Patent Application
20240397820
This application claims priority under 35 U.S.C. § 119 to Korean Patent Applications Nos. 10-2023-0063362, filed on May 16, 2023, and 10-2024-0062914, filed on May 14, 2024, in the Korean Intellectual Property Office, the disclosure of which are incorporated by reference herein in their entirety.
The disclosure relates to a condensed polycyclic compound, a light-emitting device including the same, and an electronic apparatus including the light-emitting device.
From among light-emitting devices, organic light-emitting devices (OLEDs) are self-emissive devices that, as compared with conventional devices, have wide viewing angles, high contrast ratios, short response times, and excellent characteristics in terms of luminance, driving voltage, and response speed, and produce full-color images.
In an example, an organic light-emitting device may include an anode, a cathode, and an interlayer that is arranged between the anode and the cathode and includes an emission layer. A hole transport region may be between the anode and the emission layer, and an electron transport region may be between the emission layer and the cathode. Holes provided from the anode may move toward the emission layer through the hole transport region, and electrons provided from the cathode may move toward the emission layer through the electron transport region. The holes and the electrons recombine in the emission layer to produce excitons. The excitons may transition from an excited state to a ground state, thus generating light.
Provided are a condensed polycyclic compound, a light-emitting device employing the same, and an electronic apparatus including the 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, provided is a condensed polycyclic compound which does not include a metal and includes a condensed ring, wherein the condensed ring includes a 9-membered ring including nitrogen and carbon as ring-forming atoms and a 6-membered ring including nitrogen, carbon, and boron as ring-forming atoms, wherein the 9-membered ring and the 6-membered ring are condensed with each other while sharing a nitrogen and a carbon.
According to another aspect of the disclosure, a light-emitting device includes a first electrode, a second electrode, and an interlayer arranged between the first electrode and the second electrode and including an emission layer, wherein the interlayer may include at least one condensed polycyclic compound described above.
According to another aspect of the disclosure, an electronic apparatus includes the 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 accompanying drawings, in which:
The FIGURE is a schematic cross-sectional view of a light-emitting device according to an exemplary embodiment.
Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the FIGURES, to explain aspects. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
It will be understood that when an element is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present
It will be understood that, although the terms “first,” “second,” “third” etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, “a first element,” “component,” “region,” “layer” or “section” discussed below could be termed a second element, component, region, layer or section without departing from the teachings herein.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, “a,” “an,” “the,” and “at least one” do not denote a limitation of quantity, and are intended to cover both the singular and plural, unless the context 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.
The condensed polycyclic compound i) may not include a metal, and ii) may include a condensed ring. The condensed ring may be a ring including a 9-membered ring including nitrogen and carbon as ring-forming atoms and a 6-membered ring including nitrogen, carbon, and boron as ring-forming atoms, wherein the 9-membered ring and the 6-membered ring are condensed with each other while sharing a nitrogen and a carbon. In the specification, the “condensed ring” may be the ring having the same meaning as described above.
In an embodiment, the condensed ring may include a moiety represented by Formula 1(1):
In an embodiment, at least one cyclic group selected from a C5-C60 carbocyclic group and a C3-C60 heterocyclic group may be additionally condensed with the moiety represented by Formula 1(1).
For example, the condensed ring may include a moiety represented by Formula 1(1)-a:
In one or more embodiments, in Formulae 1(1) and 1(1)-a, a boron-containing heterocyclic group may be additionally condensed with ring CY2 while sharing boron. The boron-containing heterocyclic group may be, for example, a boron-containing 6-membered ring.
In the specification, the “boron-containing 6-membered ring” may include as ring-forming atoms, for example, i) oxygen, carbon, and boron, ii) sulfur, carbon, and boron, iii) nitrogen, carbon, and boron, iv) carbon and boron, or v) silicon, carbon, and boron.
For example, the condensed ring may include at least one moiety represented by one of Formulae 1(1)-1 to 1(1)-4:
In an embodiment, in Formulae 1(1), 1(1)-a, and 1(1)-1 to 1(1)-4, at least one cyclic group selected from a C5-C60 carbocyclic group and a C3-C60 heterocyclic group may be additionally condensed with each of ring CY2, ring CY21 to CY23, and/or ring CY3.
For example, in Formulae 1(1), 1(1)-a, and 1(1)-1 to 1(1)-4, at least one of a boron-containing 6-membered ring, an aromatic 6-membered ring (for example, a benzene group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, etc.), a dibenzofuran group, a dibenzothiophene group, a carbazole group, a fluorene group, and a dibenzosilole group may be additionally condensed with each of a ring CY2, a ring CY21 to CY23, and/or a ring CY3.
For example, the condensed ring of Compound 1 includes a moiety represented by Formula 1(1)-2, the condensed ring of Compound 25 includes a moiety represented by Formula 1(1)-1, the condensed ring of Compound 90 includes a moiety represented by Formula 1(1)-4, and the condensed ring of Compound 92 includes a moiety represented by Formula 1(1)-3.
In an embodiment, the number of the moiety presented by Formula 1(1) in the condensed polycyclic compound may be 1, 2, 3, or 4. In Formula 1, when the number of condensed rings is 2, a condensed ring may be condensed with another condensed ring, wherein the two condensed rings share a B and a carbon. In Formula 1, when the number of condensed rings is 3, a condensed ring may be condensed with another condensed ring and the resulting condensed ring structure may be condensed with another condensed ring, wherein the three condensed rings share a B. For example, the number of the moiety presented by Formula 1(1) in Compound 1 is 2, and the number of the moiety presented by Formula 1(1) in Compound 14 is 1.
In one or more embodiments, the number of 9-membered rings in the condensed polycyclic compound (for example, ring CY1 in Formulae 1(1), 1(1)-1, and 1(1)-2) may be 1, 2, 3, or 4. For example, the number of 9-membered rings in Compound 1 is 2, and the number of 9-membered rings in Compound 14 is 1.
In one or more embodiments, the number of boron-containing 6-membered rings in the condensed polycyclic compound may be 1 to 10. For example, the number of boron-containing 6-membered rings in Compound 1 is 2, and the number of boron-containing 6-membered ring in Compound 73 is 4.
In one or more embodiments, the number of boron atoms included as ring-forming atoms in the condensed polycyclic compound may be 1 to 10. For example, the number of boron atoms included as ring-forming atoms in Compound 1 may be 1, and the number of boron atoms included as ring-forming atoms in Compound 73 may be 2.
The condensed polycyclic compound may be a delayed fluorescence material. That is, the condensed polycyclic compound may emit delayed fluorescence.
The condensed ring may be unsubstituted. Or, the condensed ring may be substituted with at least one substituent. The substituent is the same as described herein in connection with R1 to R3, Z1 to Z3, Z21 to Z23, T11, T12, T21, T22, T31, T32, etc.
For example, the condensed polycyclic compound may be a multiple resonance thermally activated delayed fluorescence material.
In an embodiment, the condensed polycyclic compound may be represented by Formula 1, 2, or 3:
In an embodiment, ring A1 to ring A3, ring Y1 to Y3, and ring Y21 to ring Y23 in Formulae 1 to 3 may each independently be a benzene group, a naphthalene group, a phenanthrene group, a pyridine group, a pyrimidine group, a pyridazine group, a pyrazine group, a quinoline group, an isoquinoline group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a fluorene group, a dibenzosilole group, an azadibenzofuran group, an azadibenzothiophene group, an azacarbazole group, an azafluorene group, or an azadibenzosilole group.
In one or more embodiments, ring A1 to ring A3, ring Y1 to ring Y3, and ring Y21 to ring Y23 in Formulae 1 to 3 may each independently be a benzene group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a fluorene group, or a dibenzosilole group.
One or more embodiments provide a condensed polycyclic compound represented by Formula 1, wherein n1 may be 1, W1 may be N(T11), and Condition 1A or 1B may be satisfied:
For example, Compound 1 may be a condensed polycyclic compound represented by Formula 1, wherein, in Formula 1, n1 may be 1, W1 may be N(T11), and Condition 1A may be satisfied. In Condition 1A, i) one of Z1 in the number of b1 may be a phenyl group, and T11 may be a biphenyl group, or ii) one of Z1 in the number of b1 may be a biphenyl group, and T11 may be a phenyl group.
One or more embodiments provide a condensed polycyclic compound represented by Formula 2 or 3, wherein n1 may be 1, W1 may be N(T11), and Condition 2A or 2B may be satisfied:
One or more embodiments provide a condensed polycyclic compound represented by Formula 1, wherein n2 may be 1, W2 may be N(T21), and Condition 1C or 1 D may be satisfied:
For example, Compound 7 may be a condensed polycyclic compound represented by Formula 1, wherein, in Formula 1, n2 may be 1, W2 may be N(T21), and Condition 1 D may be satisfied. In Condition 1 D, i) one of Z3 in the number of b3 may be a phenyl group, and T21 may be a biphenyl group, or ii) one of Z3 in the number of b3 may be a biphenyl group, and T21 may be a phenyl group.
One or more embodiments provide a condensed polycyclic compound represented by Formula 2 or 3, wherein n2 may be 1, W2 may be N(T21), and Condition 2C or 2D may be satisfied:
According to another embodiment, the condensed polycyclic compound represented by Formula 1 may satisfy at least one of Conditions 1E, 1F, and 1G:
In one or more embodiments, the condensed polycyclic compound represented by Formula 2 or 3 may satisfy at least one of Conditions 2E, 2F, 2G, 2H, and 2I:
In one or more embodiments, in Formulae 1 to 3,
In one or more embodiments, in Formulae 1 to 3, R1 to R3, Z1 to Z3, Z21 to Z23, T11, T12, T21, T22, T31, and T32 may each independently be:
In one or more embodiments, in Formulae 1 to 3, R1 to R3, Z1 to Z3, Z21 to Z23, T11, T12, T21, T22, T31, and T32 may each independently include:
Q1 and Q2 are each the same as described herein.
In one or more embodiments, in Formulae 1 to 3, R1 to R3, Z1 to Z3, Z21 to Z23, T11, T12, T21, T22, T31, and T32 may each independently be:
In one or more embodiments, Formulae 1 to 3 may each include deuterium, a tert-butyl group, a phenyl group, a phenyl group substituted with a tert-butyl group, a biphenyl group, a biphenyl group substituted with a tert-butyl group, an N-carbazolyl group, an N-carbazolyl group substituted with a tert-butyl group, a phenyl group substituted with an N-carbazolyl group, a diphenylamino group, a di(phenyl substituted with a tert-butyl group)amino group, or any combination thereof.
