Patent Application
20230363268
This application claims priority under 35 U.S.C. § 119 to Korean Patent Application Nos. 10-2022-0055745, filed on May 4, 2022, and 10-2023-0057363, filed on May 2, 2023, in the Korean Intellectual Property Office, the contents of which are herein incorporated by reference in their entirety.
The present disclosure 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 are self-emissive devices, which have improved characteristics in terms of viewing angles, response time, brightness, driving voltage, and response speed, and produce full-color images.
In an example, an organic light-emitting device includes an anode, a cathode, and an organic layer 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 recombine in the emission layer to produce excitons. The excitons may transition from an excited state to a ground state, thereby generating light.
The need remains for novel materials for organic light-emitting devices.
Provided are a novel 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 description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.
According to an aspect of the disclosure, there is provided a heterocyclic compound represented by Formula 1:
In Formula 1,
in Formula 1 is a group represented by Formula 4-2 or 4-3:
According to another aspect of the disclosure, 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 and including an emission layer, wherein the organic layer includes at least one heterocyclic compound represented by Formula 1.
According to another aspect of the present disclosure, an electronic apparatus includes the organic light-emitting device.
The above and other aspects, features, and advantages of certain embodiments of the disclosure will be more apparent from the following description taken in conjunction with the FIGURE which is a schematic cross-sectional view of an organic light-emitting device 10 according to an embodiment.
Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the FIGURES, to explain aspects. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
It will be understood that when an element is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present therebetween In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
It will be understood that, although the terms “first,” “second,” “third” etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, “a first element,” “component,” “region,” “layer” or “section” discussed below could be termed a second element, component, region, layer or section without departing from the teachings herein.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, “a,” “an,” “the,” and “at least one” do not denote a limitation of quantity, and are intended to cover both the singular and plural, unless the context clearly indicates otherwise. For example, “an element” has the same meaning as “at least one element,” unless the context clearly indicates otherwise.
“Or” means “and/or.” As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
Furthermore, relative terms, such as “lower” or “bottom” and “upper” or “top,” may be used herein to describe one element's relationship to another element as illustrated in the FIGURES. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the FIGURES. For example, if the device in one of the FIGURES is turned over, elements described as being on the “lower” side of other elements would then be oriented on “upper” sides of the other elements. The exemplary term “lower,” can therefore, encompasses both an orientation of “lower” and “upper,” depending on the particular orientation of the FIGURE. Similarly, if the device in one of the FIGURES is turned over, elements described as “below” or “beneath” other elements would then be oriented “above” the other elements. The exemplary terms “below” or “beneath” can, therefore, encompass both an orientation of above and below.
“About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ±30%, 20%, 10% or 5% of the stated value.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
According to an aspect, a heterocyclic compound may be represented by Formula 1:
In an embodiment, k1 may be an integer from 1 to 3.
In Formulae 1 and A, n1 may be an integer from 1 to 3.
In an embodiment, n1 may be 1.
In an embodiment, n2 may be an integer from 0 to 3.
In an embodiment, n2 may be 0.
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 C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C2-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —Ge(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q), or —P(Q8)(Q).
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 C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C2-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 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)(Qs).
At least one substituent of the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C2-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl 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 may each independently be: hydrogen; deuterium; —F; —Cl; —Br; —I; a hydroxyl group; a cyano group; a nitro group; an amidino group; a hydrazine group; a hydrazone group; a carboxylic acid group or a salt thereof; a sulfonic acid group or a salt thereof; a phosphoric acid group or a salt thereof; a C1-C60 alkyl group unsubstituted or substituted with deuterium, a C1-C60 alkyl group, a C6-C60 aryl group, or any combination thereof; a C2-C60 alkenyl group; a C2-C60 alkynyl group; a C1-C60 alkoxy group; a C3-C10 cycloalkyl group; a C1-C10 heterocycloalkyl group; a C3-C10 cycloalkenyl group; a C2-C10 heterocycloalkenyl group; a C6-C60 aryl group unsubstituted or substituted with deuterium, a C1-C60 alkyl group, a C6-C60 aryl group, or any combination thereof; a C6-C60 aryloxy group; a C6-C60 arylthio group; a C1-C60 heteroaryl group; a monovalent non-aromatic condensed polycyclic group; or a monovalent non-aromatic condensed heteropolycyclic group.
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 may each independently be an integer from 0 to 4 (e.g., 0, 1, 2, 3, or 4). When d1 is 2 or more, two or more of R1 may be identical to or different from each other, when d2 is 2 or more, two or more of R2 may be identical to or different from each other, when d3 is 2 or more, two or more of R3 may be identical to or different from each other, when d5 is 2 or more, two or more of R5 may be identical to or different from each other, and when d6 is 2 or more, 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 may be an integer from 0 to 3 (e.g., 0, 1, 2, or 3). When d4 is 2 or more, 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 may be an integer from 0 to 5 (e.g., 0, 1, 2, 3, 4, or 5). When d7 is 2 or more, two or more of R7 may be identical to or different from each other.
