrode, and the second electrode may be a cathode, which is an electron injection electrode; or the first electrode may be a cathode, which is an electron injection electrode, and the second electrode may be an anode, which is a hole injection electrode.
For example, in the organic light-emitting device, the first electrode may be an anode, the second electrode may be a cathode, and the organic layer may further include a hole transport region arranged between the first electrode and the emission layer, and an electron transport region arranged between the emission layer and the second electrode, wherein the hole transport region may include a hole injection layer, a hole transport layer, an electron blocking layer, an auxiliary layer, or a combination thereof, and the electron transport region may include a buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof.
The heterocyclic compound represented by Formula 1 may be used between a pair of electrodes of an organic light-emitting device. In one or more embodiments, at least one of the heterocyclic compounds represented by Formula 1 may be included in the emission layer. In this regard, the heterocyclic compound may act as a host, and the emission layer may further include a dopant (that is, the amount of the at least one of the heterocyclic compound represented by Formula 1 in the emission layer may be greater than an amount of the dopant in the emission layer, based on weight). The emission layer may emit, for example, a blue light.
In one or more embodiments, the heterocyclic compound may be included in the hole transport region. For example, the heterocyclic compound may be included in the auxiliary layer of the hole transport region.
In one or more embodiments, the heterocyclic compound may be included in the electron transport region. For example, the heterocyclic compound may be included in the buffer layer of the electron transport region.
In one or more embodiments, the emission layer may include a host and a dopant, and the heterocyclic compound may be included in the host. In one or more embodiments, the amount (weight) of the host in the emission layer may be greater than the amount (weight) of the dopant in the emission layer.
In one or more embodiments, the emission layer may emit a blue light, but embodiments are not limited thereto.
The dopant may be a fluorescent dopant, a phosphorescent dopant, or a combination thereof. In one or more embodiments, the dopant may be a phosphorescent dopant.
In one or more embodiments, the emission layer may include a host, a fluorescent dopant, and a phosphorescent dopant, and the host may include at least one of the heterocyclic compounds represented by Formula 1. In this regard, the phosphorescent dopant may be a sensitizer compound that is used together with a fluorescent dopant to transfer excitons to the fluorescent dopant.
The expression that an “(organic layer) includes at least one of the heterocyclic compounds of Formula 1” as used herein may be construed as meaning that the “(organic layer) may include one heterocyclic compound of Formula 1 or two or more different heterocyclic compounds of Formula 1”.
In one or more embodiments, the organic layer may include only Compound 1 as the at least one of the heterocyclic compounds of Formula 1. In this embodiment, Compound 1 may be included in the emission layer of the organic light-emitting device. In one or more embodiments, the organic layer may include Compounds 1 and 2 as the at least one of the heterocyclic compounds of Formula 1. In this embodiment, Compound 1 and Compound 2 may exist in an identical layer (for example, Compound 1 and Compound 2 all may exist in an emission layer).
The term “organic layer” as used herein refers to a single layer and/or a plurality of layers that are located between the first electrode and the second electrode of the organic light-emitting device. The “organic layer” may include, in addition to an organic compound, an organometallic complex including a metal.
The FIGURE is a schematic cross-sectional view of an organic light-emitting device 10 according to one or more embodiments. Hereinafter, the structure and manufacturing method of the organic light-emitting device 10 according to one or more embodiments of the present disclosure will be described in connection with the FIGURE, but embodiments are not limited thereto.
In the FIGURE, an organic light-emitting device 10 includes a first electrode 11, a second electrode 19 facing the first electrode 11, and an organic layer 10A arranged between the first electrode 11 and the second electrode 19.
In the FIGURE, the organic layer 15 may include an emission layer 15, a hole transport region 12 is between the first electrode 11 and an emission layer 15, and an electron transport region 17 is between the emission layer 15 and the second electrode 19.
A substrate may be additionally disposed under the first electrode 11 or on the second electrode 19. The substrate may be a conventional substrate used in organic light-emitting devices, for example, a glass substrate or a transparent plastic substrate, each having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and/or water repellency.
The first electrode 11 may be formed by, for example, depositing or sputtering, onto the substrate, a material for forming the first electrode 11. The first electrode 11 may be an anode. The material for forming the first electrode 11 may include materials with a high work function to facilitate hole injection.
The first electrode 11 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. In one or more embodiments, when the first electrode 11 may be a transmissive electrode, the material for forming the first electrode 11 may include indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), or a combination thereof. In one or more embodiments, when the first electrode 11 may be a semi-transmissive electrode or a reflective electrode, the material for forming the first electrode 11 may include magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), or a combination thereof.
The first electrode 11 may have a single-layer structure or a multi-layer structure including a plurality of layers.
A thickness of the emission layer 15 may be about 100 an angstroms (Å) to about 1,000 Å, for example, about 200 Å to about 600 Å. Without wishing to be bound to theory, when the thickness of the emission layer 15 is within these ranges, excellent luminescence characteristics may be obtained without a substantial increase in driving voltage.
A host in the emission layer 15 may include at least one of the heterocyclic compounds represented by Formula 1.
In addition to the heterocyclic compound represented by Formula 1 (for example, refer to the first host in Examples described herein), an arbitrary host (for example, refer to the second host in the Examples) may be further included. Hereinafter, a host that may be included in the emission layer 15 in addition to at least one of the heterocyclic compounds represented by Formula 1 will be described herein.
The host may not include a transition metal.
The host may be one kind of compound, or a mixture of two or more different types of compounds.
In one or more embodiments, the host may include at least one of a bipolar host, an electron-transporting host, or a hole-transporting host. The bipolar host, the electron-transporting host, and the hole-transporting host may be different from each other.
The electron-transporting host may include at least one electron-transporting group.
The hole-transporting host may not include an electron-transporting group.
The term “electron-transporting group” as used herein may include a cyano group, a π electron-deficient nitrogen-containing C1-C60 cyclic group, a group represented by one of the following formulae, or a combination thereof:
wherein, in the formulae above, *, *′, and *″ each indicate a binding site to a neighboring atom.
In one or more embodiments, the electron-transporting host may include at least one of a cyano group and a r-electron deficient nitrogen-containing C1-C60 cyclic group.
In one or more embodiments, the electron-transporting host may include at least one cyano group.
In one or more embodiments, the electron-transporting host may include at least one cyano group and a π electron deficient nitrogen-containing C1-C60 cyclic group.
In one or more embodiments, the host may include a bipolar host.
In one or more embodiments, the host may include an electron-transporting host.
In one or more embodiments, the host may include a hole-transporting host.
In one or more embodiments, the hole-transporting host may not include 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(carbazol-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,
In one or more embodiments, the electron-transporting host may include i) at least one of a cyano group, a pyrimidine group, a pyrazine group, or a triazine group, and ii) at least one of a triphenylene group or a carbazole group.
In one or more embodiments, the hole-transporting host may include at least one carbazole group.
In one or more embodiments, the electron-transporting host may include a compound represented by Formula E-1, and
[Ar301]xb11-[(L301)xb1-R301]xb21 Formula E-1
wherein, in Formula E-1,
wherein, in Formulae H-1, 11, and 12,
In one or more embodiments, Ar301 and L301 in Formula E-1 may each independently be a benzene group, a naphthalene 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 pentaphene group, an indenoanthracene group, a dibenzofuran group, a dibenzothiophene group, 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 phthalazine group, a naphthyridine group, a quinoxaline group, a quinazoline group, a cinnoline group, a phenanthridine group, an acridine group, a phenanthroline group, a phenazine group, a benzimidazole group, an iso-benzothiazole group, a benzoxazole group, a benzoisoxazole group, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, a thiadiazole group, an imidazopyridine group, an imidazopyrimidine group, or an azacarbazole group, each unsubstituted or substituted with at least one of deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a cyano group-containing phenyl group, a cyano group-containing biphenyl group, a cyano group-containing terphenyl group, a cyano group-containing naphthyl group, a pyridinyl group, a phenylpyridinyl group, a diphenylpyridinyl group, a biphenylpyridinyl group, a di(biphenyl)pyridinyl group, a pyrazinyl group, a phenylpyrazinyl group, a diphenylpyrazinyl group, a biphenylpyrazinyl group, a di(biphenyl)pyrazinyl group, a pyridazinyl group, a phenylpyridazinyl group, a diphenylpyridazinyl group, a biphenylpyridazinyl group, a di(biphenyl)pyridazinyl group, a pyrimidinyl group, phenylpyrimidinyl group, a diphenylpyrimidinyl group, a biphenylpyrimidinyl group, a di(biphenyl)pyrimidinyl group, a triazinyl group, a phenyltriazinyl group, a diphenyltriazinyl group, a biphenyltriazinyl group, a di(biphenyl)triazinyl group, —Si(Q31)(Q32)(Q33), —N(Q31)(Q32), —B(Q31)(Q32), —C(═O)(Q31), —S(═O)2(Q31), —P(═O)(Q31)(Q32), —P(Q31)(Q32), or a combination thereof,
In one or more embodiments,
wherein, in Formulae 5-1 to 5-3 and 6-1 to 6-33,
Q31 to Q33 may each be as described herein.
