Patent Application
20240276875
This application claims priority under 35 U.S.C. § 119 to Korean Patent Application No. 10-2023-0006987, filed on Jan. 17, 2023, in the Korean Intellectual Property Office, the content of which is herein incorporated by reference in its entirety.
The disclosure relates to compositions, light-emitting devices including the compositions, and electronic apparatuses including the light-emitting devices.
From among light-emitting devices, organic light-emitting devices are self-emissive devices that, as compared with devices in the art, 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 includes 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.
The need remains for novel materials for organic light-emitting devices.
Provided are a composition including a certain compound and a layer including the compound. A light-emitting device including the composition has excellent lifespan characteristics, and thus, a high-quality electronic apparatus using the light-emitting device may be implemented.
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, a composition includes
The composition may further include an emitter.
The emitter may emit blue light.
The composition may further include a sensitizer.
According to another aspect of the disclosure, a layer includes the composition.
The layer may be an emission layer.
According to another aspect of the disclosure, a light-emitting device includes the composition.
The light-emitting device may include 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 the composition.
The composition may be included in the emission layer of the light-emitting device. The emission layer may emit blue light.
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 FIGURE which is a schematic view of an organic light-emitting device according to an embodiment.
Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the figures, to explain aspects. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
It will be understood that when an element is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
It will be understood that, although the terms “first,” “second,” “third” etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, “a first element,” “component,” “region,” “layer” or “section” discussed below could be termed a second element, component, region, layer or section without departing from the teachings herein.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, “a,” “an,” “the,” and “at least one” do not denote a limitation of quantity, and are intended to cover both the singular and plural, unless the context clearly indicates otherwise. For example, “an element” has the same meaning as “at least one element,” unless the context clearly indicates otherwise.
“Or” means “and/or.” As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
Furthermore, relative terms, such as “lower” or “bottom” and “upper” or “top,” may be used herein to describe one element's relationship to another element as illustrated in the Figures. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the Figures. For example, if the device in one of the figures is turned over, elements described as being on the “lower” side of other elements would then be oriented on “upper” sides of the other elements. The exemplary term “lower,” can therefore, encompasses both an orientation of “lower” and “upper,” depending on the particular orientation of the figure. Similarly, if the device in one of the figures is turned over, elements described as “below” or “beneath” other elements would then be oriented “above” the other elements. The exemplary terms “below” or “beneath” can, therefore, encompass both an orientation of above and below.
“About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ±30%, 20%, 10% or 5% of the stated value.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
In an embodiment, a composition may include:
wherein, in Formula 1, rings A11, A12, A21, A22, A31, A32, A41, and A42 may each be a π electron-rich C5-C60 cyclic group.
The π electron-rich C5-C60 cyclic group may be, for example, 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, a benzofuran group, a benzothiophene group, a benzosilole group, a naphthopyrrole group, a naphthofuran group, a naphthothiophene group, a naphthosilole group, a benzocarbazole group, a dibenzocarbazole group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, a triindolobenzene group, a pyrrolophenanthrene group, a furanophenanthrene group, a thienophenanthrene group, a benzonaphthofuran group, a benzonapthothiophene group, an (indolo)phenanthrene group, a (benzofurano)phenanthrene group, or a (benzothieno)phenanthrene group.
For example, rings A11, A12, A21, A22, A31, A32, A41, and A42 in Formula 1 may each be a benzene group.
R1 to R3 in Formula 1 may each independently be:
For example, B′1, B′2, and B′3 may each be a benzene group unsubstituted or substituted with at least one W′1.
In an embodiment, R1 to R3 in Formula 1 may each independently be:
Herein, “N-carbazolyl group” refers to a monovalent group represented by
(here, * indicates a binding site to a neighboring atom) that may be separated from N of a carbazole group and linked to another group.
R4 to R7 and W′1 in Formula 1 may each independently be:
For example, R4 to R7 and W′1 in Formula 1 may each independently be:
The a1 to a4 in Formula 1 indicate the numbers of R1 to R4, respectively, and may each independently be an integer from 0 to 20 (for example, 0 to 8).