In an embodiment, at least one of d2 and d1 may be an integer of 1 or more. In one or more embodiments, at least one of d2 and d1 may be 4.
In an embodiment, R1 to R7 may each independently be:
In an embodiment, R5 to R7 may each independently be:
In one or more embodiments, R1 to R4 may each independently be:
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, R5 to R7 may each independently be:
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 may include at least one deuterium.
In an embodiment, the heterocyclic compound may include deuterium as a substituent or a substituent of R1 to R7.
In an embodiment, 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 an embodiment, the heterocyclic compound may satisfy at least two of Conditions 1 to 7.
In an embodiment, the heterocyclic compound may satisfy at least three of Conditions 1 to 7.
In an embodiment, the heterocyclic compound may satisfy at least four of Conditions 1 to 7.
In an embodiment, the heterocyclic compound may satisfy at least five of Conditions 1 to 7.
In an embodiment, the heterocyclic compound may satisfy at least six of Conditions 1 to 7.
In an embodiment, the heterocyclic compound may satisfy all of Conditions 1 to 7.
In an embodiment, the heterocyclic compound represented by Formula 1 may satisfy at least one of Conditions 1′ to 7′:
In an embodiment, the heterocyclic compound may satisfy at least two of Conditions 1′ to 7′.
In an embodiment, the heterocyclic compound may satisfy at least three of Conditions 1′ to 7′.
In an embodiment, the heterocyclic compound may satisfy at least four of Conditions 1′ to 7′.
In an embodiment, the heterocyclic compound may satisfy at least five of Conditions 1′ to 7′.
In an embodiment, the heterocyclic compound may satisfy at least six of Conditions 1′ to 7′.
In an embodiment, the heterocyclic compound may satisfy all of Conditions 1′ to 7′.
In an embodiment, the substitution ratio of deuterium of the heterocyclic compound represented by Formula 1 may be greater than 0% and less than or equal to about 100%.
In an embodiment, 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 an embodiment, 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” as used herein refers to the ratio of the 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 ratio of deuterium refers to, in Formulae 1 and A, the ratio of the number of deuterium atoms in R1 to R7 to the total number in R1 to R7.
In an embodiment, among R1(s) in the number of d1, each of R2(s) in the number of d2, R3(s) in the number of n1*d3, R4(s) in the number of n1*d4, R5(s) in the number of d5, R6(s) in the number of k1*n2*d6, and R7(s) in the number of k1*d7, at least 10% of the substituents may be deuterium.
In an embodiment, among R1(s) in the number of d1, R2(s) in the number of d2, R3(s) in the number of n1*d3, R4(s) in the number of n1*d4, R5(s) in the number of d5, R6(s) in the number of k1*n2*d6, and R7(s) in the number of k1*d7, at least 20% of the substituents may be deuterium.
In an embodiment, among R1(s) in the number of d1, R2(s) in the number of d2, R3(s) in the number of n1*d3, R4(s) in the number of n1*d4, R5(s) in the number of d5, R6(s) in the number of k1*n2*d6, and R7(s) in the number of k1*d7, at least 30% of the substituents may be deuterium.
In an embodiment, among R1(s) in the number of d1, R2(s) in the number of d2, R3(s) in the number of n1*d3, R4(s) in the number of n1*d4, R5(s) in the number of d5, R6(s) in the number of k1*n2*d6, and R7(s) in the number of k1*d7, at least 40% of the substituents may be deuterium.
In an embodiment, among R1(s) in the number of d1, R2(s) in the number of d2, R3(s) in the number of n1*d3, R4(s) in the number of n1*d4, R5(s) in the number of d5, R6(s) in the number of k1*n2*d6, and R7(s) in the number of k1*d7, at least 80% of the substituents may be deuterium.
In an embodiment, among R1(s) in the number of d1, R2(s) in the number of d2, R3(s) in the number of n1*d3, R4(s) in the number of n1*d4, R5(s) in the number of d5, R6(s) in the number of k1*n2*d6, and R7(s) in the number of k1*d7, at least 90% of the substituents may be deuterium.
In an embodiment, the heterocyclic compound represented by Formula 1 may be represented by Formula 1A:
In an embodiment, a moiety represented by
in Formula 1 may be a group represented by one of Formulae 2-1 to 2-4:
In an embodiment, a moiety represented by
in Formula 1 may be a group represented by one of Formulae 3-1 to 3-4:
In an embodiment, 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 an embodiment, 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 an embodiment, a group represented by one of Formulae 3-1 to 3-4 may satisfy one of Conditions 8-1 to 8-5:
In an embodiment, a moiety represented by
in Formula 1 may be a group represented by one of Formulae 3-101 to 3-112, 3-201 to 3-212, 3-301 to 3-312, and 3-401 to 3-412:
In an embodiment, the group represented by Formula A may be a group represented by Formula A-1:
In an embodiment, in Formula A-1, at least one of R71 to R75 may be deuterium.