In one or more embodiments, L301 may be a group represented by one of Formulae 5-2, 5-3, or 6-8 to 6-33.
In one or more embodiments, R301 may be a cyano group or a group represented by one of Formulae 7-1 to 7-18, and at least one Ar402 may be a group represented by one of Formulae 7-1 to 7-18:
wherein, in Formulae 7-1 to 7-18,
In Formula E-1, two or more of Ar301 may be identical to or different from each other, and two or more of L301 may be identical to or different from each other. In Formula H-1, two or more of L401 may be identical to or different from each other, and two or more of Ar402 may be identical to or different from each other.
In one or more embodiments, the electron-transporting host may be represented by Formula E-2, but embodiments are not limited thereto:
In one or more embodiments, in Formula E-2, ring CY23 and ring CY24 may each independently be a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
In one or more embodiments, ring CY23 and ring CY24 may each independently be a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a cyclopentadiene group, a 1,2,3,4-tetrahydronaphthalene group, a 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, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, or a 5,6,7,8-tetrahydroquinoline group, each unsubstituted or substituted with at least one R10a. R10a may be as described herein in connection with R23.
In one or more embodiments, ring CY23 and ring CY24 may each independently be a benzene group, a naphthalene group, or a pyridine group.
In one or more embodiments, in Formula E-2, X21 may be N or C(R21a), X22 may be N or C(R22a), and X23 may be N or C(R23a).
In one or more embodiments, in Formula E-2, at least one of X21 to X23 may be N.
For example, one of X21 to X23 may be N, two of X21 to X23 may each be N, and X21 to X23 may each be N.
In one or more embodiments, in Formula E-2, L21 and L22 may each independently be a single bond, a substituted or unsubstituted C3-C60 carbocyclic group, or a substituted or unsubstituted C1-C60 heterocyclic group.
For example, L21 and L22 may each independently be:
In one or more embodiments, in Formula E-2, L21 and L22 may each independently be:
wherein, in Formulae L-1 to L-12,
In one or more embodiments, in Formula E-2, n21 and n22 each indicate the number of L21(s) and L22(s), respectively, and may each independently be an integer from 0 to 5 (for example, 0, 1, 2, or 3). When n21 is 2 or greater, two or more of L21 may be identical to or different from each other, and when n22 is 2 or greater, two or more of L22 may be identical to or different from each other.
In one or more embodiments, in Formula E-2, R21 to R24, R21a, R22a, and R23a may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C7-C60 alkyl aryl group, a substituted or unsubstituted C7-C60 aryl alkyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C2-C60 alkyl heteroaryl group, a substituted or unsubstituted C2-C60 heteroaryl alkyl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —Ge(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q9), or —P(Q8)(Q9).
At least one substituent of the substituted C5-C30 carbocyclic group, the substituted C1-C30 heterocyclic group, the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted C1-C60 alkylthio group, the substituted C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C1-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C7-C60 alkyl aryl group, the substituted C7-C60 aryl alkyl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl group, the substituted C2-C60 alkyl heteroaryl group, the substituted C2-C60 heteroaryl alkyl group, the substituted C1-C60 heteroaryloxy group, the substituted C1-C60 heteroarylthio group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may be:
In Formula E-2, b21 to b24 each indicate the number of R21(s) to R24(s), respectively, and may each independently be an integer from 0 to 10 (for example, 0, 1, 2, or 3). When b21 is 2 or greater, two or more of R21 may be identical to or different from each other, when b22 is 2 or greater, two or more of R22 may be identical to or different from each other, when b23 is 2 or greater, two or more of R23 may be identical to or different from each other, and when b24 is 2 or greater, two or more of R24 may be identical to or different from each other.
For example, in Formula E-2, R21 to R24, R21a, R22a, and R23a may each independently be:
In one or more embodiments, R21 to R24, R21a, R22a, and R23a may each independently be:
wherein, in Formulae 9-1 to 9-61, 9-201 to 9-240, 10-1 to 10-129, and 10-201 to 10-355, * indicates a binding site to a neighboring atom, “Ph” represents a phenyl group, “TMS” represents a trimethylsilyl group, “TMG” represents a trimethylgermyl group, and “t-Bu” represents a t-butyl group.
In one or more embodiments, R21 and R22 may each independently be:
In one or more embodiments, R21 and R22 may each independently be a C6-C60 aryl group unsubstituted or substituted with at least one R10a, a group represented by Formula E-2A, or a group represented by Formula E-2B, and
wherein, in Formulae E-2A and E-2B,
Non-limiting examples of the electron-transporting host include, for example, compounds of Groups HE1 to HE8, but embodiments are not limited thereto:
In one or more embodiments, the hole-transporting host may include at least one of Compounds H-H1 to H-H103, but embodiments are not limited thereto:
In one or more embodiments, the bipolar host may be a compound of Group HEH1, but embodiments are not limited thereto:
The term “Ph” as used herein is a phenyl group.
In one or more embodiments, an example of the hole-transporting host may be Compound H1, but embodiments are not limited thereto. In one or more embodiments, an example of the electron-transporting host may be Compound H2, but embodiments are not limited thereto:
The dopant included in the emission layer 15 may include a phosphorescent dopant, a fluorescent dopant, or a combination thereof.
In one or more embodiments, the emission layer 15 may include a host, a fluorescent dopant, and a phosphorescent dopant, and the host may include at least one of the heterocyclic compounds represented by Formula 1. In this regard, the phosphorescent dopant may be a sensitizer compound that is used together with a fluorescent dopant to transfer excitons to the fluorescent dopant.
For example, the phosphorescent dopant may be a blue dopant.
In one or more embodiments, the phosphorescent dopant may include a transition metal and a tetradentate ligand. In one or more embodiments, the phosphorescent dopant may include a transition metal and at least one of a monodentate ligand, a bidentate ligand, or a tridentate ligand.
In one or more embodiments, the phosphorescent dopant may include at least one organometallic compound represented by Formula 31:
wherein, in Formula 31, M31 may be a transition metal.
In one or more embodiments, M31 may be iridium, platinum, palladium, gold, osmium, titanium, zirconium, hafnium, europium, terbium, thulium, or rhodium. In one or more embodiments, M31 may be platinum, palladium, or gold.
In Formula 31, X31 to X34 may each independently be C or N, and two of a bond between X31 and M31, a bond between X32 and M31, a bond between X33 and M31, and a bond between X34 and M31 may be coordinate bonds, and the other two may be covalent bonds.
In one or more embodiments, a bond between X31 and M31 may be a coordinate bond.
In one or more embodiments, X31 may be C, and a bond between X31 and M31 may be a coordinate bond. That is, X31 in Formula 3 may be C in a carbene moiety.
In Formula 31, ring CY31 to ring CY34 may each independently be a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
In one or more embodiments, ring CY31 to ring CY34 may each independently be:
In Formula 31, L31 may be a single bond, a double bond, *—N(R35a)—*′, *—B(R35a)—*′ *—P(R35a)—*′, *—C(R35a)(R35b)—*′, *—Si(R35a)(R35b)—*′, *—Ge(R35a)(R35b)—*′, *—S—*′, *—Se—*′, *—O—*′, *—C(═O)—*′, *—S(═O)—*′, *—S(═O)2—*′ *—C(R35a)═*′, *═C(R35a)—*′, *—C(R35a)═C(R35b)—*′, *—C(═S)—*′, *—C≡C—*′, a C5-C30 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C30 heterocyclic group unsubstituted or substituted with at least one R10a, L32 may be a single bond, a double bond, *—N(R36a)—*′, *—B(R36a)—*′, *—P(R36a)—*′, *—C(R36a)(R36b)—*′, *—Si(R36a)(R36b)—*′, *—Ge(R36a)(R36b)—*′, *—S—* , *—Se—*′, *—O—*′, *—C(═O)—*′, *—S(═O)—*′, *—S(═O)2—*′ *—C(R36a)═*′, *═C(R36a)—*′, *—C(R36a)═C(R36b)—*′, *—C(═S)—*′, *—C≡C—*′, a C5-C30 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C30 heterocyclic group unsubstituted or substituted with at least one R10a,
In Formula 31, n31 to n34 may each independently be an integer from 0 to 5, wherein three or more of n31 to n34 may each independently be an integer from 1 to 5.