The sum or a1 and a2 may be at least one and the at least one of R1 and R2 may be a tert-butyl group. The sum or a1 and a2 may be one and either R1 or R2 may be a tert-butyl group. The sum or a1 and a2 may be two and two R1(s), two R2(s), or one R1 and one R2 may be a tert-butyl group. The sum or a1 and a2 may be three and three R1(s), or three R2(s), or two R1(s) and one R2, or one R1 and two R2(s) may be a tert-butyl group. The sum or a1 and a2 may be four and two R1(s) and two R2(s) may be a tert-butyl group
The a5 in Formula 1 indicates the number of R5 and may be an integer from 0 to 4.
The a6 and a7 in Formula 1 indicate the number of R6 and R7, respectively, and may each independently be an integer from 0 to 5.
The p and s in Formula 1 may each independently be 0 or 1, wherein p+s may be 1 or 2.
In an embodiment, p in Formula 1 may be 0, and s may be 1.
In one or more embodiments, p in Formula 1 may be 1, and s may be 0.
In one or more embodiments, p and s in Formula 1 may each be 1.
The m1 in Formula 1 may be 0, 1, 2, or 3.
For example, m1 may be 0, 1, or 2.
The m2 in Formula 1 may be 1 or 2.
In an embodiment, p in Formula 1 may be 0, and a group represented by
* in Formulae ph-1 to ph-18 indicates a binding site to a neighboring atom.
In one or more embodiments, p in Formula 1 may be 1, and a group represented by
wherein, in Formulae ph-51 to ph-58,
In one or more embodiments, the first compound may be represented by Formula 1-1:
wherein, in Formula 1-1,
In one or more embodiments, the first compound may satisfy at least one of Conditions 1 to 4:
The second compound may include a triazine group.
For example, the second compound may include:
Examples of the silicon-containing group may include a group represented by *—Si(Ar11)(Ar12) (Ar13).
In an embodiment, the second compound may be a compound represented by Formula 2:
wherein, in Formula 2,
For example, at least two of X4 to X5 in Formula 2 may be N.
In an embodiment, X4 to X5 in Formula 2 may all be N.
In an embodiment, Z1 to Z3 may each independently be *—Si(Ar1)(Ar2)—*′, a benzene group unsubstituted or substituted with at least one R0, or a carbazole group unsubstituted or substituted with at least one R0.
In one or more embodiments, Z1 to Z3 may each independently be a group represented by one of Formulae 2(1) to 2(3):
wherein, in Formulae 2(1) to 2(3),
In one or more embodiments, Z1 to Z3 may each independently be a group represented by one of Formulae 2(2) and 2(3).
In one or more embodiments, in Formula 2,
In one or more embodiments, Z11 to Z13 may each independently be:
In one or more embodiments, at least one of Z11 to Z13 may each independently be:
In one or more embodiments, at least one of Z11 to Z13 may be *—Si(Ar11)(Ar12)(Ar13) or a group represented by Formula 2-CZ:
wherein, in Formula 2-CZ,
In one or more embodiments, in Formula 2,
In one or more embodiments, Ar1, Ar2, and Ar11 to Ar13 may each independently be a phenyl group unsubstituted or substituted with deuterium, a C1-C20 alkyl group, a phenyl group, an N-carbazolyl group, or a combination thereof.
In one or more embodiments, R0 and Z14 to Z16 may each independently be:
In one or more embodiments, the second compound may be a compound represented by Formula 2-1 or 2-2:
wherein, in Formulae 2-1 and 2-2,
In one or more embodiments, e2 in Formula 2-1 may not be 0.
In one or more embodiments, the sum of e1 and e2 may be at least 1. In some embodiments, e1 may be 1 and e2 may be 0. In some embodiments, e1 may be 0 and e2 may be 1. In some embodiments, e1 may be 1 and e2 may be 1.
In one or more embodiments, the second compound may be represented by Formula 2-1 or 2-2 and may satisfy at least one of Conditions 11 to 13:
In one or more embodiments, the second compound may satisfy at least one of Conditions 14 and 15:
In an embodiment, when at least one of the first compound and second compound includes at least one deuterium, the lifespan characteristics of the light-emitting device including the composition may be improved.
In one or more embodiments, the triplet (T1) energy level of the first compound may be in a range of about 2.8 electron volt (eV) or greater, about 2.8 eV to about 3.5 eV, about 2.8 eV to about 3.3 eV, or about 2.8 eV to about 3.1 eV.