In an embodiment, some or all of R71 to R75 in Formula A-1 may be deuterium.
In an embodiment, a moiety represented by
in Formula 1 may be a group represented by one of Formula 4-2 or 4-3:
In an embodiment, at least one of R51 to R55 in Formulae 4-2 and 4-3 may be deuterium.
In an embodiment, some or all of R51 to R55 in Formula 4-2 and 4-3 may be deuterium.
In an embodiment, a moiety represented by
in Formula 1 may be a group represented by one of Formulae 4-201 to 4-279 and 4-301 to 4-356:
The heterocyclic compound represented by Formula 1 may be represented by Formula 1-1 or 1-2:
In one or more embodiments, the heterocyclic compound represented by Formula 1 may be one of Compounds 1 to 160:
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 Formula 1′). Accordingly, the heterocyclic compound represented by Formula 1 may have a relatively high T1 energy level.
In addition, the heterocyclic compound represented by Formula 1 may include at least one deuterium. A distance of the C-D bond is shorter than a distance of the 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 an embodiment, the heterocyclic compound represented by Formula 1 may have a triplet energy level of greater than or equal to about 2.8 eV or in a range of 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 in a range of 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 energy level and the HOMO energy level may be evaluated based on the density functional theory (DFT).
For example, regarding Compound 6 belonging to the heterocyclic compound represented by Formula 1, the HOMO energy level, lowest unoccupied molecular orbital (LUMO) energy level, singlet (S1) energy level, triplet (T1) energy level were evaluated by using the DFT that is structurally optimized at the level of B3LYP/6-31G(d,p) (e.g., a DFT method of the Gaussian program), and results 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 with reference to Synthesis Example to be described later.
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 and including an emission layer, wherein the organic layer includes at least one heterocyclic compound represented by Formula 1.
When the organic light-emitting device includes such an organic layer including the aforementioned heterocyclic compound represented by Formula 1, long lifespan characteristics or the like may be resulted.
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 between the first electrode and the emission layer and an electron transport region 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 an embodiment, the heterocyclic compound 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 heterocyclic compound represented by Formula 1 is greater than the amount of the dopant). The emission layer may emit, for example, blue light.
In an embodiment, 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 an embodiment, 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 an embodiment, the emission layer may include a host and a dopant, and the heterocyclic compound may be included in the host. In an embodiment, the amount (weight) of the host may be greater than the amount (weight) of the dopant.
In one or more embodiments, the emission layer may emit blue light, but embodiments are not limited thereto.
The dopant may be a fluorescent dopant, a phosphorescent dopant, or any combination thereof. In an embodiment, the dopant may be a phosphorescent dopant.
In an embodiment, the emission layer may include a host, a fluorescent dopant, and a phosphorescent dopant, and the host may include the heterocyclic compound. 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 heterocyclic compound” 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 an embodiment, the organic layer may include only Compound 1 as the heterocyclic compound. 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 heterocyclic compounds. 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 arranged between the first electrode and the second electrode of the organic light-emitting device. The “organic layer” may include, in addition to an organic compound, an organometallic complex including metal.
The
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 between the first electrode 11 and the second electrode 19.
In the FIGURE, the organic layer 10A includes 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, e.g., a glass substrate or a transparent plastic substrate, each having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water repellency.
First Electrode 11
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 an embodiment, when the first electrode 11 is a transmissive electrode, the material for forming the first electrode 11 may include indium tin oxide (“ITO”), indium zinc oxide (“IZO”), tin oxide (SnO2), zinc oxide (ZnO), or any combination thereof. In one or more embodiments, when the first electrode 11 is 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 any combination thereof.
The first electrode 11 may have a single-layer structure or a multi-layer structure including a plurality of layers.
Emission Layer 15
A thickness of the emission layer 15 may be in a range of about 100 angstroms (Å) to about 1,000 Å, for example, about 200 Å to about 600 Å. 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.
Host in Emission Layer 15
A host in the emission layer 15 may include the heterocyclic compound represented by Formula 1.
In addition to the heterocyclic compound represented by Formula 1 (for example, refer to the first host in Examples below), 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 the heterocyclic compound represented by Formula 1 will be described below.
The host may not include a transition metal.
The host may be one type of compound, or a mixture of two or more different types of compounds.
In an embodiment, the host may include at least one of a bipolar host, an electron-transporting host, and 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 any combination thereof:
wherein, in the formulae above, *, *′, and *″ each indicate a binding site to a neighboring atom.
In an embodiment, the electron-transporting host may include at least one of a cyano group, a π-electron deficient nitrogen-containing C1-C60 cyclic group, or a combination thereof.