In Formula 31, when n31 is 0, L31 is absent, when n32 is 0, L32 is absent, when n33 is 0, L33 is absent, and when n34 is 0, L34 is absent.
In Formula 31, when n31 is 2 or greater, two or more of L31 may be identical to or different from each other, when n32 is 2 or greater, two or more of L32 may be identical to or different from each other, when n33 is 2 or greater, two or more of L33 may be identical to or different from each other, and when n34 is 2 or more, two or greater of L34 may be identical to or different from each other.
In Formula 31, R31 to R34, R35a, R35b, R36a, R36b, R37a, R37b, R38a, and R38b may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C7-C60 alkyl aryl group, a substituted or unsubstituted C7-C60 aryl alkyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C2-C60 heteroaryl alkyl group, a substituted or unsubstituted C2-C60 heteroaryl alkyl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —Ge(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q9), or —P(Q8)(Q9).
In one or more embodiments, R31 to R34, R35a, R35b, R36a, R36b, R37a, R37b, R38a, and R38b may each independently be:
In one or more embodiments, the phosphorescent dopant may include at least one of the organometallic compounds represented by Formulae 31-1 or 31-2:
wherein, in Formula 31, b31 to b34 may each independently be an integer from 0 to 20.
In Formula 31, at least two of R31 may optionally be bonded to each other to form a C5-C30 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C30 heterocyclic group unsubstituted or substituted with at least one R10a,
At least two of R32 may optionally be bonded to each other to form a C5-C30 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C30 heterocyclic group unsubstituted or substituted with at least one R10a,
In Formulae 31-1 and 31-2,
In one or more embodiments, in Formulae 31-1 and 31-2, R311 to R317 may each independently be:
For example, in Formulae 31-1 and 31-2, at least one of R311 to R317 may include a C1-C20 alkyl group, a C6-C60 aryl group, a C7-C60 alkyl aryl group, or a C7-C60 aryl alkyl group, each unsubstituted or substituted with at least one of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a phenyl group, a cumyl group, or a combination thereof.
In one or more embodiments, the phosphorescent dopant may include an organometallic compound represented by Formula 51:
M51(L51)n51(L52)n52 Formula 51
wherein M51 in Formula 51 may be a transition metal.
In one or more embodiments, M51 may be a first-row transition metal of the Periodic Table of Elements, a second-row transition metal of the Periodic Table of Elements, or a third-row transition metal of the Periodic Table of Elements.
In one or more embodiments, M51 may be iridium, platinum, palladium, gold, osmium, titanium, zirconium, hafnium, europium, terbium, thulium, or rhodium.
In one or more embodiments, M51 may be iridium, platinum, osmium, or rhodium.
In Formula 51, L51 may be a ligand represented by Formula 51 Å, and L52 may be a ligand represented by Formula 51B:
wherein Formulae 51A and 51B are each as described herein.
In Formula 51, n51 may be 1, 2, or 3, wherein, when n51 is 2 or greater, two or more of L51 identical to or different from each other.
In Formula 52, n52 may be 0, 1, or 2, wherein, when n52 is 2 or greater, two or more of L52 identical to or different from each other.
In Formula 51, a sum of n51 and n52 may be 2 or 3. For example, the sum of n51 and n52 may be 3.
In one or more embodiments, in Formula 51, i) M51 may be iridium, and the sum of n51+n52 may be 3; or ii) M51 may be platinum, and the sum of n51+n52 may be 2.
In one or more embodiments, in Formula 51, M51 may be iridium, and regarding n51 and n52, i) n51 may be 1, and n52 may be 2; or ii) n51 may be 2, and n52 may be 1.
In Formula 51, L51 and L52 may be different from each other.
In Formulae 51A and 51B, Y51 to Y54 may each independently be C or N. For example, Y51 and Y53 may each be N, and Y52 and Y54 may each be C.
In Formulae 51A and 51B, ring CY51 to ring CY54 may each independently be a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
For example, ring CY51 to ring CY54 may each independently be i) a third ring, ii) a fourth ring, iii) a condensed ring group in which two or more third rings are condensed with each other, iv) a condensed ring group in which two or more fourth rings are condensed with each other, or v) a condensed ring group in which at least one third ring is condensed with at least one fourth ring,
In one or more embodiments, in Formulae 51A and 5B, ring CY1 to ring CY4 may each independently be a cyclopentane group, a cyclohexane group, a cyclohexene group, a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a 1,2,3,4-tetrahydronaphthalene group, a cyclopentadiene group, a pyrrole group, a furan group, a thiophene group, a silole group, a borole group, a phosphole group, a germole group, a selenophene group, an indene group, an indole group, a benzofuran group, a benzothiophene group, a benzosilole group, a benzoborole group, a benzophosphole group, a benzogermole group, a benzoselenophene group, a fluorene group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, a dibenzosilole group, a dibenzoborole group, a dibenzophosphole group, a dibenzogermole group, a dibenzoselenophene group, a benzofluorene group, a benzocarbazole group, a naphthobenzofuran group, a naphthobenzothiophene group, a naphthobenzosilole group, a naphthobenzoborole group, a naphthobenzophosphole group, a naphthobenzogermole group, a naphthobenzoselenophene group, a dibenzofluorene group, a dibenzocarbazole group, a dinaphthofuran group, a dinaphthothiophene group, a dinaphthosilole group, a dinaphthoborole group, a dinaphthophosphole group, a dinaphthogermole group, a dinaphthoselenophene group, an indenophenanthrene group, an indolophenanthrene group, a phenanthrobenzofuran group, a phenanthrobenzothiophene group, a phenanthrobenzosilole group, a phenanthrobenzoborole group, a phenanthrobenzophosphole group, a phenanthrobenzogermole group, a phenanthrobenzoselenophene group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene group, a 5,5-dioxide group, an azaindene group, an azaindole group, an azabenzofuran group, an azabenzothiophene group, an azabenzosilole group, an azabenzoborole group, an azabenzophosphole group, an azabenzogermole group, an azabenzoselenophene group, an azafluorene group, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, an azadibenzoborole group, an azadibenzophosphole group, an azadibenzogermole group, an azadibenzoselenophene group, an azabenzofluorene group, an azabenzocarbazole group, an azanaphthobenzofuran group, an azanaphthobenzothiophene group, an azanaphthobenzosilole group, an azanaphthobenzoborole group, an azanaphthobenzophosphole group, an azanaphthobenzogermole group, an azanaphthobenzoselenophene group, an azadibenzofluorene group, an azadibenzocarbazole group, an azadinaphthofuran group, an azadinaphthothiophene group, an azadinaphthosilole group, an azadinaphthoborole group, an azadinaphthophosphole group, an azadinaphthogermole group, an azadinaphthoselenophene group, an azaindenophenanthrene group, an azaindolophenanthrene group, an azaphenanthrobenzofuran group, an azaphenanthrobenzothiophene group, an azaphenanthrobenzosilole group, an azaphenanthrobenzoborole group, an azaphenanthrobenzophosphole group, an azaphenanthrobenzogermole group, an azaphenanthrobenzoselenophene group, an azadibenzothiophene 5-oxide group, an aza9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a benzoquinoline group, a benzoisoquinoline group, a benzoquinoxaline group, a benzoquinazoline group, a phenanthroline group, a phenanthridine group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, an azasilole group, an azaborole group, an azaphosphole group, an azagermole group, an azaselenophene group, a benzopyrrole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzisoxazole group, a benzothiazole group, a benzisothiazole group, a benzioxadiazole group, a benzothiadiazole group, a pyridinopyrrole group, a pyridinopyrazole group, a pyridinoimidazole group, a pyridinooxazole group, a pyridinoisoxazole group, a pyridinothiazole group, a pyridinoisothiazole group, a pyridinooxadiazole group, a pyridinothiadiazole group, a pyrimidinopyrrole group, a pyrimidinopyrazole group, a pyrimidinoimidazole group, a pyrimidinooxazole group, a pyrimidinoisoxazole group, a pyrimidinothiazole group, a pyrimidinoisothiazole group, a pyrimidinooxadiazole group, a pyrimidinothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, a 5,6,7,8-tetrahydroquinoline group, an adamantane group, a norbornane group, a norbornene group, a benzene group condensed with a cyclohexane group, a benzene group condensed with a norbornane group, a pyridine group condensed with a cyclohexane group, or a pyridine group condensed with a norbornane group.