In one or more embodiments, the condensed polycyclic compound may include deuterium, a tert-butyl group, a phenyl group, a phenyl group substituted with a tert-butyl group, a biphenyl group, an N-carbazolyl group, an N-carbazolyl group substituted with a tert-butyl group, a diphenylamino group, a di(phenyl substituted with a tert-butyl group)amino group, or any combination thereof.
In one or more embodiments, the condensed polycyclic compound may include at least one deuterium.
In one or more embodiments, the condensed ring may include a moiety represented by one of Formulae 1A-1 to 1A-3, 1B-1 to 1B-2, 1C-1 to 1C-5, 1 D-1 to 1 D-5, and 1E-1 to 1E-5, or a moiety represented by
in Formula 1 may be represented by one of Formulae 1A-1 to 1A-3, 1B-1 to 1B-2, 1C-1 to 1C-5, 1D-1 to 1D-5, and 1E-1 to 1E-5:
In Formulae 1A-1 to 1A-3, 1B-1 to 1B-2, 1C-1 to 1C-5, 1D-1 to 1D-5, and 1E-1 to 1E-5, each ring (including ring A1 to ring A6, ring Y1 to ring Y3, ring Y31 and ring Y32) may be independently a benzene ring. In this case, for example, there may be a substituent at the para-position or meta-position of the benzene ring. The para-position and the meta-position are determined relative to the carbon linked to B atom in an adjacent ring in the benzene ring. For example, in Compound 1, a deuterated carbazolyl group is present at the para-position of the benzene ring. For example, in Formula 1A-1, a substituent may be present at the para-position or meta-position (e.g., para-position) of ring Y1, and/or a substituent may be present at the para-position or meta-position (e.g., para-position) of ring Y3. In Formula 1A-2, a substituent may be present at the meta-position of ring Y1, and/or a substituent may be present at the meta-position of ring Y3, and/or a substituent may be present at the meta-position of ring Y2. In Formula 1A-3, a substituent may be present at the para-position or meta-position of ring Y1, and/or a substituent may be present at the para-position or meta-position of ring Y3. In Formula 1B-2, a substituent may be present at the para-position or meta-position of ring Y2, and/or a substituent may be present at the para-position or meta-position of ring Y3.
In one or more embodiments, the condensed polycyclic compound represented by Formula 1 may have an asymmetric structure with respect to the bond connecting ring Y2 or ring Y1 and B in Formula 1.
In one or more embodiments, the condensed polycyclic compound represented by Formula 1 may have a symmetric structure with respect to the bond connecting ring Y2 or ring Y1 and B in Formula 1.
In the specification, “N-carbazolyl group” refers to a monovalent group wherein the N of the carbazole group is bonded to groups other than hydrogen, and is represented by
(wherein * indicates a binding site to a neighboring atom).
In various backbones such as Formulae 1A-1 to 1A-3, 1B-1 to 1B-2, 1C-1 to 1C-5, 1 D-1 to 1 D-5, and 1E-1 to 1E-5 may be unsubstituted or substituted with R1 to R3 and Z1 to Z3 as described herein according to definition of Formula 1.
In one or more embodiments, the condensed polycyclic compound may be one of Compounds 1 to 94:
The condensed polycyclic compound does not include a metal. Thus, the condensed polycyclic compound may be clearly differentiated from other various organometallic compounds including a center metal such as platinum, palladium, gold, etc. and an organic ligand bonded thereto.
In addition, the condensed polycyclic compound may include a condensed ring described above, and the condensed ring may be a ring including 9-membered ring including nitrogen and carbon as ring-forming atoms and a 6-membered ring including nitrogen, carbon, and boron as ring-forming atoms, wherein the 9-membered ring and the 6-membered ring are condensed with each other while sharing a nitrogen and a carbon. Due to the 9-membered ring condensed with the 6-membered ring, as the condensed polycyclic compound has excellent thermal and electric stability according to the shielding effect to the born atom included in the 6-membered ring, exhibits relatively less steric hindrance effect, and emits blue light having a relatively small full width at half maximum (FWHM) and shifted to a short wavelength, an electronic device employing the condensed polycyclic compound, for example, a light-emitting device employing the condensed polycyclic compound may have an improved driving voltage, higher external quantum efficiency, increased luminescence efficiency, and/or longer lifespan characteristics.
In an embodiment, the FWHM in the emission spectrum of the condensed polycyclic compound may be about 5 nm to about 30 nm, for example, about 10 nm to about 25 nm.
In one or more embodiments, the emission peak wavelength in the emission spectrum of the condensed polycyclic compound may be about 400 nm to about 500 nm, for example, about 440 nm to about 470 nm.
In one or more embodiments, the singlet (Si) energy level of the condensed polycyclic compound may be about 2.4 eV to about 3.1 eV.
In one or more embodiments, the absolute value of the difference between the singlet (Si) energy level and the triplet (Ti) energy level of the condensed polycyclic compound may be about 0 eV to about 1 eV (or, greater than about 0 eV and less than or equal to about 1 eV).
In one or more embodiments, the highest occupied molecular orbital (HOMO) energy level of the condensed polycyclic compound may be about 4.0 eV to about 6.5 eV.
Synthesis methods of the condensed polycyclic compound may be recognized by one of ordinary skill in the art by referring to the Synthesis Examples provided below.
The condensed polycyclic compound may be used as a material of an interlayer of a light-emitting device, for example, an emission layer of the interlayer, and according to another aspect of the disclosure, provided is a light-emitting device including: a first electrode; a second electrode; and an interlayer arranged between the first electrode and the second electrode and including an emission layer, wherein the interlayer may include at least one condensed polycyclic compound described above.
As the light-emitting device includes interlayer including at least one condensed polycyclic compound described above, the light-emitting device may emit blue light having a relatively small FWHM and shifted to a short wavelength, and have an improved driving voltage, higher external quantum efficiency, increased luminescence efficiency, and/or longer lifespan characteristics.
The condensed polycyclic compound may be used between a pair of electrodes of the light-emitting device. For example, the condensed polycyclic compound may be included in the emission layer. In this case, the emission layer may further include a host.
The amount (weight) of the host may be greater than the amount (weight) of the condensed polycyclic compound. The emission layer may emit red light, green light, or blue light. For example, the emission layer may emit blue light.
In an embodiment, the CIEy value of light emitted from the emission layer may be about 0.040 to about 0.170, about 0.050 to about 0.170, about 0.060 to about 0.170, about 0.040 to about 0.165, about 0.050 to about 0.165, or about 0.060 to about 0.165.
In one or more embodiments, the emission peak wavelength of light emitted from the emission layer may be about 440 nm to about 470 nm, about 445 nm to about 470 nm, about 450 nm to about 470 nm, about 455 nm to about 470 nm, about 460 nm to about 470 nm, about 440 nm to about 465 nm, about 445 nm to about 465 nm, about 450 nm to about 465 nm, about 455 nm to about 465 nm, or about 460 nm to about 465 nm.
The emission layer may further include a host. The host may be understood by referring to the description of the host provided herein.
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 interlayer 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 any 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 any combination thereof.
The term “interlayer” 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 “interlayer” may include not only organic compounds but also organometallic complexes including metals.
For example, the emission layer may have a feature described in the first embodiment or the second embodiment provided below.
The emission layer may include at least one condensed polycyclic compound described above, and the condensed polycyclic compound may function as an emitter, for example, a delayed fluorescence emitter. That is, the condensed polycyclic compound may be an emitter. For example, a ratio of a luminescent component emitted from the condensed polycyclic compound with respect to all luminescent components of the emission layer may be 80% or more, 85% or more, 90% or more, or 95% or more. Light emitted from the condensed polycyclic compound may be blue light. The emission layer may further include a sensitizer, and the sensitizer may be different from the condensed polycyclic compound. The sensitizer may be an organometallic compound, a delayed fluorescence material, a prompt fluorescence material, or any combination thereof. The amount (weight) of the sensitizer may be about 0.01 parts by weight to about 10 parts by weight based on 100 parts by weight of the emission layer.
The emission layer may include at least one condensed polycyclic compound described above, and the condensed polycyclic compound may function as a sensitizer or an auxiliary dopant. That is, the condensed polycyclic compound may be a sensitizer or an auxiliary dopant. The sensitizer may facilitate effective transfer of excitons of a host to an emitter. The emission layer may further include an emitter, and the emitter may be different from the condensed polycyclic compound. The emitter may be an organometallic compound, a delayed fluorescence material, a prompt fluorescence material, or any combination thereof.
In the specification, the emitter refers to a material capable of receiving excitons from a host, a sensitizer, and/or an auxiliary dopant and emitting light by the transition of the excitons to the ground state.
In the first and second embodiments, the amount (weight) of the condensed polycyclic compound may be about 0.01 parts by weight to about 40 parts by weight, about 0.1 parts by weight to about 20 parts by weight, or about 1 part by weight to about 20 parts by weight based on 100 parts by weight of the emission layer.
In the first and second embodiments, the organometallic compound may include a transition metal and n ligands bonded to the transition metal, wherein n may be an integer from 1 to 4.
In an embodiment, the transition metal in the organometallic compound may be platinum (Pt) or palladium (Pd), n may be 1, and the ligand may be a tetradentate ligand.
The tetradentate ligand may include, for example, a carbene moiety bonded to the transition metal.
In one or more embodiments, the organometallic compound may include a transition metal and a tetradentate ligand bonded to the transition metal, wherein the transition metal may be platinum or palladium, and the tetradentate ligand may include a carbene moiety bonded to the transition metal.
In one or more embodiments, the transition metal in the organometallic compound may be iridium (Ir) or osmium (Os), n may be 3, and at least one of the n ligands may be a bidentate ligand including —F, a cyano group, or any combination thereof or a bidentate ligand including a carbene moiety bonded to the transition metal. For example, the bidentate ligand may further include an imidazole group or a triazole group.
In one or more embodiments, the organometallic compound may be an organometallic compound represented by Formula 30 and/or an organometallic compound represented by Formula 5. Formulae 30 and 5 will be described in detail later.
In the first and second embodiments, the delayed fluorescence material may be, for example, a thermally activated delayed fluorescence material. In another embodiment, the delayed fluorescence material may be a multiple resonance thermally activated delayed fluorescence material.