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 be 1,3-bis(9-carbazolyl)benzene (“mCP”), tris(4-carbazoyl-9-ylphenyl)amine (“TCTA”), 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (“CBP”), 3,3-bis(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”), and 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, and a triazine group, and ii) at least one of a triphenylene group and 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
the hole-transporting host may include a compound represented by Formula H-1:
[Ar301]xb11−[(L301)xb1−R301]xb21 Formula E-1
Condition 1″
At least one of Ar301, L301, and R301 in Formula E-1 each independently includes a π electron-deficient nitrogen-containing C1-C60 cyclic group;
Condition 2″
Condition 3″
Ar401-(L401)xc1−(Ar402)xc11 Formula H-1
In an embodiment, 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 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 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), or any combination thereof,
In one or more embodiments,
Q31 to Q33 are each the same as described herein.
In one or more embodiments, L301 may be a group represented by one of Formulae 5-2, 5-3, and 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 of Ar402(s) in the number of xc11 may be a group represented by one of 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 an embodiment, the electron-transporting host may be represented by Formula E-2:
In an embodiment, in Formula E-2, CY23 and CY24 may each independently be a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
In an embodiment, CY23 and 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.
In an embodiment, CY23 and CY24 may each independently be a benzene group, a naphthalene group, or a pyridine group.
In an embodiment, 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 an embodiment, 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 an embodiment, 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 an embodiment, in Formula E-2, L21 and L22 may each independently be: a single bond; or a group represented by one of Formulae L-1 to L-12:
In an embodiment, in Formula E-2, n21 and n22 indicate the number of L21(s) and L22(s), respectively, and may each independently be an integer from 0 to 5 (e.g., 0, 1, 2, or 3). When n21 is 2 or more, two or more of L21 may be identical to or different from each other, and when n22 is 2 or more, two or more of L22 may be identical to or different from each other.
In an embodiment, in Formula E-2, R21 to R24, R21a, R22a, and R23a 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 C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C2-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —Si(Q1)(Q2)(Q3), —Ge(Q1)(Q2)(Q3), —N(Q4)(Q5), —B(Q6)(Q7), or —P(═O)(Q8)(Q).
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 C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C2-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl group, the substituted C1-C60 heteroaryloxy group, the substituted C1-C60 heteroarylthio group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may be:
In Formula E-2, b21 to b24 indicate the number of R21(s) to R24(s), respectively, and may each independently be an integer from 0 to 10 (e.g., 0, 1, 2, or 3). When b21 is 2 or more, two or more of R21 may be identical to or different from each other, when b22 is 2 or more, two or more of R22 may be identical to or different from each other, when b23 is 2 or more, two or more of R23 may be identical to or different from each other, and when b24 is 2 or more, 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 an embodiment, 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 an embodiment, R21 and R22 may each independently be: a phenyl group, a naphthyl group, or a carbazolyl group, each unsubstituted or substituted with deuterium, a C1-C10 alkyl group, a phenyl group, —Si(Q31)(Q32)(Q33) or any combination thereof; or —Si(Q1)(Q2)(Q3),
In an embodiment, 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
Examples of the electron-transporting host include, for example, compounds of Groups HE1 to HE8:
In an embodiment, the hole-transporting host may include at least one of Compounds H-H1 to H-H103:
In an embodiment, the bipolar host may be a compound of Group HEH1:
The term “Ph” as used herein is a phenyl group.
In an embodiment, an example of the hole-transporting host may be Compound H1. In an embodiment, an example of the electron-transporting host may be Compound H2:
Dopant in Emission Layer 15
The dopant included in the emission layer 15 may include a phosphorescent dopant, a fluorescent dopant, or any combination thereof.
In an embodiment, the emission layer 15 may include a host, a fluorescent dopant, and a phosphorescent dopant, and the host may include the heterocyclic compound. 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.
In an embodiment, the phosphorescent dopant may be a blue dopant.
Phosphorescent Dopant
In an embodiment, 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, and a tridentate ligand.
In one or more embodiments, the phosphorescent dopant may include an organometallic compound represented by Formula 31:
In an embodiment, M31 may be Pt, Pd, or Au.
In Formula 31, X31 to X34 may each independently be C or N, and
In an embodiment, a bond between X31 and M31 may be a coordinate bond.