In one or more embodiments, ring CY51 and ring CY53 may be different from each other.
In one or more embodiments, ring CY52 and ring CY54 may be different from each other.
In one or more embodiments, ring CY51 to ring CY54 may be different from each other.
In one or more embodiments, in Formulae 51A and 51B, R51 to R54 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C7-C60 alkyl aryl group, a substituted or unsubstituted C7-C60 aryl alkyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C2-C60 alkyl heteroaryl group, a substituted or unsubstituted C2-C60 heteroaryl alkyl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —Ge(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q9), or —P(Q8)(Q9). Q1 to Q9 are each as described herein.
In one or more embodiments, in Formulae 51A and 51B, R51 to R54 may each independently be:
In one or more embodiments, R51 to R54 may each independently be:
In Formulae 51A and 51B, b51 to b54 indicate the number of R51 to R54, respectively, and may each independently be an integer from 0 to 20. When b51 is 2 or greater, two or more of R51 may be identical to or different from each other, when b52 is 2 or greater, two or more of R52 may be identical to or different from each other, when b53 is 2 or greater, two or more of R53 may be identical to or different from each other, and when b54 is 2 or greater, two or more of R54 may be identical to or different from each other. For example, b51 to b54 may each independently be an integer from 0 to 8.
In one or more embodiments, the phosphorescent dopant may include at least one of Compounds P1 to P52, but embodiments are not limited thereto:
Without wishing to be bound to theory, when the phosphorescent dopant is selected from at least one of Compounds P1 to P52, exciplex formation with the aforementioned host compound may be facilitated. For example, the phosphorescent dopant may have, by including bulky substituents (for example, a tert-butyl group, a cumyl group, or the like), an energy level close to that of an energy level of the host compound, and thus exciplex formation may be facilitated. In the case of the phosphorescent dopant, an energy level gap between a LUMO level of the electron-transporting host and a HOMO level of the phosphorescent dopant may be reduced, thereby facilitating the exciplex formation.
In one or more embodiments, the emission layer may further include a fluorescent dopant. For example, the fluorescent dopant may be a thermally activated delayed fluorescence dopant and/or a blue dopant.
The fluorescent dopant may have a difference between a triplet (Ti) energy level and a singlet (Si) energy level of less than or equal to about 0.4 eV.
For example, the fluorescent dopant may be a thermally activated delayed fluorescence (TADF) dopant and/or a blue dopant.
In one or more embodiments, the fluorescent dopant may be a luminescence emitter that may emit a light by receiving excitons from the exciplex of the host and the phosphorescent dopant according to one or more embodiments so that the received excitons transition to a ground state.
In one or more embodiments, the fluorescent dopant may be at least one compound represented by Formula 41, but embodiments are not limited thereto:
wherein, in Formula 41,
In one or more embodiments, R41 to R49 may each independently be:
In one or more embodiments, the compound represented by Formula 41 may be represented by at least one of Formulae 41-1 to 41-9:
wherein, in Formulae 41-1 to 41-9,
In one or more embodiments, the fluorescent dopant may be at least one of Compounds D1 to D30, but embodiments are not limited thereto:
In one or more embodiments, the fluorescent dopant may be included in the emission layer in an amount of about 0 wt % to about 5 wt %, based on total weight of the emission layer.
The hole transport region 12 may be arranged between the first electrode 11 and the emission layer 15 of the organic light-emitting device 10.
The hole transport region 12 may have a single-layer structure or a multi-layer structure.
For example, the hole transport region 12 may have a hole injection layer, a hole transport layer, a hole injection layer/hole transport layer structure, a hole injection layer/first hole transport layer/second hole transport layer structure, a hole injection layer/first hole transport layer/second hole transport layer/electron blocking layer structure, a hole transport layer/organic layer structure, a hole injection layer/hole transport layer/organic layer structure, a hole transport layer/electron blocking layer structure, or a hole injection layer/hole transport layer/electron blocking layer structure.
The hole transport region 12 may include any compound having hole-transporting properties.
The hole transport region 12 may include at least one of the heterocyclic compounds represented by Formula 1. For example, the heterocyclic compound may be included in a hole transport layer, a hole transport layer, an electron blocking layer, or a combination thereof of the hole transport region 12.
For example, the hole transport region 12 may include an amine-based compound.
In one or more embodiments, the hole transport region 12 may include 4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (TDATA), 4,4′,4″-tris{N-(2-naphthyl)-N-phenylamino}-triphenylamine (2-TNATA), N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine (NPB), β-NPB, N,N bis(3-rethylphenyl)-N,N′-diphenyl-[1,1-biphenyl]-4,4′-diamine (TPD), spiro-TPD, spiro-NPB, methylated-NPB, 4,4′-cyclohexylidene bis[N,N-bis(4-methylphenyl)benzenamine] (TAPC), HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor-sulfonic acid (PANI/CSA), polyaniline/poly(4-styrene sulfonate) (PANI/PSS), a compound represented by one of Formulae 201 to 205, or a combination thereof, but embodiments are not limited thereto:
wherein, in Formulae 201 to 205,
For example,
R201 to R206 may each independently be a phenyl group, a biphenyl group, a terphenyl group, a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptalenyl group, an indacenyl group, an acenaphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenalenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a naphthacenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group, an ovalenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, a pyridinyl group, an indeno carbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, or a benzothienocarbazolyl group, each unsubstituted or substituted with at least one of deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, a phenyl group, a biphenyl group, a terphenyl group, a phenyl group substituted with a C1-C10 alkyl group, a phenyl group substituted with —F, a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptalenyl group, an indacenyl group, an acenaphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenalenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a naphthacenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group, an ovalenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, a pyridinyl group, —Si(Q31)(Q32)(Q33), —N(Q31)(Q32), or a combination thereof.
Q11 to Q13 and Q31 to Q33 may each independently be a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 alkylthio group, a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group.
In one or more embodiments, the hole transport region 12 may include a carbazole-containing amine compound.
In one or more embodiments, the hole transport region 12 may include a carbazole-containing amine compound and a carbazole-free amine compound.
The carbazole-containing amine compound may include, for example, one or more compounds represented by Formula 201 including a carbazole group and further including at least one of a dibenzofuran group, a dibenzothiophene group, a fluorene group, a spiro-bifluorene group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, or a benzothienocarbazole group.
The carbazole-free amine compound may include, for example, one or more compounds represented by Formula 201 not including a carbazole group and including at least one of a dibenzofuran group, a dibenzothiophene group, a fluorene group, a spiro-bifluorene group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, or a benzothienocarbazole group.
In one or more embodiments, the hole transport region 12 may include a compound represented by Formula 201, a compound represented by Formula 202, or a combination thereof.
In one or more embodiments, the hole transport region 12 may include a compound represented by Formula 201-1, 202-1, or 201-2, or a combination thereof:
wherein, in Formulae 201-1, 202-1, and 201-2,
In one or more embodiments, the hole transport region 12 may include one of Compounds HT1 to HT39, or a combination thereof, but embodiments are not limited thereto:
In one or more embodiments, the hole transport region 12 of the organic light-emitting device 10 may further include a p-dopant. When the hole transport region 12 further includes a p-dopant, the hole transport region 12 may have a matrix (for example, at least one of compounds represented by Formulae 201 to 205) and a p-dopant included in the matrix. The p-dopant may be uniformly or non-uniformly doped in the hole transport region 12.
In one or more embodiments, the LUMO energy level of the p-dopant may be less than or equal to about −3.5 eV.
The p-dopant may include a quinone derivative, a metal oxide, a cyano group-containing compound, or a combination thereof.
For example, the p-dopant may include:
wherein, in Formula 221,
The compound represented by Formula 221 may include, for example, Compound HT-D2:
The hole transport region 12 may have a thickness of about 100 Å to about 10,000 Å, for example, about 400 Å to about 2,000 Å, and the emission layer 15 may have a thickness of about 100 Å to about 3,000 Å, for example, about 300 Å to about 1,000 Å. Without wishing to be bound to theory, when the thickness of each of the hole transport region 12 and the emission layer 15 is within these ranges, satisfactory hole transportation characteristics and/or luminescence characteristics may be obtained without a substantial increase in driving voltage.