The multiple resonance thermally activated delayed fluorescence material may be a polycyclic compound i) which does not include a transition metal, and ii) includes a core in which two or more C3-C60 cyclic groups are condensed with each other. In this regard, two C3-C60 cyclic groups of the core may be condensed with each other while sharing boron (B) or nitrogen (N).
In an embodiment, the delayed fluorescence material may be a polycyclic compound represented by Formula 4. Formula 4 will be described in detail later.
The prompt fluorescence material in the first and second embodiments may be an amino group-containing compound, a styryl group-containing compound, etc. For example, the prompt fluorescence material may include a naphthalene group, a fluorene group, a spiro-bifluorene group, a benzofluorene group, a dibenzofluorene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a naphthacene group (tetracene group), a picene group, a perylene group, a pentaphene group, an indenoanthracene group, a group represented by one of Formulae 501-1 to 501-21, or any combination thereof:
In one or more embodiments, the prompt fluorescence material may include a compound represented by Formula 501A or 501B:
In one or more embodiments, the prompt fluorescence material may include a compound represented by Formula 501A or 501B, wherein in Formula 501A, xd4 may be 1, 2, 3, 4, 5, or 6, and in Formula 501B, xd4 may be 2, 3, or 4.
The host in the emission layer may include a hole-transporting compound, an electron-transporting compound, a bipolar compound, or any combination thereof. The host may not include a transition metal.
For example, the host in the emission layer may include a hole-transporting compound and an electron-transporting compound, wherein the hole-transporting compound and the electron-transporting compound may be different from each other.
In an embodiment, the hole-transporting compound may include at least one π electron-rich C3-C60 cyclic group and may not include an electron-transporting group.
Examples of the electron-transporting groups may include a cyano group, a fluoro group, a π electron-depleted nitrogen-containing cyclic group, a phosphine oxide group, a sulfoxide group, etc.
The “π electron-depleted nitrogen-containing cyclic group” as used herein may be a C1-C60 heterocyclic group including at least one *—N═*′ moiety as a ring-forming moiety.
Examples of the π electron-depleted nitrogen-containing cyclic group may include a triazine group, an imidazole group, and the like.
The “π electron-rich C3-C60 cyclic group” as used herein may be a C3-C60 cyclic group which does not include a *—N═*′ moiety as a ring-forming moiety. Examples of the π electron-rich C3-C60 cyclic group may include a benzene group, a naphthalene group, a triphenylene group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, an indolodibenzofuran group, an indolodibenzothiophene group, an indolocarbazole group, a naphthobenzofuran group, a naphthobenzothiophene group, a benzocarbazole group, a phenanthrenobenzofuran group, a phenanthrenobenzothiophene group, a naphthocarbazole group, a dinaphthofuran group, a dinaphthothiophene group, a dibenzocarbazole group, and the like.
For example, the hole-transporting compound may include two or more carbazole groups.
In an embodiment, the electron-transporting compound may be a compound including at least one electron-transporting group. The electron-transporting group may be a cyano group, a fluoro group, a π electron-depleted nitrogen-containing C1-C60 cyclic group, a phosphine oxide group, a sulfoxide group, or a combination thereof. In an embodiment, the electron-transporting compound may include a triazine group.
For example, the electron-transporting compound may include at least one electron-transporting group (for example, a triazine group) and at least one π electron-rich C3-C60 cyclic group (for example, a benzene group, a naphthalene group, a triphenylene group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, an indolodibenzofuran group, an indolodibenzothiophene group, an indolocarbazole group, a naphthobenzofuran group, a naphthobenzothiophene group, a benzocarbazole group, a phenanthrenobenzofuran group, a phenanthrenobenzothiophene group, a naphthocarbazole group, a dinaphthofuran group, a dinaphthothiophene group, a dibenzocarbazole group, or any combination thereof).
In an embodiment, the hole-transporting compound may be a compound represented by Formula 6:
In one or more embodiments, the hole-transporting compound may be a compound represented by Formula 6-1, 6-2, or 6-3:
In one or more embodiments, the hole-transporting compound may be one of Compounds HTH1 to HTH6:
In one or more embodiments, the electron-transporting compound may be a compound represented by Formula 7:
In one or more embodiments, X74 to X76 in Formula 7 may each be N.
In one or more embodiments, L71 to L73 in Formula 7 may each independently be a benzene group, a naphthalene group, a triphenylene group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, an indolodibenzofuran group, an indolodibenzothiophene group, an indolocarbazole group, a naphthobenzofuran group, a naphthobenzothiophene group, a benzocarbazole group, a phenanthrenobenzofuran group, a phenanthrenobenzothiophene group, a naphthocarbazole group, a dinaphthofuran group, a dinaphthothiophene group, or a dibenzocarbazole group, each unsubstituted or substituted with deuterium, —F, a cyano group, a C1-C20 alkyl group, a deuterated C1-C20 alkyl group, a fluorinated C1-C20 alkyl group, a phenyl group, a deuterated phenyl group, a fluorinated phenyl group, a (C1-C20 alkyl)phenyl group, a biphenyl group, a deuterated biphenyl group, a fluorinated biphenyl group, a (C1-C20 alkyl)biphenyl group, —Si(Q33)(Q34)(Q35), or any combination thereof.
In one or more embodiments, in Formula 7, at least one of L71 in the number of e71, at least one of L72 in the number of e72, at least one of L73 in the number of e73, or any combination thereof may each independently be a dibenzofuran group, a dibenzothiophene group, a carbazole group, an indolodibenzofuran group, an indolodibenzothiophene group, an indolocarbazole group, a naphthobenzofuran group, a naphthobenzothiophene group, a benzocarbazole group, a phenanthrenobenzofuran group, a phenanthrenobenzothiophene group, a naphthocarbazole group, a dinaphthofuran group, a dinaphthothiophene group, or a dibenzocarbazole group, each unsubstituted or substituted with deuterium, —F, a cyano group, a C1-C20 alkyl group, a deuterated C1-C20 alkyl group, a fluorinated C1-C20 alkyl group, a phenyl group, a deuterated phenyl group, a fluorinated phenyl group, a (C1-C20 alkyl)phenyl group, a biphenyl group, a deuterated biphenyl group, a fluorinated biphenyl group, a (C1-C20 alkyl)biphenyl group, —Si(Q33)(Q34)(Q35), or any combination thereof.
In one or more embodiments, in Formula 7, at least one of L71 in the number of e71, at least one of L72 in the number of e72, at least one of L73 in the number of e73, or any combination thereof may include a carbazole group, an indolocarbazole group, a benzocarbazole group, a naphthocarbazole group, or a dibenzocarbazole group, wherein a nitrogen atom of a pyrrole group of, the carbazole group, the indolocarbazole group, the benzocarbazole group, the naphthocarbazole group, or the dibenzocarbazole group, may be linked to a carbon atom of a 6-membered ring including X74 to X76 in Formula 7 via a single bond or with neighboring L71, L72, and/or L73 located therebetween.
In one or more embodiments, e71 to e73 in Formula 7 indicate the numbers of L71 to L73, respectively, and may each independently be 1, 2, 3, 4, or 5.
In one or more embodiments, R71 to R76 in Formula 7 may each independently be:
In one or more embodiments, the electron-transporting compound may be one of Compounds ETH1 to ETH7:
In the first and second embodiments, the organometallic compound may be represented by Formula 30:
In an embodiment, M31 in Formula 30 may be Pt, Pd, or Au.
In one or more embodiments, M31 in Formula 30 may be Pt or Pd.
In one or more embodiments, in Formula 30, a bond between X11 and M31 may be a coordinate bond.
In one or more embodiments, in Formula 30, X11 may be C, and a bond between X11 and M31 may be a coordinate bond. That is, X11 in Formula 30 may be C in a carbene moiety.
In one or more embodiments, ring CY31 to ring CY34 in Formula 30 may each independently be i) a first ring, ii) a second ring, iii) a condensed ring in which two or more first rings are condensed with each other, iv) a condensed ring in which two or more second rings are condensed with each other, or v) a condensed ring in which at least one first ring is condensed with at least one second ring,
In an embodiment, R31 to R34, R35a, R35b, R36a, R36b, R37a, R37b, R38a, and R38b may each independently be:
In an embodiment, the organometallic compound represented by Formula 30 may be an organometallic compound represented by Formula 3-1 or 3-2:
In Formula 3-1, a bond between carbon of an imidazole group and M31 may be a coordinate bond. That is, the imidazole group in Formula 3-1 may include a carbene moiety bonded to M31.
In Formula 3-2, a bond between carbon of a benzimidazole group and M31 may be a coordinate bond. That is, the benzimidazole group in Formula 3-2 may include a carbene moiety bonded to M31.
Therefore, Formula 3-1′ in which the carbon bonded to M31 in the imidazole group is carbene, is the same as Formula 3-1, and Formula 3-2′ in which the carbon bonded to M31 in the benzimidazole group is carbene, is the same as Formula 3-2:
In Formulae 3-1 and 3-2,
In an embodiment, in Formulae 3-1 and 3-2,
For example, in Formulae 3-1 and 3-2, 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 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.
According to an embodiment, the organometallic compound represented by Formula 30 may be an organometallic compound represented by Formula 3-1(1) or an organometallic compound represented by Formula 3-2(1):
In Formulae 3-1(1) and 3-2(1),
In the first and second embodiments, the organometallic compound may be an organometallic compound represented by Formula 5:
M51(L51)n51(L52)n52 Formula 5
In some embodiments, M51 may be a first-row transition metal, a second-row transition metal, or a third-row transition metal.
In some 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 some embodiments, M51 may be Ir, Pt, Os, or Rh.
In one or more embodiments, M51 may be Ir or Os.
In Formula 5, L51 may be a ligand represented by Formula 5A, and L52 may be a ligand represented by Formula 5B:
n51 in Formula 5 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.
52 in Formula 5 may be 0, 1, or 2, wherein, when n52 is 2, two L52 may be identical to or different from each other.
The sum of n51 and n52 in Formula 5 may be 2 or 3. For example, the sum of n51 and n52 may be 3.
In an embodiment, in Formula 5, i) M may be Ir, and n51+n52=3; or ii) M may be Pt, and n51+n52=2.
In one or more embodiments, in Formula 5, M may be Ir, and i) n51 may be 1, and n52 may be 2, or ii) n51 may be 2, and n52 may be 1.
L51 and L52 in Formula 5 may be different from each other.