In an embodiment, 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, CY31 to CY34 may each independently be a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
In an embodiment, CY31 to 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, L33 may be a single bond, a double bond, *—N(R37a)—*′, *—B(R37a)—*′, *—P(R37a)—*, *—C(R37a)(R37b)—*′, *—Si(R37a)(R37b)—*′, *—Ge(R37a)(R37b)—*′, *—S—*′, *—Se—*′, *—O—*′, *—C(═O)—*′, *—S(═O)—*′, *—S(═O)2—*′ *—C(R37a)=*′, *═C(R37a)—*′, *—C(R37a)═C(R37b)—*′, *—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, and L34 may be a single bond, a double bond, *—N(R38a)—*′, *—B(R38a)—*′, *—P(R38a)—*′, *—C(R38a)(R38b)—*′, *—Si(R38a)(R38b)—*′, *—Ge(R38a)(R38b)—*′, *—S—*′, *—Se—*′, *—O—*′, *—C(═O)—*′, *—S(═O)—*′, *—S(═O)2—*′ *—C(R38a)=*′, *═C(R38a)—*′, *—C(R38a)═C(R38b)—*′, *—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 more, two or more of L31 may be identical to or different from each other, when n32 is 2 or more, two or more of L32 may be identical to or different from each other, when n33 is 2 or more, two or more of L33 may be identical to or different from each other, and when n34 is 2 or more, two or more 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 amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C2-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C7-C60 arylalkyl 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 heteroarylalkyl 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 an embodiment, R31 to R34, R35a, R35b, R36a, R36b, R37a, R37b, R38a, and R38b may each independently be: hydrogen, deuterium, —F, —Cl, —Br, —I, -CD3, -CD2H, -CDH2, —CF3, —CF2H, —CFH2, a cyano group, a nitro group, an amino group, a C1-C20 alkyl group, or a C1-C20 alkoxy group;
In an embodiment, the phosphorescent dopant may include an organometallic compound represented by Formula 31-1 or 31-2:
In Formula 31, b31 to b34 may each independently be an integer from 0 to 20.
In Formula 31, at least two of R31(s) in the number of b31 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 R31 to R34, R35a, R35b, R36a, R36b, R37a, R37b, R38a, and R38b 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, and
In Formulae 31-1 and 31-2,
In an embodiment, 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, or a C7-C60 arylalkyl 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
In an embodiment, M51 may be a first-row transition metal, a second-row transition metal, or a third-row transition metal of the Periodic Table of Elements.
In one or more embodiments, M51 may be iridium (Ir), platinum (Pt), osmium (Os), titanium (Ti), zirconium (Zr), hafnium (Hf), europium (Eu), terbium (Tb), thulium (Tm), or rhodium (Rh).
In one or more embodiments, M51 may be Ir, Pt, Os, or Rh.
In Formula 51, L51 may be a ligand represented by Formula 51 Å, and L52 may be a ligand represented by Formula 51B:
In Formula 51, n51 may be 1, 2, or 3, wherein, when n51 is 2 or more, two or more of L51 may be identical to or different from each other.
In Formula 52, n52 may be 0, 1, or 2, wherein, when n52 is 2 or more, two or more of L52 may be identical to or different from each other.
In Formula 51, the sum of n51 and n52 may be 2 or 3. For example, the sum of n51 and n52 may be 3.
In an embodiment, in Formula 51, i) M51 may be Ir, and the sum of n51+n52 may be 3; or ii) M51 may be Pt, and the sum of n51+n52 may be 2.
In one or more embodiments, in Formula 51, M51 may be Ir, 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, CY51 to CY54 may each independently be a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
For example, CY51 to CY54 may each independently be i) a third ring, ii) a fourth ring, iii) a condensed cyclic group in which two or more third rings are condensed with each other, iv) a condensed cyclic group in which two or more fourth rings are condensed with each other, or v) a condensed cyclic 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 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 benzoxadiazole group, a benzothiadiazole group, a pyridinopyrrole group, a pyridinopyrazole group, a pyridinoimidazole group, a pyridinoxazole group, a pyridinoisoxazole group, a pyridinothiazole group, a pyridinoisothiazole group, a pyridinoxadiazole group, a pyridinothiadiazole group, a pyrimidinopyrrole group, a pyrimidinopyrazole group, a pyrimidinoimidazole group, a pyrimidinoxazole group, a pyrimidinoisoxazole group, a pyrimidinothiazole group, a pyrimidinoisothiazole group, a pyrimidinoxadiazole 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 an embodiment, CY51 and CY53 may be different from each other.
In one or more embodiments, CY52 and CY54 may be different from each other.
In one or more embodiments, CY51 to CY54 may be different from each other.
In an embodiment, 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 C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C2-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —Si(Q1)(Q2)(Q3), —Ge(Q1)(Q2)(Q3), —N(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q), or —P(Q8)(Q). Q1 to Q9 are each the same as described herein.
In an embodiment, 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(s) to R54(s), respectively, and may each independently be an integer from 0 to 20. When b51 is 2 or more, two or more of R51 may be identical to or different from each other, when b52 is 2 or more, two or more of R52 may be identical to or different from each other, when b53 is 2 or more, two or more of R53 may be identical to or different from each other, and when b54 is 2 or more, 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 an embodiment, the phosphorescent dopant may include one of Compounds P1 to P52:
When the phosphorescent dopant is selected from 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 (e.g., a tert-butyl group, a cumyl group, etc.), an energy level close to that of the host compound, and thus exciplex formation may be facilitated. In the case of the phosphorescent dopant, a 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.
Fluorescent Dopant
In an embodiment, the emission layer 15 may further include a fluorescent dopant. For example, the fluorescent dopant may be a thermally activated delayed fluorescence dopant and a blue dopant.
The fluorescent dopant may have a difference between a triplet energy level and a singlet energy level of less than or equal to about 0.4 eV.