The hole transport region 12 may further include a buffer layer.
The buffer layer may compensate for an optical resonance distance according to a wavelength of light emitted from the emission layer 15, and thus, efficiency of a formed organic light-emitting device may be further improved.
The hole transport region 12 may further include an electron blocking layer. The electron blocking layer may include a known material, for example, mCP or 2,8-bis(diphenylphosphineoxide)dibenzofuran (DBFPO), but embodiments are not limited thereto:
The electron transport region 17 may be arranged between the emission layer 15 and the second electrode 19 of the organic light-emitting device 10.
The electron transport region 17 may have a single-layer structure or a multi-layer structure.
For example, the electron transport region 17 may have an electron transport layer, an electron transport layer/electron injection layer structure, a buffer layer/electron transport layer structure, hole blocking layer/electron transport layer structure, a buffer layer/electron transport layer/electron injection layer structure, or a hole blocking layer/electron transport layer/electron injection layer structure. The electron transport region 17 may further include an electron control layer.
The electron transport region 17 may include at least one of the heterocyclic compounds represented by Formula 1. For example, the heterocyclic compound may be included in a buffer layer or the like of the electron transport region 17.
The electron transport region 17 may include a known electron-transporting materials.
The electron transport region 17 (for example, a buffer layer, a hole blocking layer, an electron control layer, or an electron transport layer in the electron transport region) may include a metal-free compound containing at least one π electron-deficient nitrogen-containing C1-C60 cyclic group. The π electron-deficient nitrogen-containing C1-C60 cyclic group may be as described herein.
For example, the electron transport region 17 may include a compound represented by Formula 601, but embodiments are not limited thereto:
[Ar601]xe11-[(L601)xe1-R601]xe21 Formula 601
wherein, in Formula 601,
In one or more embodiments, at least one of Ar601 and R601 may include the π electron-deficient nitrogen-containing C1-C60 cyclic group.
In one or more embodiments, Ar601 and L601 in Formula 601 may each independently be a benzene group, a naphthalene 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 pentaphene group, an indenoanthracene group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, 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 pyrimidine group, a pyridazine group, an indazole group, a purine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a phthalazine group, a naphthyridine group, a quinoxaline group, a quinazoline group, a cinnoline group, a phenanthridine group, an acridine 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, or an azacarbazole group, each unsubstituted or substituted with at least one of deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazino group, a hydrazono group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, —Si(Q31)(Q32)(Q33), —S(═O)2(Q31), —P(═O)(Q31)(Q32), —P(Q31)(Q32), or a combination thereof, and
When xe11 in Formula 601 is 2 or more, two or more of Ar601 may be linked to each other via a single bond.
In one or more embodiments, Ar601 in Formula 601 may be an anthracene group.
In one or more embodiments, the compound represented by Formula 601 may be represented by Formula 601-1:
wherein, in Formula 601-1,
In one or more embodiments, xe1 and xe611 to xe613 in Formulae 601 and 601-1 may each independently be 0, 1, or 2.
In one or more embodiments, R601 and R611 to R613 in Formulae 601 and 601-1 may each independently be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, a pyridinyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a thiadiazolyl group, an oxadiazolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a benzimidazolyl group, an isobenzothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, or an azacarbazolyl group, each unsubstituted or substituted with at least one of deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazino group, a hydrazono group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, a pyridinyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a thiadiazolyl group, an oxadiazolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a benzimidazolyl group, an isobenzothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an azacarbazolyl group, or a combination thereof; or
The electron transport region 17 may include one of Compounds ET1 to ET36 or a combination thereof, but embodiments are not limited thereto:
In one or more embodiments, the electron transport region 17 may include 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), Alq3, BAlq, 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole (NTAZ), 2,8-bis(diphenyl phosphineoxide)dibenzofuran (DBFPO), or a combination thereof. For example, when the electron transport region 17 includes a hole blocking layer, the hole blocking layer may include BCP or Bphen, but embodiments are not limited thereto:
Thicknesses of the buffer layer, the hole blocking layer, and the electron control layer may each independently be about 20 Å to about 1,000 Å, for example, about 30 Å to about 300 Å. Without wishing to be bound to theory, when the thicknesses of the buffer layer, the hole blocking layer, and the electron control layer are within these ranges, excellent hole blocking characteristics or excellent electron control characteristics may be obtained without a substantial increase in driving voltage.
A thickness of the electron transport layer may be about 100 Å to about 1,000 Å, for example, about 150 Å to about 500 Å. Without wishing to be bound to theory, when the thickness of the electron transport layer is within these ranges, satisfactory electron transporting characteristics may be obtained without a substantial increase in driving voltage.
The electron transport region 17 (for example, the electron transport layer in the electron transport region 17) may further include, in addition to the aforementioned materials, a metal-containing material.
The metal-containing material may include an alkali metal complex, an alkaline earth metal complex, or a combination thereof. A metal ion of the alkali metal complex may include a Li ion, a Na ion, a K ion, a Rb ion, a Cs ion, or a combination thereof, and a metal ion of the alkaline earth metal complex may include a Be ion, a Mg ion, a Ca ion, a Sr ion, a Ba ion, or a combination thereof. A ligand coordinated with the metal ion of the alkali metal complex or the alkaline earth-metal complex may include a hydroxyquinoline, a hydroxyisoquinoline, a hydroxybenzoquinoline, a hydroxyacridine, a hydroxyphenanthridine, a hydroxyphenyloxazole, a hydroxyphenylthiazole, a hydroxydiphenyloxadiazole, a hydroxydiphenylthiadiazole, a hydroxyphenylpyridine, a hydroxyphenylbenzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or a combination thereof.
In one or more embodiments, the metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 (LiQ) or ET-D2, but embodiments are not limited thereto:
The electron transport region 17 may include an electron injection layer that facilitates the injection of electrons from the second electrode 19. The electron injection layer may directly contact the second electrode 19.
The electron injection layer may have i) a single-layer structure consisting of a single layer including a single material, ii) a single-layer structure consisting of a single layer including multiple materials that are different from each other, or iii) a multi-layer structure consisting of multiple layers including multiple materials that are different from each other.
The electron injection layer may include an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal compound, an alkaline earth-metal compound, a rare earth metal compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or a combination thereof.
The alkali metal may include Li, Na, K, Rb, Cs, or a combination thereof. In one or more embodiments, the alkali metal may be Li, Na, or Cs. In one or more embodiments, the alkali metal may be Li or Cs.
The alkaline earth metal may include Mg, Ca, Sr, Ba, or a combination thereof.
The rare earth metal may include Sc, Y, Ce, Tb, Yb, Gd, or a combination thereof.
The alkali metal compound, the alkaline earth metal compound, and the rare earth metal compound may include oxides and halides (for example, fluorides, chlorides, bromides, or iodides) of the alkali metal, the alkaline earth metal, and the rare earth metal, or a combination thereof.
The alkali metal compound may include one of alkali metal oxides such as Li2O, Cs2O, K2O, or the like, or a combination thereof; one of alkali metal halides such as LiF, NaF, CsF, KF, LiI, NaI, CsI, KI, or the like, or a combination thereof; or a combination thereof. In one or more embodiments, the alkali metal compound may include LiF, Li2O, NaF, LiI, NaI, CsI, KI, or a combination thereof.
The alkaline earth-metal compound may include one of alkaline earth-metal compounds, such as BaO, SrO, CaO, BaxSr1-xO (wherein 0<x<1), or BaxCa1-xO (wherein 0<x<1), or the like, or a combination thereof. In one or more embodiments, the alkaline earth metal compound may include BaO, SrO, CaO, or the like, or a combination thereof.
The rare earth metal compound may include YbF3, ScF3, Sc2O3, Y2O3, Ce2O3, GdF3, TbF3, or the like, or a combination thereof. In one or more embodiments, the rare earth metal compound may include YbF3, ScF3, TbF3, YbI3, ScI3, TbI3, or the like, or a combination thereof.
The alkali metal complex, the alkaline earth metal complex, and the rare earth metal complex may include an ion of an alkali metal, an alkaline earth metal, and/or a rare earth metal as described above, and a ligand coordinated with a metal ion of the alkali metal complex, the alkaline earth metal complex, or the rare earth metal complex may include hydroxy quinoline, hydroxy isoquinoline, hydroxy benzoquinoline, hydroxy acridine, hydroxy phenanthridine, hydroxy phenyloxazole, hydroxy phenylthiazole, hydroxy diphenyloxadiazole, hydroxy diphenylthiadiazole, hydroxy phenylpyridine, hydroxy phenylbenzimidazole, hydroxy phenylbenzothiazole, bipyridine, phenanthroline, cyclopentadiene, or the like, or a combination thereof.