Y51 to Y54 in Formulae 5A to 5B may each independently be C or N. For example, Y51 and Y53 may each be N, and Y52 and Y54 may each be C.
Ring CY51 to ring CY54 in Formulae 5A and 5B may each independently be a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
For example, ring CY51 to ring CY54 in Formulae 5A and 5B may each independently include i) a third ring, ii) a fourth ring, iii) a condensed ring in which two or more third rings are condensed with each other, iv) a condensed ring in which two or more fourth rings are condensed with each other, or v) a condensed ring in which at least one third ring is condensed with at least one fourth ring,
In some embodiments, in Formulae 5A 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 5,5-dioxide group, an azaindene group, an azaindole group, an azabenzofuran group, an azabenzothiophene group, an azabenzosilole group, an azabenzoborole group, an azabenzophosphole group, an azabenzogermole group, an azabenzoselenophene group, an azafluorene group, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, an azadibenzoborole group, an azadibenzophosphole group, an azadibenzogermole group, an azadibenzoselenophene group, an azabenzofluorene group, an azabenzocarbazole group, an azanaphthobenzofuran group, an azanaphthobenzothiophene group, an azanaphthobenzosilole group, an azanaphthobenzoborole group, an azanaphthobenzophosphole group, an azanaphthobenzogermole group, an azanaphthobenzoselenophene group, an azadibenzofluorene group, an azadibenzocarbazole group, an azadinaphthofuran group, an azadinaphthothiophene group, an azadinaphthosilole group, an azadinaphthoborole group, an azadinaphthophosphole group, an azadinaphthogermole group, an azadinaphthoselenophene group, an azaindenophenanthrene group, an azaindolophenanthrene group, an azaphenanthrobenzofuran group, an azaphenanthrobenzothiophene group, an azaphenanthrobenzosilole group, an azaphenanthrobenzoborole group, an azaphenanthrobenzophosphole group, an azaphenanthrobenzogermole group, an azaphenanthrobenzoselenophene group, an azadibenzothiophene 5-oxide group, an aza9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a benzoquinoline group, a benzoisoquinoline group, a benzoquinoxaline group, a benzoquinazoline group, a phenanthroline group, a phenanthridine group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isooxazole 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 pyridinooxazole group, a pyridinoisoxazole group, a pyridinothiazole group, a pyridinoisothiazole group, a pyridinooxadiazole group, a pyridinothiadiazole group, a pyrimidinopyrrole group, a pyrimidinopyrazole group, a pyrimidinoimidazole group, a pyrimidinooxazole group, a pyrimidinoisoxazole group, a pyrimidinothiazole group, a pyrimidinoisothiazole group, a pyrimidinooxadiazole group, a pyrimidinothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, a 5,6,7,8-tetrahydroquinoline group, an adamantane group, a norbornane group, a norbornene group, a benzene group condensed with a cyclohexane group, a benzene group condensed with a norbornane group, a pyridine group condensed with a cyclohexane group, or a pyridine group condensed with a norbornane group.
For example, ring CY51 and ring CY53 in Formulae 5A and 5B may be different from each other.
In one or more embodiments, ring CY52 and ring CY54 in Formulae 5A and 5B may be different from each other.
In one or more embodiments, ring CY51 to ring CY54 in Formulae 5A and 5B may be different from each other.
R51 to R54 in Formulae 5A and 5B 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, —N(Q51)(Q52), —Si(Q53)(Q54)(Qss), —Ge(Q53)(Q54)(Q55), —B(Q56)(Q57), —P(═O)(Q58)(Q59), or —P(Q58)(Q59). 051 to Q59 are each the same as described in the specification.
In an embodiment, R51 to R54 in Formulae 5A and 5B may each independently be:
In one or more embodiments, R51 to R54 may each independently be:
b51 to b54 in Formulae 5A and 5B indicate the numbers of R51 to R54, 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, in Formula 5A, Y52 may be C, a bond between Y52 and M51 may be a covalent bond, and at least one of R52 in the number of b52 may be a cyano group or —F.
In one or more embodiments, in Formula 5A, Y51 may be N, a bond between Y51 and M51 may be a coordinate bond, CY51 may be an imidazole group, a triazole group, a benzimidazole group, or a triazolopyridine group, and at least one of R52 in the number of b52 may be a cyano group or —F.
In one or more embodiments, in Formula 5A, Y51 may be C, and a bond between Y51 and M51 may be a coordinate bond.
In one or more embodiments, in Formula 5A, Y51 may be C, a bond between Y51 and M51 may be a coordinate bond, and CY51 may be a benzimidazole group or an imidazopyrazine group.
Specific examples of an organometallic compound are represented by Formula 30 or 5.
For example, the organometallic compound represented by Formula 30 or 5 may be one of Compounds P1 to P52:
In the first and second embodiments, the delayed fluorescence material may be a polycyclic compound represented by Formula 4:
In an embodiment, ring CY41 to ring CY43 may each independently be i) a benzene group, or ii) a polycyclic group in which two or more C3-C30 cyclic groups are condensed with each other. In this regard, two C3-C30 cyclic groups of the polycyclic group may be condensed with each other while sharing boron (B) or nitrogen (N).
In one or more embodiments, at least one of b41 to b43 or at least two of b41 to b43 may each be 1. In one or more embodiments, two of b41 to b43 may be 1, and the other one may be 0.
In one or more embodiments, R41 to R49 may each independently be:
In one or more embodiments, the polycyclic compound represented by Formula 4 may be a polycyclic compound represented by one of Formulae 4-1 to 4-9:
Specific examples of a polycyclic compound represented by Formula 4.
The polycyclic compound represented by Formula 4 may be selected from Compounds D1 to D30:
The FIGURE is a schematic cross-sectional view of an organic light-emitting device 10 according to an embodiment. Hereinafter, the structure and manufacturing method of the organic light-emitting device 10 according to an embodiment of the disclosure will be described in connection with the FIGURE.
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 interlayer 10A between the first electrode 11 and the second electrode 19.
In the FIGURE, the interlayer 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.
The first electrode 11 may be produced by 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. 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 combinations thereof. In some embodiments, when the first electrode 11 is a semi-transmissive electrode or a reflective electrode, a 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-layered structure or a multi-layered structure including a plurality of layers.
A thickness of the emission layer 15 may be in a range of about 100 ANGSTROM to about 1,000 ANGSTROM, for example, about 200 ANGSTROM to about 600 ANGSTROM. When the thickness of the emission layer is within these ranges, excellent light-emission characteristics may be obtained without a substantial increase in driving voltage.
In an embodiment, the condensed polycyclic compound described above may be included in the emission layer 15. The emission layer 15 may have a feature described in the first and second embodiments.
The emission layer 15 may further include a host as described above in addition to the condensed polycyclic compound, sensitizer, and emitter described above.
The hole transport region 12 may be located 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-layered structure or a multi-layered 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.
For example, the hole transport region 12 may include an amine-based compound.
In an embodiment, the hole transport region 12 may include, for example, m-MTDATA, TDATA, 2-TNATA, NPB, p-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (PANI/CSA), polyaniline/poly(4-styrenesulfonate) (PANI/PSS), one of a compound represented by Formula 201 to a compound represented by Formula 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 an embodiment, 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, and a benzothienocarbazole group.
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, and a benzothienocarbazole group.
In one or more embodiments, the hole transport region 12 may include a compound represented by Formula 201, a compound represented by Formula 202, or any combination thereof.
In an embodiment, 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 about −3.5 eV or less.
The p-dopant may include a quinone derivative, a metal oxide, a cyano group-containing compound, or any combination thereof.
In an embodiment, 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 of about 100 ANGSTROM to about 10,000 ANGSTROM, for example, about 400 ANGSTROM to about 2000 ANGSTROM, and the emission layer 15 may have a thickness of about 100 ANGSTROM to about 3,000 ANGSTROM, for example, about 300 ANGSTROM to about 1,000 ANGSTROM. When the thickness of each of the hole transport region 12 and the emission layer 15 is within these ranges described above, satisfactory hole transportation characteristics and/or luminescent characteristics may be obtained without a substantial increase in driving voltage.
The hole transport region 12 may further include a buffer layer.
Also, the buffer layer may compensate for an optical resonance distance according to a wavelength of light emitted from the emission layer, and thus, efficiency of a formed organic light-emitting device may be improved.
The hole transport region 12 may further include an electron-blocking layer. The electron-blocking layer may include a known material, for example, mCP or DBFPO:
The electron transport region 17 is placed 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-layered structure or a multi-layered 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 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-depleted nitrogen-containing C1-C60 cyclic group. The π electron-depleted nitrogen-containing C1-C60 cyclic group is the same as described above.
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 in the number of xe11 and R601 in the number of xe21 may include the π electron-depleted 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, a benzoisothiazole 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, 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,
Q31 to Q33 may each independently be a C1-C10 alkyl group, a C1-C10 alkoxy group, a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group.
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, a benzoisothiazolyl group, a benzoxazolyl group, a benzoisoxazolyl 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, a benzoisothiazolyl group, a benzoxazolyl group, a benzoisoxazolyl 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 one of Compounds ET1 to ET36 or any combination thereof:
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 the range of about 20 ANGSTROM to about 1,000 ANGSTROM, for example, about 30 ANGSTROM to about 300 ANGSTROM. 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 the range of about 100 ANGSTROM to about 1,000 ANGSTROM, for example, about 150 ANGSTROM to about 500 ANGSTROM. When the thickness of the electron transport layer is within the range described above, the electron transport layer may have satisfactory electron-transporting characteristics 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 materials described above, 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.
In an embodiment, 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-layered structure including a single layer including a single material, ii) a single-layered structure including a single layer including a plurality of different materials, or iii) a multi-layered structure having a plurality of layers including a plurality of different materials.
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, or K2O; one of alkali metal halides such as LiF, NaF, CsF, KF, LiI, NaI, CsI, or KI; or any combination thereof. In an embodiment, the alkali metal compound may include LiF, Li2O, NaF, LiI, NaI, CsI, 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, YbI3, 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 further 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, 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 ANGSTROM to about 100 ANGSTROM, and, for example, about 3 ANGSTROM to about 90 ANGSTROM. When the thickness of the electron injection layer is within the ranges described above, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.
The second electrode 19 is arranged on the aforementioned interlayer 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 lithium (Li), silver (Ag), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (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-layered structure having a single layer or a multi-layered structure including two or more layers.