In one or more embodiments, the triplet (T1) energy level of the second compound may be in a range of about 2.3 eV to about 3.5 eV, about 2.4 eV to about 3.2 eV, about 2.5 eV to about 3.1 eV, or about 2.6 eV to about 3.0 eV.
The triplet (T1) energy level may be evaluated by the density functional theory (DFT), for example, the DFT method of the Gaussian program. For example, the evaluation method of the triplet energy level may be understood by referring to the following Evaluation Example 1.
If the triplet energy level range of the first compound satisfies the above range, the light-emitting device including the composition may have excellent color purity, luminescence efficiency, and/or lifespan characteristics. For example, the light-emitting device may emit blue light having excellent color purity in addition to having excellent luminescence efficiency and/or lifespan characteristics.
The weight ratio of the first compound and the second compound in the composition may be in a range of about 1:99 to about 99:1, about 10:90 to about 90:10, about 20:80 to about 80:20, about 30:70 to about 70:30, or about 40:60 to about 60:40. When the weight ratio of the first compound and the second compound satisfies the above range, a balance between holes and electrons in the emission layer using the composition may be effectively achieved, and thus, a light-emitting device having excellent luminescence efficiency and/or lifespan characteristics may be implemented.
The “first compound” as described herein may refer to a single compound represented by Formula 1 or a combination of two or more different compounds represented by Formula 1.
The “second compound” as described herein may refer to a single compound represented by Formula 2 (for example, Formulae 2-1 and 2-2) or a combination of two or more different compounds represented by Formula 2 (for example, Formulae 2-1 and 2-2).
In an embodiment, the first compound may be, for example, one of Compounds H1 to H66, a compound in which at least one hydrogen is substituted with deuterium from among Compounds H2, H3, and H6 to H16, or a combination thereof:
In one or more embodiments, the second compound may be one of Compounds E1 to E47, a compound from which deuterium is replaced with a hydrogen from among Compounds E19 to E23, E25, E26, E28, E30, E31, and E35 to E43, a compound of which the substitution location of deuterium and/or the number of deuterium is changed from among Compounds E19 to E23, E25, E26, E28, E30, E31, and E35 to E43, a compound in which at least one hydrogen is substituted with deuterium from among Compounds E1 to E18, E24, E27, E29, E32 to E34, and E44 to E47, or a combination thereof:
The first compound of the above compound is represented by Formula 1, wherein, in Formula 1, i) p+s may be 1 or 2, ii) R7 may be: hydrogen, deuterium, a C1-C60 alkyl group, a deuterated C1-C60 alkyl group; or a phenyl group or a biphenyl group, each unsubstituted or substituted with deuterium, a C1-C60 alkyl group, a phenyl group, a biphenyl group, or a combination thereof; (that is, R7 may not include a carbazolyl group), and iii) m2 may be 1 or 2. As a result, the composition including the first compound and the second compound may have a long lifespan, electrical characteristics suitable for blue light emission, and thermal stability, then a light-emitting device of high quality may be manufactured by using the composition.
The composition may further include an emitter. The emitter is a material that may emit light by transition to a ground state by receiving excitons generated from the first compound, the second compound, and/or the sensitizer.
If the composition further includes an emitter, the amount (weight) of the emitter may be in a range of about 0.5 parts by weight to about 30 parts by weight per 100 parts by weight of the composition.
For example, the composition may include a non-emissive material and an emitter, and the first compound and the second compound may be included in the non-emissive material.
As another example, the composition may include a host and an emitter, and the first compound and the second compound may be included in the host.
The emitter may be a compound that may emit phosphorescence or fluorescence.
For example, the emitter may be a phosphorescent compound, a fluorescent compound (e.g., a delayed fluorescent compound, a prompt fluorescent compound, etc.), or a combination thereof.
The emitter may emit blue light.
For example, the emitter may emit blue light having a maximum emission wavelength in a range of about 400 nanometers (nm) to about 490 nm, about 410 nm to about 470 nm, or about 420 nm to about 450 nm.