The electron injection layer may consist of an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal compound, an alkaline earth-metal compound, a rare earth metal compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or a combinations thereof, as described above. In one or more embodiments, the electron injection layer may further include an organic material. When the electron injection layer further includes an organic material, an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal compound, an alkaline earth-metal compound, a rare earth metal compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or a combination thereof may be homogeneously or non-homogeneously dispersed in a matrix including the organic material.
A thickness of the electron injection layer may be about 1 Å to about 100 Å, and, for example, about 3 Å to about 90 Å. Without wishing to be bound to theory, when the thickness of the electron injection layer is within these ranges, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.
The second electrode 19 may be arranged on the aforementioned organic layer 10A. The second electrode 19 may be a cathode which is an electron injection electrode, and in this regard, a material for forming the second electrode 19 may be selected from a metal, an alloy, an electrically conductive compound, and a combination thereof, which have a relatively low work function.
The second electrode 19 may include Li, Ag, Mg, Al, Al—Li, Ca, Mg—In, Mg—Ag, ITO, IZO, or a combination thereof. The second electrode 19 may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode.
The second electrode 19 may have a single-layer structure having a single layer or a multi-layer structure including two or more layers.
The term “C1-C60 alkyl group” as used herein refers to a linear or branched saturated aliphatic hydrocarbons monovalent group having 1 to 60 carbon atoms, and the term “C1-C60 alkylene group, as used here refers to a divalent group having the same structure as the C1-C60 alkyl group.
Non-limiting examples of the C1-C60 alkyl group, the C1-C20 alkyl group, and/or the C1-C10 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, or a tert-decyl group, each unsubstituted or substituted with at least one of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, or the like, or a combination thereof.
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 non-limiting examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, or the like.
The term “C1-C60 alkylthio group” as used herein refers to a monovalent group represented by —SA101, (wherein A101, is the C1-C60 alkyl group).
The term “C2-C60 alkenyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60 alkyl group, and non-limiting examples thereof include an ethenyl group, a propenyl group, a butenyl group, or the like. The term “C2-C60 alkenylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60 alkyl group, and non-limiting examples thereof include an ethynyl group, a propynyl group, or the like. 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 ring group having 3 to 10 carbon atoms, and the term “C3-C10 cycloalkylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkyl group.
Non-limiting examples of the C3-C10 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group (a bicyclo[2.2.1]heptyl group), a bicyclo[1.1.1]pentyl group, a bicyclo[2.1.1]hexyl group, a bicyclo[2.2.2]octyl group, or the like.
The term “C1-C10 heterocycloalkyl group” as used herein refers to a monovalent monocyclic group that includes at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and 1 to 10 carbon atoms as ring-forming atom(s), and the term “the C1-C10 heterocycloalkylene group” as used herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkyl group.
Non-limiting examples of the C1-C10 heterocycloalkyl group include a silolanyl group, a silinanyl group, tetrahydrofuranyl group, a tetrahydro-2H-pyranyl group, a tetrahydrothiophenyl group, or the like.
The term “C3-C10 cycloalkenyl group” as used herein refers to a monovalent cyclic group that includes 3 to 10 carbon atoms and at least one carbon-carbon double bond in the ring thereof and has no aromaticity, and non-limiting examples thereof include a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, or the like. The term “C3-C10 cycloalkenylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkenyl group.
The term “C1-C10 heterocycloalkenyl group” as used herein refers to a monovalent monocyclic group that has at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom, 1 to 10 carbon atoms as ring-forming atom(s), and at least one double bond in the ring thereof. Non-limiting examples of the C1-C10 heterocycloalkenyl group include a 2,3-dihydrofuranyl group, a 2,3-dihydrothiophenyl group, or the like. The term “C1-C10 heterocycloalkenylene group” as used herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as used herein refers to a monovalent group having a carbocyclic aromatic ring 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 ring 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, a chrysenyl group, or the like. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the rings may be fused to each other.
The term “C7-C60 alkyl aryl group” as used herein refers to a C6-C60 aryl group substituted with at least one C1-C60 alkyl group. The term “C7-C60 aryl alkyl group” as used herein refers to a C1-C60 alkyl group substituted with at least one C6-C60 aryl group.
The term “C1-C60 heteroaryl group” as used herein refers to a monovalent group that includes at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and a heterocyclic aromatic ring system having 1 to 60 carbon atoms as ring-forming atom(s), and the term “C1-C60 heteroarylene group” as used herein refers to a divalent group that includes at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and a heterocyclic aromatic ring system having 1 to 60 carbon atoms as ring-forming atom(s).
Non-limiting examples of the C1-C60 heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, or the like. When the C1-C60 heteroaryl group and the C1-C60 heteroarylene group each include two or more rings, the rings may be fused to each other.
The term “C2-C60 alkyl heteroaryl group” as used herein refers to a C1-C60 heteroaryl group substituted with at least one C1-C60 alkyl group. The term “C2-C60 heteroaryl alkyl group” as used herein refers to a C1-C60 alkyl group substituted with at least one C1-C60 heteroaryl group.
The term “C6-C60 aryloxy group” as used herein indicates —OA102 (wherein A102 is the C6-C60 aryl group), and the term “C6-C60 arylthio group” as used herein indicates —SA103 (wherein A103 is the C6-C60 aryl group).
The term “C1-C60 heteroaryloxy group” as used herein indicates —OA102′ (wherein A102′ is the C1-C60 heteroaryl group), and the term “C1-C60 heteroarylthio group” as used herein indicates —SA103′ (wherein A103′ is the C1-C60 heteroaryl group).
The term “monovalent non-aromatic condensed polycyclic group” as used herein refers to a monovalent group in which two or more rings are condensed with each other, only carbon is used as a ring-forming atom (for example, the number of carbon atoms may be 8 to 60), and the whole molecule is a non-aromatic group. Non-limiting examples of the monovalent non-aromatic condensed polycyclic group include a fluorenyl group or the like. 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 described above.
The term “monovalent non-aromatic condensed heteropolycyclic group” as used herein refers to a monovalent group having two or more rings condensed with each other, a heteroatom selected from N, O, P, Si, S, Se, Ge, and B, other than carbon atoms (for example, having 1 to 60 carbon atoms), as a ring-forming atom, and no aromaticity in the entire molecular structure thereof. Non-limiting examples of the monovalent non-aromatic condensed heteropolycyclic group include a carbazolyl group or the like. 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 described above.
The term “π electron-depleted nitrogen-containing C1-C60 cyclic group” as used herein refers to a ring group having 1 to 60 carbon atoms and including at least one *—N═*′ (wherein * and *′ each indicate a binding site to a neighboring atom) as a ring-forming moiety. For example, the π electron-depleted nitrogen-containing C1-C60 cyclic group may be a) a first ring, b) a condensed ring in which at least two first rings are condensed, or c) a condensed ring in which at least one first ring and at least one second ring are condensed.
The term “π electron-rich C3-C60 cyclic group” as used herein refers to a ring group having 3 to 60 carbon atoms and not including at least one *—N═*′ (wherein * and *′ each indicate a binding site to a neighboring atom) as a ring-forming moiety. For example, the π electron-rich C3-C60 cyclic group may be a) a second ring or b) a condensed ring in which at least two second rings are condensed.
The term “C5-C60 cyclic group” as used herein refers to a monocyclic or polycyclic group having 5 to 60 carbon atoms, and may be, for example, a) a third ring or b) a condensed ring group in which at least two third rings are condensed to each other.
The “C1-C60 heterocyclic group” as used herein refers to a monocyclic or polycyclic group including at least one heteroatom and 1 to 60 carbon atoms, and may be, for example, a) a fourth ring, b) a condensed ring in which at least two fourth rings are condensed, or c) a condensed ring in which at least one third ring is condensed with at least one fourth ring.
The “first ring” as used herein 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, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, or a thiadiazole group.
The “second ring” as used herein may be a benzene group, a cyclopentadiene group, a pyrrole group, a furan group, a thiophene group, or a silole group.
The “third ring” as used herein may be a cyclopentane group, a cyclopentadiene group, an indene group, an adamantane group, a norbornene group, a bicyclo[1.1.1]pentane group, a bicyclo[2.1.1]hexane group, a bicyclo[2.2.1]heptane group (a norbornane group), a bicyclo[2.2.2]octane group, a cyclohexane group, a cyclohexene group, or a benzene group.