The term “C1-C60 alkyl group” as used herein refers to a linear or branched saturated aliphatic hydrocarbons monovalent group having 1 to 60 carbon atoms, and the term “C1-C60 alkylene group” as used here refers to a divalent group having the same structure as the C1-C60 alkyl group.
Examples of the C1-C60 alkyl group, the C1-C20 alkyl group, and/or the C1-C11 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 include 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 include an ethenyl group, a propenyl group, and a butenyl group. The term “C2-C60 alkenylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethynyl group, and a propynyl group. The term “C2-C60 alkynylene group” as used herein refers to a divalent group having the same structure as 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, 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 include a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group. The term “C3-C10 cycloalkenylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkenyl group.
The term “C2-C10 heterocycloalkenyl group” as used herein refers to a monovalent monocyclic group that has at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom, 2 to 10 carbon atoms, and at least one carbon-carbon double bond in its ring. Examples of the C2-C10 heterocycloalkenyl group are a 2,3-dihydrofuranyl group, and a 2,3-dihydrothiophenyl group. The term “C2-C10 heterocycloalkenylene group” as used herein refers to a divalent group having the same structure as the C2-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as used herein refers to a monovalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms, and the term “C6-C60 arylene group” as used herein refers to a divalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms. Examples of the C6-C60 aryl group 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 a heterocyclic aromatic system having at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and 1 to 60 carbon atoms as a ring-forming atoms, and the term “C1-C60 heteroarylene group” as used herein refers to a divalent group that includes a heterocyclic aromatic system having at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and 1 to 60 carbon atoms as a ring-forming atom. 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 C1-C60 heteroaryl group and the C1-C60 heteroarylene group each include two or more rings, the rings may be fused to each other.
The term “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 having two or more rings condensed and only carbon atoms (for example, the number of carbon atoms may be in a range of 8 to 60) as ring-forming atoms, wherein the molecular structure as a whole is non-aromatic. Examples of the monovalent non-aromatic condensed polycyclic group include a fluorenyl group. The term “divalent non-aromatic condensed polycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed polycyclic group 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 its entire molecular structure. Examples of the monovalent non-aromatic condensed heteropolycyclic group include a carbazolyl group. The term “divalent non-aromatic condensed heteropolycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed heteropolycyclic group 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 an adjacent 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 an adjacent 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 carbocyclic group” and “C5-C30 carbocyclic group” as used herein refers to a monocyclic or polycyclic group only having 5 to 60 or 5 to 30 carbon atoms as a ring-forming atom, respectively, and may be, for example, a) a third ring or b) a condensed ring in which two or more third rings are condensed with each other.
The term “C1-C60 heterocyclic group” and “C1-C30 heterocyclic group” as used herein refers to a monocyclic or polycyclic group that has 1 to 60 or 1 to 30 carbon atoms and at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom, respectively, and may be, for example, a) a fourth ring, b) a condensed ring in which two or more fourth rings are condensed with each other, 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, an oxatriazole group, an isoxatriazole group, a thiazole group, an isothiazole group, a thiadiazole group, an isothiadiazole group, a thiatriazole group, an isothiatriazole 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.
In some embodiments, 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, a benzoisothiazole 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, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, an acridine group, or a pyridopyrazine group.
In some embodiments, 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 indolophenanthrene group, a benzofuranophenanthrene group, or a benzothienophenanthrene group.
For example, the C5-C60 carbocyclic group or the C5-C30 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, a 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 or the C1-C30 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-depleted nitrogen-containing C1-C60 cyclic group, a π electron-rich C3-C60 cyclic group, a C5-C60 carbocyclic group, a C5-C30 carbocyclic group, a C1-C60 heterocyclic group, and a C1-C30 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.
Substituents of the substituted π electron-depleted nitrogen-containing C1-C60 cyclic group, the substituted π electron-rich C3-C60 cyclic group, the substituted C5-C60 carbocyclic group, the substituted C5-C30 carbocyclic group, the substituted C1-C60 heterocyclic group, the substituted C1-C30 heterocyclic group, the substituted C1-C60 alkylene group, the substituted C2-C60 alkenylene group, the substituted C2-C60 alkynylene group, the substituted C3-C10 cycloalkylene group, the substituted C1-C10 heterocycloalkylene group, the substituted C3-C10 cycloalkenylene group, the substituted C1-C10 heterocycloalkenylene group, the substituted C6-C60 arylene group, the substituted C1-C60 heteroarylene group, the substituted divalent non-aromatic condensed polycyclic group, the substituted divalent non-aromatic condensed heteropolycyclic group, the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted 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 used 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 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 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-C1 heterocycloalkyl group; a C3-C10 cycloalkenyl group; a C1-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” used herein refers to a temperature of about 25° C.
The terms “a biphenyl group, a terphenyl group, and a quaterphenyl group” used herein respectively refer to monovalent groups in which two, three, or four phenyl groups which are linked together via a single bond.
Hereinafter, a compound and a light-emitting device according to embodiments are described in detail with reference to Synthesis Examples and Examples. However, the compound and the light-emitting device are 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.
2-bromo-2′-chloro-1,1′-biphenyl (40.0 g, 149.50 mmol), bis(pinacolato)diboron (B2pin2) (58.236 g, 229.33 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (PdCl2(dppf)) (5.593 g, 7.64 mmol), potassium acetate (KOAc) (37.514 g, 382.21 mmol), and 300 ml of 1,4-dioxane were added into a round bottom flask, and the mixture was stirred while refluxing at 120° C. in a nitrogen atmosphere. After the reaction was completed, an organic solvent layer was concentrated and then purified by column chromatography to obtain Intermediate 1(a) (47 g, yield: 100%).
LC-MS (calculated: 314.12 g/mol, found: 315.12 (M+1))
580 ml of a mixture of toluene and ethanol was added to Intermediate 1(a) (40.42 g, 128.68 mmol), 2-bromoaniline (20.0 g, 116.98 mmol), tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) (6.776 g, 5.85 mmol), and sodium carbonate (24.79 g, 233.96 mmol, 2.0 eq) and then stirred at 80° C. After the reaction was completed, a resultant product was cooled to room temperature and then subjected to an extraction process using distilled water and dichloromethane. Residual water was removed therefrom by using anhydrous magnesium sulfate, and the resultant product was filtered under reduced pressure. An organic layer thus obtained was concentrated under reduced pressure, and a solid obtained therefrom was separated and purified by column chromatography to obtain Intermediate 1(b) (14.22 g, yield: 44%).
LC-MS (calculated: 279.08 g/mol, found: 280.08 (M+1))
Intermediate 1(c) (24.2 g, yield: 80%) was synthesized in the same manner as in the synthesis of Intermediate 1(b) of Synthesis Example 1, except that Intermediate 1(b) (14.0 g, 50.16 mmol) and 2,2′-(4,6-difluoro-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (9.18 g, 25.08 mmol) were respectively used instead of 2-bromoaniline and Intermediate 1(a).
LC-MS (calculated: 600.24 g/mol, found: 601.24 (M+1))
Intermediate 1(c) (22.0 g, 36.65 mmol), potassium carbonate (10.131 g, 73.30 mmol), and N,N-dimethylformamide (0.1 M) were mixed and stirred at 110° C. After the reaction was completed, the resultant product was cooled to room temperature, methanol was added thereto, and the mixture was filtered by using silica gel. After an organic layer thus obtained was concentrated and dissolved again in toluene, the organic layer was filtered by using silica gel and then concentrated. A resultant product obtained therefrom was recrystallized by using toluene to thereby obtain Intermediate 1(d) as a yellow solid (18.3 g, yield: 89%).
LC-MS (calculated: 560.23 g/mol, found: 561.2 g/mol (M+1))
Intermediate 1(d) (8.00 g, 14.28 mmol), 1-bromo-3-iodobenzene (80.79 g, 285.6 mmol), cuprous iodide (5.44 g, 28.56 mmol), and 75 ml of tetraethoxysilane (TEOS) (0.2 M) were mixed and stirred at 155° C. for 18 hours. After the reaction was completed, and the resultant product was cooled to room temperature, dichloromethane was added thereto, and the mixture was filtered by using silica gel. An organic layer thus obtained was concentrated under reduced pressure, and a solid obtained therefrom was separated and purified by column chromatography to obtain Intermediate 1(e) (11.6 g, yield: 94%).
LC-MS (calculated: 870.11 g/mol, found: 871.11 (M+1))
Intermediate 1(e) (3.0 g, 3.46 mmol), boron triiodide (B13) (8.118 g, 20.73 mmol), and 20 ml of dichlorobenzene (0.2 M) were mixed and stirred at 155° C. for 5 hours. After the reaction was completed, the resultant product was quenched by using methanol and then filtered. An organic layer obtained through an extraction process using dichloromethane was concentrated under reduced pressure. A solid obtained therefrom was separated and purified by column chromatography to obtain Intermediate 1(f) (0.57 g, yield: 19%).
LC-MS (calculated: 876.09 g/mol, found: 877.09 (M+1))
Intermediate 1(f) (1.50 g, 1.71 mmol), carbazole-d8 (0.69 g, 3.94 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) (0.157 g, 0.17 mmol), sodium tert-butoxide (0.494 g, 5.14 mmol), S-phos (0.141 g, 0.34 mmol), and 10 ml of xylene (0.2 M) were mixed and stirred at 125° C. for 1 hour. After the reaction was completed, dichloromethane was added to the resultant product which was cooled to room temperature, and an organic layer obtained by filtration using silica gel was concentrated under reduced pressure. A solid obtained therefrom was separated and purified by column chromatography to obtain Compound 1 (1.2 g, yield: 66%).
LC-MS (calculated: 1066.49 g/mol, found: 1067.49 (M+1))
Compound 2 (1.67 g, yield: 80%) was synthesized in the same manner as in the synthesis of Compound 1 of Synthesis Example 1, except that (3-(9H-carbazol-9-yl-d8)phenyl)boronic acid) (available from HANCHEM Co. Ltd) (1.162 g, 3.94 mmol) was used instead of carbazole-d8.
LC-MS (calculated: 1218.55 g/mol, found: 1219.55 (M+1)) Synthesis Example 3 (Compound 3)
Intermediate 3(a) (32.1 g, yield: 99%) was synthesized in the same manner as in the synthesis of Intermediate 1(a) of Synthesis Example 1, except that 2,4-dibromo-3-(tert-butyl)-1,5-difluorobenzene (25.0 g, 76.71 mmol) was used instead of 2-bromo-2′-chloro-1,1′-biphenyl.