In one or more embodiments, the emitter may be an organometallic compound, the organometallic compound may include a transition metal and n ligands linked to the transition metal, and n may be an integer from 1 to 4. Thus, the emitter may be a phosphorescent dopant.
In an embodiment, a transition metal of 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 linked to the transition metal.
In one or more embodiments, the transition metal of 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 a combination thereof, or a bidentate ligand including a carbene moiety linked 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 3 and/or an organometallic compound represented by Formula 5. Formulae 3 and 5 are each as described herein.
In an embodiment, the emitter may be a delayed fluorescence material. For example, the emitter may be a thermally activated delayed fluorescence material. In an embodiment, the emitter may be a multiple resonance thermally activated delayed fluorescence material.
The multiple resonance thermally activated delayed fluorescence material may be a polycyclic compound i) not including a transition metal and ii) including a core in which two or more C3-C60 cyclic groups are condensed to each other. Here, at least two C3-C60 cyclic groups of the core may be condensed to each other while sharing boron (B) or nitrogen (N).
In an embodiment, the emitter may be a polycyclic compound represented by Formula 4. Formula 4 will be described in detail below.
In one or more embodiments, the composition may further include a sensitizer.
An amount (weight) of the sensitizer may be about 0.01 parts by weight to about 10 parts by weight per 100 parts by weight of the composition.
For example, the sensitizer may be an organometallic compound including a transition metal and a tetradentate ligand linked to the transition metal, the transition metal may be platinum (Pt) or palladium (Pd), and the tetradentate ligand may include a carbene moiety linked to the transition metal.
In an embodiment, the composition may further include an emitter and a sensitizer, in addition to the first compound and the second compound described herein. Excitons generated in the first compound and the second compound may be effectively transferred to the emitter through the sensitizer.
In an embodiment, the emitter may be a delayed fluorescence material as described herein, and the sensitizer may be an organometallic compound as described herein. For example, the emitter may be a polycyclic compound represented by Formula 4, and the sensitizer may be an organometallic compound represented by Formula 3.
The emitter and the sensitizer as described herein may each be an organometallic compound represented by Formula 3:
wherein, in Formula 3,
In an embodiment, M31 in Formula 3 may be Pt, Pd, or Au.
In one or more embodiments, M31 in Formula 3 may be Pt or Pd.
In one or more embodiments, a bond between X11 and M31 in Formula 3 may be a coordinate bond.
In one or more embodiments, in Formula 3, X11 may be C, and a bond between X11 and M31 may be a coordinate bond. That is, X11 in Formula 3 may be C in a carbene moiety.
In one or more embodiments, ring CY31 to ring CY34 in Formula 3 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 3 may be an organometallic compound represented by Formula 3-1 or an organometallic compound represented by Formula 3-2:
A bond between a carbon of an imidazole group and M31 in Formula 3-1 may be a coordinate bond. That is, the imidazole group of Formula 3-1 may include a carbene moiety linked to M31.
A bond between a carbon of a benzimidazole group and M31 in Formula 3-2 may be a coordinate bond. That is, the benzimidazole group of Formula 3-2 may include a carbene moiety linked to M31.
In Formulae 3-1 and 3-2,
In an embodiment, in Formulae 3-1 and 3-2, R311 to R317 may each independently be:
For example, in Formulae 3-1 and 3-2,
The emitter as used herein may be an organometallic compound represented by Formula 5:
M51(L51)n51(L52)n52 Formula 5
wherein, in Formula 5, M51 may be a transition metal.
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 (T1), 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:
wherein Formulae 5A and 5B are each as described herein.
In Formula 5, n51 may be 1, 2, or 3, wherein, when n51 is 2 or more, two or more of L51 (s) may be identical to or different from each other.
In Formula 5, n52 may be 0, 1, or 2, wherein, when n52 is 2, two L52(s) 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, the third ring may be a cyclopentane group, a cyclopentene group, a furan group, a thiophene group, a pyrrole group, a silole group, a borole group, a phosphole group, a germole group, a selenophene group, an oxazole group, an oxadiazole group, an oxatriazole group, a thiazole group, a thiadiazole group, a thiatriazole group, a pyrazole group, an imidazole group, a triazole group, a tetrazole group, or an azasilole group, and the fourth ring may be an adamantane group, a norbornane group, a norbornene group, a cyclohexane group, a cyclohexene group, a benzene group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, or a triazine group.