For example, the fluorescent dopant may be a thermally activated delayed fluorescence dopant and a blue dopant.
In an embodiment, the fluorescent dopant may be a luminescence emitter that may emit light by receiving excitons from the exciplex of the host and the phosphorescent dopant according to an embodiment so that the received excitons transition to a ground state.
In an embodiment, the fluorescent dopant may be a compound represented by Formula 41:
In an embodiment, R41 to R49 may each independently be:
In an embodiment, Formula 41 may be selected from Formulae 41-1 to 41-9:
In an embodiment, the fluorescent dopant may be selected from Compounds D1 to D30:
In an embodiment, the fluorescent dopant may be included in the emission layer in an amount in a range of 0 weight percent (wt %) to about 5 wt %.
Hole Transport Region 12
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 the heterocyclic compound 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 any combination thereof of the hole transport region 12.
For example, the hole transport region 12 may include an amine-based compound.
In an embodiment, the hole transport region 12 may include m-MTDATA, TDATA, 2-TNATA, NPB, β-NPB, TPD, spiro-TPD, spiro-NPB, methylated-NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (“PANI/DBSA”), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (“PEDOT/PSS”), polyaniline/camphor-sulfonic acid (“PANI/CSA”), polyaniline/poly(4-styrene sulfonate) (“PANI/PSS”), a compound represented by one of Formulae 201 to 205, or any combination thereof:
For example,
In one or more embodiments, the hole transport region 12 may include a carbazole-containing amine-based compound.
In one or more embodiments, the hole transport region 12 may include a carbazole-containing amine-based compound and a carbazole-free amine-based compound.
The carbazole-containing amine-based compound may include, for example, 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, a benzothienocarbazole group, or any combination thereof.
The carbazole-free amine-based compound may include, for example, 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, a benzothienocarbazole group, or any combination thereof.
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 any 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 any combination thereof:
In an embodiment, the hole transport region 12 may include one of Compounds HT1 to HT39 or any combination thereof:
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 an embodiment, 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 any combination thereof.
For example, the p-dopant may include:
The compound represented by Formula 221 may include, for example, Compound HT-D2:
The hole transport region 12 may have a thickness in a range 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 in a range of about 100 Å to about 3,000 Å, for example, about 300 Å to about 1,000 Å. 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 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 DBFPO:
Electron Transport Region 17
The electron transport region 17 is 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 the heterocyclic compound 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 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 is the same as described herein.
For example, the electron transport region 17 may include a compound represented by Formula 601:
[Ar601]xe11-[(L601)xe1-R601]xe21. Formula 601
In an embodiment, at least one of Ar601(s) in the number of xe11 and R601(s) in the number of xe21 may include the π electron-deficient nitrogen-containing C1-C60 cyclic group.
In an embodiment, 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 deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C20 alkyl group, a C1-C20 alkoxy 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), or any 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:
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 deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C20 alkyl group, a C1-C20 alkoxy 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 any combination thereof; or
The electron transport region 17 may include at least one of Compounds ET1 to ET36:
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, BAIq, 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (“TAZ”), NTAZ, DBFPO, or any combination thereof. For example, when the electron transport region 17 includes a hole blocking layer, the hole blocking layer may include BCP or Bphen:
Thicknesses of the buffer layer, the hole blocking layer, and the electron control layer may each independently be in a range of about 20 Å to about 1,000 Å, for example, about 30 Å to about 300 Å. 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 in a range of about 100 Å to about 1,000 Å, for example, about 150 Å to about 500 Å. When the thickness of the electron transport layer is within 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 any 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 any 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 any 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 any combination thereof.
For example, the metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 (LiQ) or ET-D2:
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 any combinations thereof.
The alkali metal may include Li, Na, K, Rb, Cs, or any combination thereof. In an embodiment, 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 any combination thereof.
The rare earth metal may include Sc, Y, Ce, Tb, Yb, Gd, or any 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 any combination thereof.
The alkali metal compound may include: one of alkali metal oxides such as Li2O, Cs2O, K2O, and the like; one of alkali metal halides such as LiF, NaF, CsF, KF, LiI, Nal, Csl, KI, and the like; or any combination thereof. In an embodiment, the alkali metal compound may include LiF, Li2O, NaF, Lil, Nal, Csl, KI, or any 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 any combination thereof. In an embodiment, the alkaline earth metal compound may include BaO, SrO, CaO, or any combination thereof.
The rare earth metal compound may include YbF3, ScF3, ScO3, Y2O3, Ce2O3, GdF3, TbF3, or any combination thereof. In an embodiment, the rare earth metal compound may include YbF3, ScF3, TbF3, Ybl3, ScI3, Tbl3, or any combination thereof.
The alkali metal complex, the alkaline earth metal complex, and the rare earth metal complex may include an ion of alkali metal, alkaline earth metal, and 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 any 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 any 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 any 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 in a range of about 1 Å to about 100 Å, and, for example, about 3 Å to about 90 Å. When the thickness of the electron injection layer is within these ranges, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.