LC-MS (calculated: 422.26 g/mol, found: 423.26 (M+1))
Intermediate 3(c) (24.2 g, yield: 74%) was synthesized in the same manner as in the synthesis of Compound 1(c) of Synthesis Example 1, except that Intermediate 3(a) (21.183 g, 50.16 mmol) was used instead of 2,2′-(4,6-difluoro-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane).
LC-MS (calculated: 656.30 g/mol, found: 657.30 (M+1))
Intermediate 3(d) (7.4 g, yield: 79%) was synthesized in the same manner as in the synthesis of Compound 1(d) of Synthesis Example 1, except that Intermediate 3(c) (10.0 g, 15.24 mmol) was used instead of Intermediate 1(c).
LC-MS (calculated: 616.29 g/mol, found: 617.29 (M+1))
Intermediate 3(e) (8.4 g, yield: 80%) was synthesized in the same manner as in the synthesis of Compound 1(e) of Synthesis Example 1, except that Intermediate 3(d) (7.0 g, 11.36 mmol) was used instead of Intermediate 1(d).
LC-MS (calculated: 924.17 g/mol, found: 925.17 (M+1))
Intermediate 3(f) (0.34 g, yield: 17%) was synthesized in the same manner as in the synthesis of Compound 1(f) of Synthesis Example 1, except that Intermediate 3(e) (2.0 g, 2.16 mmol) was used instead of Intermediate 1(e).
LC-MS (calculated: 932.16 g/mol, found: 933.16 (M+1))
Compound 3 (0.96 g, yield: 80%) was synthesized in the same manner as in the synthesis of Compound 1 of Synthesis Example 1, except that Intermediate 3(f) (1.0 g, 1.07 mmol) was used instead of Intermediate 1(f).
LC-MS (calculated: 1122.55 g/mol, found: 1123.55 (M+1))
Compound 4 (0.78 g, yield: 57%) was synthesized in the same manner as in the synthesis of Compound 2 of Synthesis Example 2, except that Intermediate 3(f) (1.0 g, 1.07 mmol) was used instead of Intermediate 1(f).
LC-MS (calculated: 1274.62 g/mol, found: 1275.62 (M+1))
Intermediate 5(e) (9.2 g, yield: 88%) was synthesized in the same manner as in the synthesis of Intermediate 3(e) of Synthesis Example 3, except that 1-bromo-4-iodobenzene (64.267 g, 227.17 mmol) was used instead of 1-bromo-3-iodobenzene.
LC-MS (calculated: 924.17 g/mol, found: 925.17 (M+1))
Intermediate 5(f) (0.18 g, yield: 20%) was synthesized in the same manner as in the synthesis of Intermediate 1(f) of Synthesis Example 1, except that Intermediate 5(e) (0.90 g, 0.97 mmol) was used instead of Intermediate 1(e).
LC-MS (calculated: 932.16 g/mol, found: 933.16 (M+1))
Compound 5 (0.45 g, yield: 52%) was synthesized in the same manner as in the synthesis of Compound 1 of Synthesis Example 1, except that Intermediate 5(f) (0.72 g, 0.77 mmol) was used instead of Intermediate 1(f).
LC-MS (calculated: 1122.55 g/mol, found: 1123.55 (M+1))
Compound 6 (0.85 g, yield: 62%) was synthesized in the same manner as in the synthesis of Compound 2 of Synthesis Example 2, except that Intermediate 5(f) (1.0 g, 1.07 mmol) was used instead of Intermediate 1(f).
LC-MS (calculated: 1274.61 g/mol, found: 1275.61 (M+1))
Intermediate 7(a) (17.8 g, yield: 88%) was synthesized in the same manner as in the synthesis of Intermediate 1(b) of Synthesis Example 1, except that (5-bromo-2-fluorophenyl)boronic acid (13.52 g, 62.04 mmol) and 2-bromo-2′-chloro-1,1′-biphenyl (15.0 g, 56.40 mmol) were used instead of Intermediate 1(a) and 2-bromoaniline, respectively.
LC-MS (calculated: 359.97 g/mol, found: 360.97 (M+1))
Intermediate 7(b) (15.4 g, yield: 91%) was synthesized in the same manner as in the synthesis of Intermediate 1(a) of Synthesis Example 1, except that Intermediate 7(a) and phenylboronic acid (6.340 g, 51.95 mmol) were used instead of 2-bromo-2′-chloro-1,1′-biphenyl and bis(pinacolato)diboron, respectively.
LC-MS (calculated: 358.09 g/mol, found: 359.09 (M+1))
Intermediate 7(c) (21 g, yield: 95%) was synthesized in the same manner as in the synthesis of Intermediate 1(a) of Synthesis Example 1, except that Intermediate 7(b) (17.5 g, 48.87 mmol) was used instead of 2-bromo-2′-chloro-1,1′-biphenyl.
LC-MS (calculated: 450.22 g/mol, found: 451.22 (M+1))
Intermediate 7(d) (15.40 g, yield: 91%) was synthesized in the same manner as in the synthesis of Intermediate 1(b) of Synthesis Example 1, except that Intermediate 7(c) (20.277 g, 45.04 mmol) was used instead of Intermediate 1(a).
LC-MS (calculated: 415.17 g/mol, found: 416.17 (M+1))
Intermediate 7(e) (12.2 g, yield: 85%) was synthesized in the same manner as in the synthesis of Intermediate 1(d) of Synthesis Example 1, except that Intermediate 7(d) (15.0 g, 36.13 mmol) was used instead of Intermediate 1(c).
LC-MS (calculated: 395.17 g/mol, found: 396.17 (M+1))
Intermediate 7(e) (5.47 g, 1.74 mmol), 9-(3,5-dibromo-4-chlorophenyl)-9H-carbazole (available from HANCHEM Co. Ltd) (3.0 g, 6.93 mmol), Pd2(dba)3 (0.635 g, 0.69 mmol), S-Phos (0.57 g, 1.39 mmol), and NaOtBu (1.998 g, 20.79 mmol) were mixed with toluene (35 ml), and the mixture was heated and stirred in a nitrogen atmosphere at 120° C. for 2 hours. The solvent was removed by using a rotary evaporator, and 200 ml of dichloromethane was added thereto to dissolve the crude product, followed by washing twice with water (200 ml). Next, the organic layer was dried using anhydrous MgSO4, filtered, and the filtrate was concentrated using a rotary evaporator. A purification process through column chromatography was performed thereon to synthesize Intermediate 7(f) (4.3 g, yield: 58%).
LC-MS (calculated: 1063.37 g/mol, found: 1064.37 (M+1))
Intermediate 7(f) (4.00 g, 3.76 mmol) and t-butyl benzene (100 ml) were mixed, and 1.6 M of tert-BuLi in pentane solution (9.40 mmol) was added thereto in a nitrogen atmosphere at −78° C. Then, the temperature was raised to 60° C., and the mixture was heated and stirred for 1 hour. After the reaction was completed, the mixture was cooled to −40° C., and BBr3 (1.885 g, 7.52 mmol) was added thereto. Then, the mixture was stirred at room temperature for 1 hour and cooled again to −40° C. Next, N,N-diisopropylethylamine (0.972 g, 7.52 mmol) was added thereto, and the mixture was heated and stirred at 120° C. for 4 hours. After the mixture was cooled to room temperature, a NaOAc sat. aq. solution and 200 ml of ethyl acetate (EA) was added thereto, followed by washing using water (300 ml). The organic layer was dried using anhydrous MgSO4, filtered, and the filtrate was concentrated using a rotary evaporator. A purification process through column chromatography was performed thereon to synthesize Compound 7 (1.32 g, yield: 34%).
LC-MS (calculated: 1037.39 g/mol, found: 1038.39 (M+1))
Intermediate 8(b) (7.23 g, yield: 90%) was synthesized in the same manner as in the synthesis of Intermediate 7(b) of Synthesis Example 7, except that (4-(tert-butyl)phenyl)boronic acid (4.503 g, 25.28 mmol) was used instead of phenylboronic acid.
LC-MS (calculated: 414.16 g/mol, found: 415.17 (M+1))
Intermediate 8(c) (8.5 g, yield: 97%) was synthesized in the same manner as in the synthesis of Intermediate 7(c) of Synthesis Example 7, except that Intermediate 8(b) (7.2 g, 17.38 mmol) was used instead of Intermediate 7(b).
LC-MS (calculated: 506.28 g/mol, found: 507.28 (M+1))
Intermediate 8(d) (4.13 g, yield: 68%) was synthesized in the same manner as in the synthesis of Intermediate 7(d) of Synthesis Example 7, except that Intermediate 8(c) (8.5 g, 16.73 mmol) was used instead of Intermediate 7(c).
LC-MS (calculated: 471.24 g/mol, found: 472.24 (M+1))
Intermediate 8(e) (3.8 g, yield: 85%) was synthesized in the same manner as in the synthesis of Intermediate 7(e) of Synthesis Example 7, except that Intermediate 8(d) (4.1 g, 9.88 mmol) was used instead of Intermediate 7(d).
LC-MS (calculated: 451.23 g/mol, found: 452.23 (M+1))
Intermediate 8(f) (2.98 g, yield: 61%) was synthesized in the same manner as in the synthesis of Intermediate 7(f) of Synthesis Example 7, except that Intermediate 8(e) (3.753 g, 8.32 mmol) was used instead of Intermediate 7(e).
LC-MS (calculated: 1175.49 g/mol, found: 1176.49 (M+1))
Compound 8 (1.12 g, yield: 39%) was synthesized in the same manner as in the synthesis of Compound 7 of Synthesis Example 7, except that Intermediate 8(f) (2.9 g, 2.47 mmol) was used instead of Intermediate 7(f).
LC-MS (calculated: 1149.52 g/mol, found: 1150.52 (M+1))
Intermediate 9(b) (21.2 g, yield: 92%) was synthesized in the same manner as in the synthesis of Intermediate 7(b) of Synthesis Example 7, except that (3-(tert-butyl)phenyl)boronic acid (12.86 g, 72.23 mmol) was used instead of phenylboronic acid.
LC-MS (calculated: 414.16 g/mol, found: 415.17 (M+1))
Intermediate 9(c) (20.4 g, yield: 79%) was synthesized in the same manner as in the synthesis of Intermediate 7(c) of Synthesis Example 7, except that Intermediate 9(b) (21.0 g, 50.71 mmol) was used instead of Intermediate 7(b).