In some embodiments, in Formulae 5A and 5B, ring CY51 to ring CY54 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 benzoisothiazolyl 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 as described herein.
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:
The 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(s) may be identical to or different from each other, when b52 is 2 or more, two or more of R52(s) may be identical to or different from each other, when b53 is 2 or more, two or more of R53(s) may be identical to or different from each other, and when b54 is 2 or more, two or more of R54(s) 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, Y52 in Formula 5A 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. When b52 is at least two, the at least two of R52 may be a cyano group, —F, or a combination thereof.
In one or more embodiments, Y51 in Formula 5A 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. When b52 is at least two, the at least two of R52 may be a cyano group, —F, or a combination thereof.
In one or more embodiments, Y51 in Formula 5A may be C, and a bond between Y51 and M51 may be a coordinate bond.
In one or more embodiments, Y51 in Formula 5A 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.
Examples of an organometallic compound represented by Formula 3 and an organometallic compound represented by Formula 5.
For example, the organometallic compound represented by Formula 3 and the organometallic compound represented by Formula 5 may be one of Compounds P1 to P52:
The emitter as used herein may be a polycyclic compound represented by Formula 4:
wherein, in Formula 4,
In an embodiment, rings CY41 to CY43 may each independently be i) a benzene group or ii) a polycyclic group in which two or more C3-C60 cyclic groups are condensed with each other. At least two C3-C60 cyclic groups in 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 an embodiment, two of b41 to b43 may be 1, and the other 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 represented by one of Formulae 4-1 to 4-9:
wherein, in Formulae 4-1 to 4-9,
Example of polycyclic compound represented by Formula 4
The polycyclic compound represented by Formula 4 may be selected from Compounds, D1 to D30:
In an embodiment, a layer may include the composition described herein.
For example, when the composition further includes an emitter, the layer may be an emission layer.
In one or more embodiments, a light-emitting device, for example, an organic light-emitting device may include: 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 the composition as described herein.
In an embodiment, the composition may be included in the emission layer of the light-emitting device. The emission layer may emit blue light. For example, the emission layer may emit blue light having a maximum emission wavelength range of about 400 nm to about 490 nm, about 410 nm to about 470 nm, or about 420 nm to about 450 nm.
Because the organic light-emitting device includes the composition as described above, the organic light-emitting device may have excellent luminescence efficiency and lifespan characteristics.
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 a combination thereof, and the electron transport region may include a buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof.
The 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.
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 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.
First electrode 11
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 a combination 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 a 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 angstroms (Å) to about 1,000 Å, for example, about 200 Å to about 600 Å. 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 emission layer 15 may include the composition as described herein.
The hole transport region 12 may be arranged between the first electrode 11 and the emission layer 15 of the organic light-emitting device 10.
The hole transport region 12 may have a single-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, β-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (“TCTA”), polyaniline/dodecylbenzenesulfonic acid (“PANI”/“DBSA”), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (“PEDOT”/“PSS”), polyaniline/camphor sulfonic acid (“PANI”/“CSA”), polyaniline/poly(4-styrenesulfonate) (“PANI”/“PSS”), one of a compound represented by Formula 201 to a compound represented by Formula 205, or a combination thereof:
wherein, in Formulae 201 to 205,
For example, L201 to L209 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 pentaphene group, a hexacene group, a pentacene group, a rubicene group, a coronene group, an ovalene group, a pyrrole group, an isoindole group, an indole group, a furan group, a thiophene group, a benzofuran group, a benzothiophene group, a benzocarbazole group, a dibenzocarbazole group, a dibenzofuran group, a dibenzothiophene group, a dibenzothiophene sulfone group, a carbazole group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, or a triindolobenzene group, each unsubstituted or substituted with deuterium, a C1-C10 alkyl group, a C1-C10 alkoxy group, a phenyl group, a naphthyl group, a fluorenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a triphenylenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, —Si(Q11)(Q12)(Q13), or a combination thereof, xa1 to xa9 may each independently be 0, 1, or 2, and R201 to R206 may each independently be a phenyl group, a biphenyl group, a terphenyl group, a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptalenyl group, an indacenyl group, an acenaphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenalenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a naphthacenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group, an ovalenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, a pyridinyl group, an indeno carbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, or a benzothienocarbazolyl group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazine group, a hydrazone group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, a phenyl group, a biphenyl group, a terphenyl group, a phenyl group substituted with a C1-C10 alkyl group, a phenyl group substituted with —F, a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptalenyl group, an indacenyl group, an acenaphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenalenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a naphthacenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group, an ovalenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, a pyridinyl group, —Si(Q31)(Q32)(Q33), —N(Q31)(Q32), or a combination thereof.