Second Electrode 19
The second electrode 19 is 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 any 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.
Explanation of Terms
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.
Examples of the C1-C60 alkyl group, the C1-C20 alkyl group, and/or the C1-C10 alkyl group are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an 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 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 any 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 examples thereof are a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.
The term “C2-C60 alkenyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof are an ethenyl group, a propenyl group, and a butenyl group. The term “C2-C60 alkenylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof are an ethynyl group, and a propynyl group. The term “C2-C60 alkynylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkynyl group.
The term “C3-C10 cycloalkyl group” as used herein refers to a monovalent saturated hydrocarbon cyclic 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.
Examples of the C3-C10 cycloalkyl group are 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, and a bicyclo[2.2.2]octyl group.
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, 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.
Examples of the C1-C10 heterocycloalkyl group are a silolanyl group, a silinanyl group, tetrahydrofuranyl group, a tetrahydro-2H-pyranyl group, and a tetrahydrothiophenyl group.
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 examples thereof are a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group. The term “C3-C10 cycloalkenylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkenyl group.
The term “C2-C10 heterocycloalkenyl group” as used herein refers to a monovalent monocyclic group that has at least one hetero atom selected from B, N, O, P, Si, S, Se, Ge, and B as a ring-forming atom, 2 to 10 carbon atoms, and at least one carbon-carbon double bond in the ring thereof. Examples of the C2-C10 heterocycloalkenyl group are a 2,3-dihydrofuranyl group and a 2,3-dihydrothiophenyl group. The term “C2-C10 heterocycloalkenylene group” as used herein refers to a divalent group having the same structure as the C2-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as used herein refers to a monovalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms, and the term “C6-C60 arylene group” as used herein refers to a divalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms. Examples of the C6-C60 aryl group are a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a chrysenyl group. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the rings may be fused to each other.
The term “C1-C60 heteroaryl group” as used herein refers to a monovalent group that includes at least one heteroatom selected from B, N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and a heterocyclic aromatic system having 1 to 60 carbon atoms, and the term “C1-C60 heteroarylene group” as used herein refers to a divalent group that includes at least one heteroatom selected from B, N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and a heterocyclic aromatic system having 1 to 60 carbon atoms. Examples of the C1-C60 heteroaryl group are a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, and an isoquinolinyl group. When the C6-C60 heteroaryl group and the C6-C60 heteroarylene group each include two or more rings, the rings may be fused to each other.
The term “C6-C60 aryloxy group” as used herein indicates -OA102 (wherein A102 is the C6-C60 aryl group), and the term “C6-C60 arylthio group” as used herein indicates -SA103 (wherein A103 is the C6-C60 aryl group).
The term “monovalent non-aromatic condensed polycyclic group” as used herein refers to a monovalent group 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-aromaticity group. An example of the monovalent non-aromatic condensed polycyclic group is a fluorenyl group. The term “divalent non-aromatic condensed polycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed polycyclic group 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. An example of the monovalent non-aromatic condensed heteropolycyclic group is a carbazolyl group. The term “divalent non-aromatic condensed heteropolycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed heteropolycyclic group described above.
The term “π electron-depleted nitrogen-containing C1-C60 cyclic group” as used herein refers to a cyclic 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 cyclic 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, e.g., a) a third ring or b) a condensed ring in which at least two third rings are condensed.
The “C1-C6 heterocyclic group” as used herein refers to a monocyclic or polycyclic group including at least one heteroatom and 1 to 60 carbon atoms, e.g., 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 pyridopyrazine 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 benzonapthothiophene 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 group, depending on the formula structure.
As used herein, the number of carbons in each group that is substituted (e.g., C1-C60) excludes the number of carbons in the substituent. For example, a C1-C60 alkyl group can be substituted with a C1-C60 alkyl group. The total number of carbons included in the C1-C60 alkyl group substituted with the C1-C60 alkyl group is not limited to 60 carbons. In addition, more than one C1-C60 alkyl substituent may be present on the C1-C60 alkyl group. This definition is not limited to the C1-C60 alkyl group and applies to all substituted groups that recite a carbon range.
At least one substituent 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 C2-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 C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C2-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl 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 described herein may each independently be: hydrogen; deuterium; —F; —Cl; —Br; —I; a hydroxyl group; a cyano group; a nitro group; an amidino group; a hydrazine group; a hydrazone group; a carboxylic acid or a salt thereof; a sulfonic acid or a salt thereof; a phosphoric acid or a salt thereof; a C1-C60 alkyl group which is unsubstituted or substituted with deuterium, a C1-C60 alkyl group, a C6-C60 aryl group, or any combination thereof; a C2-C60 alkenyl group; a C2-C60 alkynyl group; a C1-C60 alkoxy group; a C3-C10 cycloalkyl group; a C1-C10 heterocycloalkyl group; a C3-C10 cycloalkenyl group; a C2-C10 heterocycloalkenyl group; a C6-C60 aryl group which is unsubstituted or substituted with deuterium, a C1-C60 alkyl group, a C6-C60 aryl group, or any combination thereof; a C6-C60 aryloxy group; a C6-C60 arylthio group; a C1-C60 heteroaryl group; a monovalent non-aromatic condensed polycyclic group; or a monovalent non-aromatic condensed heteropolycyclic group.