The “fourth ring” as used herein may be a furan group, a thiophene group, a pyrrole group, a silole group, an oxazole group, an isoxazole group, an oxadiazole group, an isoxadiazole group, oxatriazole group, an isoxatriazole group, a thiazole group, an isothiazole group, a thiadiazole group, an isothiadiazole group, a thiatriazole group, an isotriazole group, a pyrazole group, an imidazole group, a triazole group, a tetrazole group, an azasilole group, a diazasilole group, a triazasilole group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, or a triazine group.
For example, the π electron-depleted nitrogen-containing C1-C60 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, an acridine 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 azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, an acridine group, or a pyridinopyrazole group.
For example, the π electron-rich C3-C60 cyclic group may be a benzene group, a heptalene group, an indene group, a naphthalene group, an azulene group, an indacene group, an 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, a furan group, a thiophene group, an isoindole group, an indole group, an indene group, a benzofuran group, a benzothiophene group, a benzosilole group, a naphthopyrrole group, a naphthofuran group, a naphthothiophene group, a naphthosilole group, a benzocarbazole group, a dibenzocarbazole 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, a triindolobenzene group, a pyrrolophenanthrene group, a furanophenanthrene group, a thienophenanthrene group, a benzonaphthofuran group, a benzonaphthothiophene group, an (indolo)phenanthrene group, a (benzofurano)phenanthrene group, or a (benzothieno)phenanthrene group.
For example, the C5-C60 carbocyclic group may be a cyclopentane group, a cyclohexane group, a cyclohexene group, a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a 1,2,3,4-tetrahydronaphthalene group, cyclopentadiene group, an indene group, a fluorene group, a 5,6,7,8-tetrahydroisoquinoline group, a 5,6,7,8-tetrahydroquinoline group, an adamantane group, a norbornane group, or a norbornene group.
For example, the C1-C60 heterocyclic group may be a thiophene group, a furan group, a pyrrole group, a cyclopentadiene group, a silole group, a borole group, a phosphole group, a selenophene group, a germole group, a benzothiophene group, a benzofuran group, an indole group, an indene group, a benzosilole group, a benzoborole group, a benzophosphole group, a benzoselenophene group, a benzogermole group, a dibenzothiophene group, a dibenzofuran group, a carbazole group, a dibenzosilole group, a dibenzoborole group, a dibenzophosphole group, a dibenzoselenophene group, a dibenzogermole group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azabenzothiophene group, an azabenzofuran group, an azaindole group, an azaindene group, an azabenzosilole group, an azabenzoborole group, an azabenzophosphole group, an azabenzoselenophene group, an azabenzogermole group, an azadibenzothiophene group, an azadibenzofuran group, an azacarbazole group, an azafluorene group, an azadibenzosilole group, an azadibenzoborole group, an azadibenzophosphole group, an azadibenzoselenophene group, an azadibenzogermole group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, or a benzothiadiazole group.
The terms “a π electron-deficient nitrogen-containing C1-C60 cyclic group, a π electron-rich C3-C60 cyclic group, a C5-C60 cyclic group, and a C1-C60 heterocyclic group” as used herein each refer to a part of a condensed ring or a monovalent, a divalent, a trivalent, a tetravalent, a pentavalent, or a hexavalent ring group, depending on the formula structure.
Substituents of the substituted π electron-deficient nitrogen-containing C1-C60 cyclic group, the substituted π electron-rich C3-C60 cyclic group, the substituted C5-C60 cyclic group, the substituted C1-C60 heterocyclic group, the substituted C1-C60 alkylene group, the substituted C2-C60 alkenylene group, the substituted C2-C60 alkynylene group, the substituted C3-C10 cycloalkylene group, the substituted C1-C10 heterocycloalkylene group, the substituted C3-C10 cycloalkenylene group, the substituted C1-C10 heterocycloalkenylene group, the substituted C6-C60 arylene group, the substituted C1-C60 heteroarylene group, the substituted divalent non-aromatic condensed polycyclic group, the substituted divalent non-aromatic condensed heteropolycyclic group, the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted C1-C60 alkylthio group, the substituted C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C1-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C7-C60 alkyl aryl group, the substituted C7-C60 aryl alkyl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl group, the substituted C2-C60 alkyl heteroaryl group, the substituted C2-C60 heteroaryl alkyl group, the substituted C1-C60 heteroaryloxy group, the substituted C1-C60 heteroarylthio group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may each independently be:
Q1 to Q9, Q11 to Q19, Q21 to Q29, and Q31 to Q39 as described herein may each independently be 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 substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C7-C60 alkyl aryl group, a substituted or unsubstituted C7-C60 aryl alkyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C2-C60 alkyl heteroaryl group, a substituted or unsubstituted C2-C60 heteroaryl alkyl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group.
For example, Q1 to Q9, Q11 to Q19, Q21 to Q29, and Q31 to Q39 as described herein may each independently be:
The term “room temperature” as used herein refers to a temperature of about 25° C.
The terms “a biphenyl group, a terphenyl group, and a tetraphenyl group” as used herein each refer to a monovalent group having two, three, or four phenyl groups linked via a single bond, respectively.
Hereinafter, a compound and an organic light-emitting device according to exemplary embodiments are described in further detail with reference to Synthesis Examples 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.
Compound 331 was synthesized according to the following reaction scheme:
1-bromo-3-iodobenzene (35 grams (g), 123.7 millimoles (mmol)), (phenyl-d5)boronic acid (13 g, 103 mmol), tetrakis(triphenylphosphine)palladium(0) (5.95 g, 5.15 mmol), and sodium bicarbonate (21.6 g, 257 mmol), were mixed with 400 milliliters (mL) of toluene, 100 mL of ethanol, and 100 mL of deionized (DI) water, and the mixed solution was heated at 120° C. for 16 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and an organic layer was obtained by extraction using ethyl acetate, dried using anhydrous magnesium sulfate (MgSO4), concentrated under reduced pressure, and then purified by a silica column, to synthesize Intermediate 1. (28.3 g, 118.8 mmol, yield of 96%). The product was identified by liquid chromatography-mass spectrometry (LC-MS).
LC-MS: calculated: 237.02, found (M+1): m/z=238.04.
Intermediate 1 (28.1 g, 118.8 mmol), 9H-carbazole-1,2,3,4,5,6,7,8-d8 (20.8 g, 118.8 mmol), sodium tert-butoxide (17.1 g, 178.3 mmol), tris(dibenzylideneacetone)dipalladium(0) (5.4 g, 5.9 mmol), and tri-tert-butylphosphine (4.8 mL, 11.9 mmol) were mixed with 550 mL of toluene, and the mixed solution was heated at 130° C. for 16 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and an organic layer was obtained by extraction using ethyl acetate, dried using anhydrous MgSO4, concentrated under reduced pressure, and then purified by a silica column, to synthesize Intermediate 2 (19.5 g, 60.5 mmol, yield of 51%). The product was identified by LC-MS.
LC-MS: calculated: 332.22, found (M+1): m/z=333.25.
Intermediate 2 (20.1 g, 60.5 mmol) was mixed with 600 mL of dimethyl formamide (DMF), and the mixed solution was stirred at 0° C. While maintaining the temperature at 0° C., N-bromosuccinimide (10.2 g, 57.5 mmol) dissolved in 50 mL of DMF was added dropwise thereto and stirred at room temperature for 16 hours. After completion of the reaction, an organic layer was obtained by extraction using ethyl acetate, dried using anhydrous MgSO4, concentrated under reduced pressure, and then purified by a silica column, to synthesize Intermediate 3 (23.2 g, 56.6 mmol, yield of 93%). The product was identified by LC-MS.
LC-MS: calculated: 409.12, found (M+1): m/z=410.13.
Intermediate 3 (23.2 g, 56.6 mmol), 9H-carbazole-1,2,3,4,5,6,7,8-d8 (10.4 g, 59.4 mmol), sodium tert-butoxide (8.2 g, 84.9 mmol), tris(dibenzylideneacetone)dipalladium(0) (2.1 g, 2.3 mmol), and tri-tert-butylphosphine (1.8 mL, 4.5 mmol) were mixed with 280 mL of toluene, and the mixed solution was heated at 130° C. for 16 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and an organic layer was obtained by extraction using ethyl acetate, dried using anhydrous MgSO4, concentrated under reduced pressure, and then purified by a silica column, to synthesize Intermediate 4 (19.5 g, 38.6 mmol, yield of 68%). The product was identified by LC-MS.