Q11 to Q13 and Q31 to Q33 may each independently be a C1-C10 alkyl group, a C1-C10 alkoxy group, a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group.
In one or more embodiments, the hole transport region 12 may include a carbazole-containing amine-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 a 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 a combination thereof:
wherein, in Formulae 201-1, 202-1, and 201-2, L201 to L203, L205, xa1 to xa3, xa5, R201, and R202 may respectively be as described for L201 to L203, L205, xa1 to xa3, xa5, R201, and R202, and R211 to R213 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a biphenyl group, a terphenyl group, a phenyl group substituted with a C1-C10 alkyl group, a phenyl group substituted with —F, a naphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a triphenylenyl 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, or a pyridinyl group.
For example, the hole transport region 12 may include one of Compounds HT1 to HT39 or a combination thereof:
In one or more embodiments, 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−3.5 eV or less.
The p-dopant may include a quinone derivative, a metal oxide, a cyano group-containing compound, or a combination thereof.
In an embodiment, the p-dopant may include at least one selected from: a quinone derivative, such as tetracyanoquinodimethane (“TCNQ”), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), and F6-TCNNQ;
In Formula 221,
The compound represented by Formula 221 may include, for example, Compound HT-D2:
The hole transport region 12 may have a thickness of about 100 Å to about 10000 Å, for example, about 400 Å to about 2000 Å, and the emission layer 15 may have a thickness of about 100 Å to about 3000 Å, for example, about 300 Å to about 1000 Å. 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 transport materials.
The electron transport region 17 (for example, a buffer layer, a hole blocking layer, an electron control layer, or an electron transport layer in the electron transport region) may include a metal-free compound containing at least one π electron-deficient nitrogen-containing C1-C60 cyclic group. The π electron-deficient nitrogen-containing C1-C60 cyclic group is 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
wherein, in Formula 601,
In an embodiment, at least one of Ar601(s) in the number of xe11 and R601(s) in the number of xe21 may include the π electron-deficient nitrogen-containing C1-C60 cyclic group.
In an embodiment, Ar601 and L601 in Formula 601 may each independently be a benzene group, a naphthalene group, a fluorene group, a spiro-bifluorene group, a benzofluorene group, a dibenzofluorene group, a phenalene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a naphthacene group, a picene group, a perylene group, a pentaphene group, an indenoanthracene group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, an imidazole group, a pyrazole group, a thiazole group, an isothiazole group, an oxazole group, an isoxazole group, a pyridine group, a pyrazine group, a pyrimidine group, a pyridazine group, an indazole group, a purine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a phthalazine group, a naphthyridine group, a quinoxaline group, a quinazoline group, a cinnoline group, a phenanthridine group, an acridine group, a phenanthroline group, a phenazine group, a benzimidazole group, an isobenzothiazole group, a benzoxazole group, an isobenzoxazole group, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, a thiadiazole group, an imidazopyridine group, an imidazopyrimidine group, or an azacarbazole group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, —Si(Q31)(Q32)(Q33), —S(═O)2(Q31), —P(═O)(Q31)(Q32), or a combination thereof,
When xe11 in Formula 601 is 2 or more, two or more of Ar601(s) may be linked to each other via a single bond.
In one or more embodiments, Ar601 in Formula 601 may be an anthracene group.
In one or more embodiments, the compound represented by Formula 601 may be represented by Formula 601-1:
wherein, in Formula 601-1,
In one or more embodiments, xe1 and xe611 to xe613 in Formulae 601 and 601-1 may each independently be 0, 1, or 2.