LC-MS (calculated: 506.28 g/mol, found: 507.28 (M+1))
Intermediate 9(d) (11.1 g, yield: 81%) was synthesized in the same manner as in the synthesis of Intermediate 7(d) of Synthesis Example 7, except that Intermediate 9(c) (19.25 g, 38.02 mmol) was used instead of Intermediate 7(c).
LC-MS (calculated: 471.24 g/mol, found: 472.24 (M+1))
Intermediate 9(e) (3.98 g, yield: 83%) was synthesized in the same manner as in the synthesis of Intermediate 7(e) of Synthesis Example 7, except that Intermediate 9(d) (5.0 g, 10.61 mmol) was used instead of Intermediate 7(d).
LC-MS (calculated: 451.23 g/mol, found: 452.23 (M+1))
Intermediate 9(f) (2.98 g, yield: 58%) was synthesized in the same manner as in the synthesis of Intermediate 7(f) of Synthesis Example 7, except that Intermediate 9(e) (3.96 g, 8.78 mmol) was used instead of Intermediate 7(e).
LC-MS (calculated: 1175.49 g/mol, found: 1176.49 (M+1))
Compound 9 (0.9 g, yield: 32%) was synthesized in the same manner as in the synthesis of Compound 7 of Synthesis Example 7, except that Intermediate 9(f) (2.9 g, 2.47 mmol) was used instead of Intermediate 7(f).
LC-MS (calculated: 1149.52 g/mol, found: 1150.52 (M+1))
Intermediate 10(f) (5.66 g, yield: 80%) was synthesized in the same manner as in the synthesis of Intermediate 9(f) of Synthesis Example 9, except that 1,3-dibromo-5-(tert-butyl)benzene (2.0 g, 6.85 mmol) was used instead of 9-(3,5-dibromo-4-chlorophenyl)-9H-carbazole.
LC-MS (calculated: 1032.54 g/mol, found: 1033.54 (M+1))
Compound 10 (1.1 g, yield: 22%) was synthesized in the same manner as in the synthesis of Intermediate 1(f) of Synthesis Example 1, except that Intermediate 10(f) (5.0 g, 4.84 mmol) was used instead of Intermediate 1(e).
LC-MS (calculated: 1040.52 g/mol, found: 1041.52 (M+1))
Intermediate 11(b) (36.2 g, yield: 92%) was synthesized in the same manner as in the synthesis of Intermediate 1(a) of Synthesis Example 1, except that Intermediate 11(a) (30.0 g, 96.81 mmol) was used instead of 2-bromo-2′-chloro-1,1′-biphenyl.
LC-MS (calculated: 406.25 g/mol, found: 407.25 (M+1))
Intermediate 11(c) (14.2 g, yield: 72%) was synthesized in the same manner as in the synthesis of Intermediate 1(b) of Synthesis Example 1, except that Intermediate 11(b) (32.5 g, 80.02 mmol) and bis(2-bromophenyl)amine were used instead of Intermediate 1(a) and 2-bromoaniline.
LC-MS (calculated: 319.14 g/mol, found: 320.14 (M+1))
Intermediate 11(c) (2.9 g, 9.09 mmol) was dissolved in 40 ml of N,N-dimethylformamide (DMF) in a round flask and then cooled and stirred at 0° C. N-bromosuccinimide (3.56 g, 20.0 mmol) dissolved in 20 ml of DMF was slowly added dropwise thereto, followed by stirring at room temperature for reaction. After the reaction was completed, a sodium thiosulfate solution of 2 mol concentration was added thereto, and an organic layer obtained through an extraction process performed by adding dichloromethane thereto was concentrated under reduced pressure. The obtained product was separated by column chromatography to obtain Intermediate 11(d)′ (2.3 g, yield: 64%) and Intermediate 11(d) (1.6 g, yield: 36%) as white solids.
11(d)′: LC-MS (calculated: 397.05 g/mol, found: 398.05 (M+1))
11(d): LC-MS (calculated: 474.96 g/mol, found: 475.96 (M+1))
Intermediate 11(e) (2.45 g, yield: 82%) was synthesized in the same manner as in the synthesis of Intermediate 1(a) of Synthesis Example 1, except that Intermediate 11(d) (3.0 g, 6.32 mmol) and phenylboronic acid (1.0 g, 8.21 mmol) were used instead of 2-bromo-2′-chloro-1,1′-biphenyl and bis(pinacolato)diboron, respectively.
LC-MS (calculated: 471.2 g/mol, found: 472.2 (M+1)
Intermediate 11(f) (1.35 g, yield: 44%) was synthesized in the same manner as in the synthesis of Intermediate 7(f) of Synthesis Example 7, except that Intermediate 11(e) (2.4 g, 5.08 mmol) was used instead of Intermediate 7(e).
LC-MS (calculated: 1215.43 g/mol, found: 1216.43 (M+1))
Compound 11 (0.23 g, yield: 18%) was synthesized in the same manner as in the synthesis of Compound 7 of Synthesis Example 7, except that Intermediate 11(f) (1.3 g, 1.07 mmol) was used instead of Intermediate 7(f).
LC-MS (calculated: 1189.46 g/mol, found: 1189.46 (M+1))
Intermediate 12(a) (17.23 g, yield: 70%) was synthesized in the same manner as in the synthesis of Intermediate 7(f) of Synthesis Example 7, except that Intermediate 11(c) (15.0 g, 50.03 mmol) and 1-bromo-2-fluoro-4-iodobenzene (17.56 g, 55.03 mmol) were used instead of Intermediate 7(e) and 9-(3,5-dibromo-4-chlorophenyl)-9H-carbazole, respectively.
LC-MS (calculated: 491.07 g/mol, found: 492.07 (M+1))
Intermediate 12(b) (14.3 g, yield: 77%) was synthesized in the same manner as in the synthesis of Intermediate 1(a) of Synthesis Example 1, except that Intermediate 12(a) (17.0 g, 34.62 mmol) was used instead of 2-bromo-2′-chloro-1,1′-biphenyl.
LC-MS (calculated: 539.24 g/mol, found: 540.24 (M+1))
Intermediate 12(c) (8.8 g, yield: 62%) was synthesized in the same manner as in the synthesis of Intermediate 1(c) of Synthesis Example 1, except that Intermediate 12(b) (15.07 g, 27.95 mmol) and Intermediate 1(b) (6.0 g, 21.50 mmol) were used instead of 2,2′-(4,6-difluoro-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxoborolane) and Intermediate 1(b), respectively.
LC-MS (calculated: 656.26 g/mol, found: 657.26 (M+1))
Intermediate 12(d) (4.3 g, yield: 74%) was synthesized in the same manner as in the synthesis of Intermediate 1(d) of Synthesis Example 1, except that Intermediate 12(c) (6.0 g, 9.14 mmol) was used instead of Intermediate 1(c).
LC-MS (calculated: 636.26 g/mol, found: 637.26 (M+1))
Intermediate 12(e) (3.56 g, yield: 72%) was synthesized in the same manner as in the synthesis of Intermediate 1(e) of Synthesis Example 1, except that Intermediate 12(d) (4.0 g, 6.29 mmol) was used instead of Intermediate 1(d).
LC-MS (calculated: 790.20 g/mol, found: 791.20 (M+1))
Intermediate 12(f) (0.55 g, yield: 16%) was synthesized in the same manner as in the synthesis of Intermediate 1(f) of Synthesis Example 1, except that Intermediate 12(e) (3.5 g, 4.43 mmol) was used instead of Intermediate 1(e).
LC-MS (calculated: 798.18 g/mol, found: 799.20 g/mol (M+1))
Compound 12 (14.6 g, yield: 22%) was synthesized in the same manner as in the synthesis of Compound 1 of Synthesis Example 1, except that Intermediate 12(f) (0.55 g, 1.74 mmol) was used instead of Intermediate 1(f).
LC-MS (calculated: 893.38 g/mol, found: 894.38 (M+1))
Intermediate 13(a)′ (9.76 g, yield: 80%) was synthesized in the same manner as in the synthesis of Intermediate 7(f) of Synthesis Example 7, except that carbazole and Intermediate 11(d) (10.09, 25.19 mmol) were used instead of Intermediate 7(e) and 9-(3,5-dibromo-4-chlorophenyl)-9H-carbazole, respectively.
LC-MS (calculated: 484.19 g/mol, found: 485.19 (M+1))
Intermediate 113(a) (8.8 g, yield: 68%) was synthesized in the same manner as in the synthesis of Intermediate 7(f) of Synthesis Example 7, except that Intermediate 13(a)′ (9.5 g, 19.62 mmol) and 1-bromo-2-fluoro-4-iodobenzene were used instead of Intermediate 7(e) and 9-(3,5-dibromo-4-chlorophenyl)-9H-carbazole, respectively.
LC-MS (calculated: 656.13 g/mol, found: 657.13 (M+1))
Intermediate 13(b) (9.1 g, yield: 99%) was synthesized in the same manner as in the synthesis of Intermediate 1(a) of Synthesis Example 1, except that Intermediate 13(a) (8.5 g, 12.95 mmol) was used instead of 2-bromo-2′-chloro-1,1′-biphenyl.
LC-MS (calculated: 704.30 g/mol, found: 705.30 (M+1))
Intermediate 13(c) (6.6 g, yield: 83%) was synthesized in the same manner as in the synthesis of Intermediate 1(b) of Synthesis Example 1, except that Intermediate 13(b) (8.858 g, 12.58 mmol) and Intermediate 1(b) were used instead of Intermediate 1(a) and 2-bromoaniline.
LC-MS (calculated: 821.32 g/mol, found: 822.32 (M+1))
Intermediate 13(d) (4.3 g, yield: 68%) was synthesized in the same manner as in the synthesis of Intermediate 1(d) of Synthesis Example 1, except that Intermediate 13(c) (6.5 g, 7.91 mmol) was used instead of Intermediate 1(c).
LC-MS (calculated: 801.31 g/mol, found: 802.31 (M+1))
Intermediate 13(e) (5.34 g, yield: 89%) was synthesized in the same manner as in the synthesis of Intermediate 1(e) of Synthesis Example 1, except that Intermediate 13(d) (4.0 g, 6.29 mmol) was used instead of Intermediate 1(d).