For example, Q1 to Q9, Q11 to Q19, Q21 to Q29, and Q31 to Q39 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, and four phenyl groups linked via a single bond, respectively.
Hereinafter, a compound and an organic light-emitting device according to embodiments are described in detail with reference to Synthesis 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 6 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 distilled 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, and then subjected to silica column chromatography, so as to provide Intermediate 1. (28.3 g, 118.8 mmol, yield of 96%).
LCMS (calculated: 237.02, found (M+1): 238.04 mass to charge ratio (m/z)).
Intermediate 1 (28.3 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 (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, and then subjected to silica column chromatography, so as to provide Intermediate 2. (19.5 g, 60.5 mmol, yield of 51%).
LCMS (calculated: 332.22, found (M+1): 333.25 m/z).
Intermediate 2 (19.5 g, 60.5 mmol) was mixed with 600 mL of dimethyl formamide, 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 dimethyl formamide was added dropwise thereto and stirred at room temperature 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, and then subjected to silica column chromatography, so as to provide Intermediate 3. (23.2 g, 56.6 mmol, yield of 93%).
LCMS (calculated: 409.12, found (M+1): 410.13 m/z).
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, and then subjected to a silica column, so as to synthesize Compound 6 (19.5 g, 38.6 mmol, yield of 68%).
LCMS (calculated: 504.32, found (M+1): 505.33 m/z).
Compound 26 was synthesized according to the following reaction scheme:
Intermediate 4 was synthesized (yield of 85%) in the same 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.
LCMS (calculated: 237.02, found (M+1): 238.04 m/z).
Compound 26 was synthesized in the same manner as used to synthesize Compound 6 of Synthesis Example 1, except that, in the synthesis of Compound 6, Intermediate 4 was used instead of Intermediate 1, Intermediate 5 was used instead of Intermediate 2, and Intermediate 6 was used instead of Intermediate 3.
LCMS (calculated: 504.32, found (M+1): 505.33 m/z).
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 distilled water. After the completion of ultrasonication using distilled water, cleaning by ultrasonication using a solvent, such as 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 on the ITO electrode on the glass substrate to form a hole injection layer having a thickness of 100 Å, Compound HT3 was deposited on the hole injection layer to form a hole transport layer having a thickness of 1,300 Å, and mCP was deposited 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 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 6) 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 on the hole blocking layer to form an electron transport layer having a thickness of 300 Å, LiQ was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and 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 the same manner as in Example 1, except that compounds shown in Table 2 were each used instead of Compound 6 in forming the emission layer.
For each of the organic light-emitting devices of Examples 1 and 2 and Comparative Examples 1 to 4, the lifespan (T95 at 1,000 nit, hr) 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) is a measure of the time required for the luminance to decline to 95% of the initial luminance of 100%. The lifespans (T95 at 1,000 nit, hr) of the organic light-emitting devices of Examples 1 and 2 and Comparative Examples 1 to 4 were represented as relative values (%) compared to the lifespan of the organic light-emitting device of Comparative Example 3.
Referring to Table 2, it was confirmed that the organic light-emitting devices of Examples 1 and 2 had excellent external quantum efficiency and lifespan effect compared to the organic light-emitting devices of Comparative Examples 1 to 4.
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 distilled water. After the completion of ultrasonication using distilled water, cleaning by ultrasonication using a solvent, such as 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 on the ITO electrode on the glass substrate to form a hole injection layer having a thickness of 100 Å, Compound HT3 was deposited on the hole injection layer to form a hole transport layer having a thickness of 1,300 Å, and mCP was deposited 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 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 6) 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 on the hole blocking layer to form an electron transport layer having a thickness of 300 Å, LiQ was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and 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 the same manner as in Example 3, except that compounds shown in Table 3 were each used instead of Compound 6 in forming the emission layer.
For each of the organic light-emitting devices of Examples 3 and 4 and Comparative Examples 5 to 8, the lifespan (T95 at 1,000 nit, hr) 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) is a measure of the time required for the luminance to decline to 95% of the initial luminance of 100%. The lifespans of the organic light-emitting devices of Examples 3 and 4 and Comparative Examples 5 to 8 were represented as relative values (%) compared to the lifespan of the organic light-emitting device of Comparative Example 7.
Referring to Table 3, it was confirmed that the organic light-emitting devices of Examples 3 and 4 had excellent lifespan effect compared to the organic light-emitting devices of Comparative Examples 5 to 8.
According to the one or more embodiments, use of a heterocyclic compound 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.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0055745 | May 2022 | KR | national |
| 10-2023-0057363 | May 2023 | KR | national |