LC-MS: calculated: 504.32, found (M+1): m/z=505.33.
Intermediate 5 was synthesized in a similar manner as used to synthesize Intermediate 3, except that Intermediate 4 was used instead of Intermediate 2 (yield of 72%). The product was identified by LC-MS.
LC-MS: calculated: 581.22, found (M+1): m/z=582.23.
Compound 331 was synthesized in a similar manner as used to synthesize Intermediate 4, except that Intermediate 5 was used instead of Intermediate 3 (yield of 52%). The product was identified by LC-MS.
LC-MS: calculated: 676.42, found (M+1): m/z=677.45.
Compound 339 was synthesized according to the following reaction scheme:
Intermediate 6 was synthesized (yield of 85%) in a similar manner as used to synthesize Intermediate 1 of Synthesis Example 1, except that 1-bromo-4-iodobenzene was used instead of 1-bromo-3-iodobenzene. The product was identified by LC-MS.
LC-MS: calculated: 237.02, found (M+1): m/z=238.04.
Compound 339 was synthesized in a similar manner as used to synthesize Intermediate 4 of Synthesis Example 1, except that Intermediate 6 was used instead of Intermediate 1, Intermediate 7 was used instead of Intermediate 2, Intermediate 7 was used instead of Intermediate 3, and 9H-3,9′-bicarbazole-1,1′,2,2′,3′,4,4′,5,5′,6,6′,7,7′,8,8′-d15 was used instead of 9H-carbazole-1,2,3,4,5,6,7,8-d8. The product was identified by LC-MS.
LC-MS: calculated: 676.42, found (M+1): m/z=677.45.
Compound 183 was synthesized according to the following reaction scheme:
Intermediate 9 was synthesized (yield of 55%) in a similar manner as used to synthesize Intermediate 2 of Synthesis Example 1, except that 2-bromo-9H-carbazole-1,3,4,5,6,7,8-d7 was used instead of 9H-carbazole-1,2,3,4,5,6,7,8-d8. The product was identified by LC-MS.
LC-MS: calculated: 409.12, found (M+1): m/z=410.13.
Compound 183 was synthesized in a similar manner as used to synthesize Intermediate 4 of Synthesis Example 1, except that Intermediate 9 was used instead of Intermediate 3 and 9H-3,9′-bicarbazole-1,1′,2,2′,3′,4,4′,5,5′,6,6′,7,7′,8,8′-d15 was used instead of H-carbazole-1,2,3,4,5,6,7,8-d8. The product was identified by LC-MS.
LC-MS: calculated: 676.42, found (M+1): m/z=677.45.
A glass substrate on which a 1,500 Å-thick indium tin oxide (ITO) electrode (first electrode, anode) was formed was cleaned by ultrasonication using DI water. After the completion of ultrasonication using the DI water, cleaning by ultrasonication using a solvent, including each of isopropyl alcohol, acetone, and methanol, was performed, and the glass substrate was dried and transferred to a plasma cleaner. The glass substrate was cleaned by using oxygen plasma for 5 minutes, and then transferred to a vacuum laminator.
Compound HT3 and Compound HT-D2 were co-deposited by vacuum on the ITO electrode on the glass substrate to form a hole injection layer having a thickness of 100 Å, Compound HT3 was deposited by vacuum on the hole injection layer to form a hole transport layer having a thickness of 1,300 Å, and mCP was deposited by vacuum on the hole transport layer to form an electron blocking layer having a thickness of 100 Å, so as to form a hole transport region.
On the hole transport region, a host and Compound P31 as a dopant were co-deposited by vacuum at a weight ratio of 85:15 to form an emission layer having a thickness of 300 Å. For the host, a first host (Compound 331) and a second host (Compound E1) were used, and a weight ratio thereof was adjusted to 6:4.
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 co-deposited by vacuum on the hole blocking layer to form an electron transport layer having a thickness of 300 Å, LiQ was deposited by vacuum on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and an Al second electrode (cathode) having a thickness of 1,200 Å was formed on the electron injection layer, thereby completing the manufacture of an organic light-emitting device.
Organic light-emitting devices were manufactured in a similar manner as in Example 1, except that compounds shown in Table 2 were each used instead of Compound 331 in forming the emission layer.
For each of the organic light-emitting devices of Examples 1 to 3 and Comparative Examples 1 to 3, the lifespan (T95 at 1,000 cd/A2, relative %) was evaluated with a current-voltage meter (Keithley 2400) and a luminance meter (Minolta Cs-1000A), and results thereof are shown in Table 2. Here, the lifespan (T95) was a measure of the time required for the luminance to decline to 95% of the initial luminance of 100%. The T95 lifespans of the organic light-emitting devices of Examples 1 to 3 were represented as relative values (%) compared to the T95 lifespans of the organic light-emitting devices of Comparative Examples 1 to 3, respectively.
Referring to Table 2, it was confirmed that the organic light-emitting device of Example 1 had a T95 lifespan improvement of up to 178% compared to the organic light-emitting device of Comparative Example 1, the organic light-emitting device of Example 2 had a T95 lifespan improvement of up to 157% compared to the organic light-emitting device of Comparative Example 2, and the organic light-emitting device of Example 3 had a T95 lifespan improvement of up to 188% compared to the organic light-emitting device of Comparative Example 3.
A glass substrate on which a 1,500 Å-thick indium tin oxide (ITO) electrode (first electrode, anode) was formed was cleaned by ultrasonication using DI water. After the completion of ultrasonication using DI water, cleaning by ultrasonication using a solvent, including isopropyl alcohol, acetone, and methanol, was performed, and the glass substrate was dried and transferred to a plasma cleaner. The glass substrate was cleaned by using oxygen plasma for 5 minutes, and then transferred to a vacuum laminator.
Compound HT3 and Compound HT-D2 were co-deposited by vacuum on the ITO electrode on the glass substrate to form a hole injection layer having a thickness of 100 Å, Compound HT3 was deposited by vacuum on the hole injection layer to form a hole transport layer having a thickness of 1,300 Å, and mCP was deposited by vacuum on the hole transport layer to form an electron blocking layer having a thickness of 100 Å, so as to form a hole transport region.
On the hole transport region, a host, a phosphorescent dopant (Compound P31), and a fluorescent dopant (Compound D3) were co-deposited by vacuum at a weight ratio of 85:14:1 to form an emission layer having a thickness of 300 Å. For the host, a first host (Compound 331) and a second host (Compound E1) were used, and a weight ratio thereof was adjusted to 6:4.
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 co-deposited by vacuum on the hole blocking layer to form an electron transport layer having a thickness of 300 Å, LiQ was deposited by vacuum on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and an Al second electrode (cathode) having a thickness of 1,200 Å was formed on the electron injection layer, thereby completing the manufacture of an organic light-emitting device.
Organic light-emitting devices were manufactured in a similar manner as in Example 2, except that compounds shown in Table 3 were each used instead of Compound 331 in forming the emission layer.
For each of the organic light-emitting devices of Examples 4 to 6 and Comparative Examples 4 to 6, the lifespan (T95 at 1,000 cd/cm2, hours) was evaluated with a current-voltage meter (Keithley 2400) and a luminance meter (Minolta Cs-1000A), and results thereof are shown in Table 3. Here, the lifespan (T95, relative %) was a measure of the time required for the luminance to decline to 95% of the initial luminance of 100%. The T95 lifespans of the organic light-emitting devices of Examples 4 to 6 were represented as relative values (%) compared to the T95 lifespans of the organic light-emitting devices of Comparative Examples 4 to 6, respectively.
Referring to Table 3, it was confirmed that the organic light-emitting device of Example 4 had a T95 lifespan improvement of up to 158% compared to the organic light-emitting device of Comparative Example 4, the organic light-emitting device of Example 5 had a T95 lifespan improvement of up to 158% compared to the organic light-emitting device of Comparative Example 5, and the organic light-emitting device of Example 6 had a T95 lifespan improvement of up to 149% compared to the organic light-emitting device of Comparative Example 6.
According to the one or more exemplary embodiments, use of at least one of the heterocyclic compounds represented by Formula 1 may provide an organic light-emitting device having long lifespan characteristics, and an electronic apparatus including the organic light-emitting device may also have long lifespan characteristics.
It should be understood that the exemplary embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each exemplary embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more exemplary embodiments have been described with reference to the FIGURE, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0055745 | May 2022 | KR | national |
| 10-2023-0057772 | May 2023 | KR | national |