LC-MS (calculated: 955.26 g/mol, found: 956.26 g/mol (M+1))
Intermediate 13(f) (0.88 g, yield: 17%) was synthesized in the same manner as in the synthesis of Intermediate 1(f) of Synthesis Example 1, except that Intermediate 13(e) (5.0 g, 5.23 mmol) was used instead of Intermediate 1(e).
LC-MS (calculated: 963.24 g/mol, found: 963.24 g/mol (M+1))
Compound 13 (0.15 g, yield: 53%) was synthesized in the same manner as in the synthesis of Compound 1 of Synthesis Example 1, except that Intermediate 13(f) (0.88 g, 0.91 mmol) and carbazole were used instead of Intermediate 1(f) and carbazole-d8, respectively.
LC-MS (calculated: 1050.39 g/mol, found: 1051.39 (M+1))
Intermediate 14(a) (14.3 g, yield: 61%) was synthesized in the same manner as in the synthesis of Intermediate 7(f) of Synthesis Example 7, except that [1,1′: 3′, 1″-terphenyl]-2′-amine (15.0 g, 51.37 mmol) and 1,3-dibromo-5-(tert-butyl)benzene (13.85 g, 56.50 mmol) were used instead of Intermediate 7(e) and 9-(3,5-dibromo-4-chlorophenyl)-9H-carbazole, respectively.
LC-MS (calculated: 455.12 g/mol, found: 456.12 g/mol (M+1))
Intermediate 14(b) (17.09 g, yield: 80%) was synthesized in the same manner as in the synthesis of Intermediate 7(f) of Synthesis Example 7, except that Intermediate 11(c) (10.79 g, 33.84 mmol) and Intermediate 14(a) (14.0 g, 30.76 mmol) were used instead of Intermediate 7(e) and 9-(3,5-dibromo-4-chlorophenyl)-9H-carbazole, respectively.
LC-MS (calculated: 694.33 g/mol, found: 695.33 g/mol (M+1))
Intermediate 14(e) (16.6 g, yield: 80%) was synthesized in the same manner as in the synthesis of Intermediate 1(e) of Synthesis Example 1, except that Intermediate 14(b) (17.0 g, 24.48 mmol) was used instead of Intermediate 1(d).
LC-MS (calculated: 848.28 g/mol, found: 849.28 g/mol (M+1))
Intermediate 14(f) (1.8 g, yield: 12%) was synthesized in the same manner as in the synthesis of Intermediate 1(f) of Synthesis Example 1, except that Intermediate 14(e) (15.0 g, 17.68 mmol) was used instead of Intermediate 1(e).
LC-MS (calculated: 856.26 g/mol, found: 857.26 g/mol (M+1)) Synthesis of Compound 14
Compound 14 (1.12 g, yield: 56%) was synthesized in the same manner as in the synthesis of Compound 1 of Synthesis Example 1, except that Intermediate 14(f) (1.8 g, 2.1 mmol) was used instead of Intermediate 1(f).
LC-MS (calculated: 951.46 g/mol, found: 952.46 (M+1))
Intermediate 15(a) (13.7 g, yield: 66%) was synthesized in the same manner as in the synthesis of Intermediate 7(f) of Synthesis Example 7, except that [1,1′:3′,1″-terphenyl]-2′-amine (13.49 g, 55.03 mmol) and 1-bromo-2-fluoro-4-iodobenzene (15.0 g, 50.03 mmol) were used instead of Intermediate 7(e) and 9-(3,5-dibromo-4-chlorophenyl)-9H-carbazole, respectively.
LC-MS (calculated: 417.05 g/mol, found: 418.05 g/mol (M+1))
Intermediate 15(b) (13.3 g, yield: 97%) was synthesized in the same manner as in the synthesis of Intermediate 1(a) of Synthesis Example 1, except that Intermediate 15(a) (12.3 g, 29.49 mmol) was used instead of 2-bromo-2′-chloro-1,1′-biphenyl.
LC-MS (calculated: 465.23 g/mol, found: 466.23 g/mol (M+1))
Intermediate 15(c) (10.1 g, yield: 81%) was synthesized in the same manner as in the synthesis of Intermediate 1(b) of Synthesis Example 1, except that Intermediate 15(b) (13.0 g, 27.95 mmol) and Intermediate 1(b) were used instead of Intermediate 1(a) and 2-bromoaniline, respectively.
LC-MS (calculated: 582.25 g/mol, found: 583.25 g/mol (M+1))
Intermediate 15(d) (8.8 g, yield: 91%) was synthesized in the same manner as in the synthesis of Intermediate 1(d) of Synthesis Example 1, except that Intermediate 15(c) (10.0 g, 17.17 mmol) was used instead of Intermediate 1(c).
LC-MS (calculated: 562.24 g/mol, found: 563.24 g/mol (M+1))
Intermediate 15(e) (9.64 g, yield: 73%) was synthesized in the same manner as in the synthesis of Intermediate 1(e) of Synthesis Example 1, except that Intermediate 15(d) (8.5 g, 15.12 mmol) was used instead of Intermediate 1(d).
LC-MS (calculated: 870.12 g/mol, found: 871.12 g/mol (M+1))
Intermediate 15(f) (2.08 g, yield: 22%) was synthesized in the same manner as in the synthesis of Intermediate 1(f) of Synthesis Example 1, except that Intermediate 15(e) (9.5 g, 10.92 mmol) was used instead of Intermediate 1(e).
LC-MS (calculated: 878.12 g/mol, found: 880.12 g/mol (M+1))
Compound 15 (1.79 g, yield: 75%) was synthesized in the same manner as in the synthesis of Compound 1 of Synthesis Example 1, except that Intermediate 15(f) (2.0 g, 2.28 mmol) and carbazole were used instead of Intermediate 1(f) and carbazole-d8, respectively.
LC-MS (calculated: 1052.41 g/mol, found: 1053.46 (M+1))
1,3-Dibromo-5-(tert-butyl)benzene (0.2 g, 0.68 mmol), 9H-tetrabenzo[b,d,f,h]azonine (0.481 g, 1.51 mmol), Pd2(dba)3 (0.157 g, 0.17 mmol), SPhos (0.155 g, 0.38 mmol) and LHMDS (0.344 g, 2.05 mmol) were mixed with xylene (10 ml), and the mixture was heated and stirred in a nitrogen atmosphere at 120° C. for 3 hours. The solvent was removed by using a rotary evaporator, and 200 ml of dichloromethane was added thereto to dissolve the crude product, followed by washing twice with water (200 ml). The organic layer was dried using anhydrous MgSO4, filtered, and then the solvent was removed from the filtrate by using a rotary evaporator. A purification process through column chromatography was performed thereon to synthesize Intermediate 94(a) (0.11 g, yield: 40%).
LC-MS (calculated: 769.00 g/mol, found: 770.0 (M+1))
Compound 94 (0.02 mg, yield: 18%) was synthesized in the same manner as in the synthesis of Intermediate 1(f) of Synthesis Example 1, except that Intermediate 94(a) (0.11 g, 0.14 mmol) was used instead of Intermediate 1(e).
LC-MS (calculated: 776.79 g/mol, found: 777.8 (M+1))
A peak wavelength of a peak having the maximum emission intensity in a photoluminescence (PL) spectrum (PLmax), a full width at half maximum (FWHM) of the peak having the maximum emission intensity in the PL spectrum and a triplet (Ti) energy level of each compound in Table 2 were evaluated according to the methods indicated in Table 1, and the results thereof are shown in Table 2.
A glass substrate with an ITO electrode having a thickness of 1,500 ANGSTROM formed thereon was cut to a size of 50 mm×50 mm×0.5 mm, sonicated in acetone, isopropyl alcohol and pure water, each for 15 minutes, and then washed by exposure to UV ozone for 30 minutes.
m-MTDATA was deposited on the ITO electrode (anode) on the glass substrate to form a hole injection layer having a thickness of 600 ANGSTROM, and α-NPD was deposited on the hole injection layer to form a hole transport layer having a thickness of 250 ANGSTROM.
Compound 1 (emitter) and mCP (host) were co-deposited at a weight ratio of 10:90 on the hole transport layer to form an emission layer having a thickness of 400 ANGSTROM.
BAlq was deposited on the emission layer to form a hole-blocking layer having a thickness of 50 ANGSTROM, Alq3 was deposited on the hole-blocking layer to form an electron transport layer having a thickness of 300 ANGSTROM, LiF was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 ANGSTROM, and then, Al was vacuum deposited on the electron injection layer to form a second electrode (cathode) having a thickness of 1,200 ANGSTROM, thereby completing the manufacture of a light-emitting device having a structure of ITO/m-MTDATA (600 ANGSTROM)/α-NPD (250 ANGSTROM)/mCP+Compound 1 (10 wt %) (400 ANGSTROM)/BAIq (50 ANGSTROM)/Alq3 (300 ANGSTROM)/LiF (10 ANGSTROM)/Al (1,200 ANGSTROM).
Light-emitting devices were manufactured in the same manner as in Example 1, except that the compounds shown in Table 3 were used instead of Compound 1 as an emitter when forming an emission layer.
For each of the light-emitting devices manufactured according to Examples 1 and 2 and Comparative Examples A and B, the emission peak wavelength (maximum emission peak wavelength) of the electroluminescence (EL) spectrum, driving voltage, and external quantum efficiency (EQE) were evaluated, and the results thereof are shown in Table 3. For each of the light-emitting devices, the emission peak wavelength of the EL spectrum was evaluated from the EL spectrum (at 1,000 cd/m2) measured by using a luminance meter (Minolta Cs-1000A). The driving voltage and the FOE were evaluated by using a current-voltmeter (Keithley 2400) and a luminance meter (Minolta Cs-1000A). The driving voltage and FOE values of the organic light-emitting devices according to Examples 1 and 2 and Comparative Examples A and B shown in Table 3 are provided in relative values based on Comparative Example A (%).
From Table 3, it was confirmed that Examples 1 and 2 show improved driving voltage and EQE, compared to Comparative Examples A and B.
Accordingly, as the condensed polycyclic compound has excellent thermal and electric stability according to the shielding effect, exhibits relatively less steric hindrance effect, and emits blue light having a relatively small FWHM and shifted to a short wavelength, an electronic device employing the condensed polycyclic compound, for example, a light-emitting device may have an improved driving voltage, higher EQE, increased luminescence efficiency, and/or longer lifespan characteristics.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2023-0063362 | May 2023 | KR | national |
| 10-2024-0062914 | May 2024 | KR | national |