In one or more embodiments, R601 and R611 to R613 in Formulae 601 and 601-1 may each independently be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, a pyridinyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a thiadiazolyl group, an oxadiazolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a benzimidazolyl group, an isobenzothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, or an azacarbazolyl group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, a pyridinyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a thiadiazolyl group, an oxadiazolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a benzimidazolyl group, an isobenzothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an azacarbazolyl group, or a combination thereof; or
The electron transport region 17 may include one of Compounds ET1 to ET36 or a 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 a combination thereof. For example, when the electron transport region 17 includes a hole blocking layer, the hole blocking layer may include BCP or Bphen:
Thicknesses of the buffer layer, the hole blocking layer, and the electron control layer may each independently be in the range of about 20 Å to about 1,000 Å, for example, about 30 Å to about 300 Å. When the thicknesses of the buffer layer, the hole blocking layer, and the electron control layer are within these ranges, excellent hole blocking characteristics or excellent electron control characteristics may be obtained without a substantial increase in driving voltage.
A thickness of the electron transport layer may be in the range of about 100 Å to about 1,000 Å, for example, about 150 Å to about 500 Å. When the thickness of the electron transport layer is within the range described above, the electron transport layer may have satisfactory electron 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 a combination thereof. A metal ion of the alkali metal complex may include a Li ion, a Na ion, a K ion, a Rb ion, a Cs ion, or a combination thereof, and a metal ion of the alkaline earth metal complex may include a Be ion, a Mg ion, a Ca ion, a Sr ion, a Ba ion, or a combination thereof. A ligand coordinated with the metal ion of the alkali metal complex or the alkaline earth-metal complex may include a hydroxyquinoline, a hydroxyisoquinoline, a hydroxybenzoquinoline, a hydroxyacridine, a hydroxyphenanthridine, a hydroxyphenyloxazole, a hydroxyphenylthiazole, a hydroxydiphenyloxadiazole, a hydroxydiphenylthiadiazole, a hydroxyphenylpyridine, a hydroxyphenylbenzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or a combination thereof.
In 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 a combination thereof.
The alkali metal may include Li, Na, K, Rb, Cs, or a 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 a combination thereof.
The rare earth metal may include Sc, Y, Ce, Tb, Yb, Gd, or a combination thereof.
The alkali metal compound, the alkaline earth metal compound, and the rare earth metal compound may include oxides and halides (for example, fluorides, chlorides, bromides, or iodides) of the alkali metal, the alkaline earth metal, and the rare earth metal, or a combination thereof.
The alkali metal compound may include: one of alkali metal oxides such as Li2O, Cs2O, or K2O; one of alkali metal halides such as LiF, NaF, CsF, KF, Lil, Nal, Csl, or KI; or a combination thereof. In an embodiment, the alkali metal compound may include LiF, Li2O, NaF, Lil, Nal, Csl, KI, or a combination thereof.
The alkaline earth-metal compound may include one of alkaline earth-metal compounds, such as BaO, SrO, CaO, BaxSr1-xO (wherein 0<x<1), or BaxCa1-xO (wherein 0<x<1), or a combination thereof. In an embodiment, the alkaline earth metal compound may include BaO, SrO, CaO, or a combination thereof.
The rare earth metal compound may include YbF3, ScF3, Sc2O3, Y2O3, Ce2O3, GdF3, TbF3, or a combination thereof. In an embodiment, the rare earth metal compound may include YbF3, ScF3, TbF3, YbI3, ScI3, TbI3, or a combination thereof.
The alkali metal complex, the alkaline earth metal complex, and the rare earth metal complex may include an ion of an alkali metal, an alkaline earth metal, and a rare earth metal as described above, and a ligand coordinated with a metal ion of the alkali metal complex, the alkaline earth metal complex, or the rare earth metal complex may include hydroxy quinoline, hydroxy isoquinoline, hydroxy benzoquinoline, hydroxy acridine, hydroxy phenanthridine, hydroxy phenyloxazole, hydroxy phenylthiazole, hydroxy diphenyloxadiazole, hydroxy diphenylthiadiazole, hydroxy phenylpyridine, hydroxy phenylbenzimidazole, hydroxy phenylbenzothiazole, bipyridine, phenanthroline, cyclopentadiene, or a combination thereof.
The electron injection layer may consist of an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal compound, an alkaline earth-metal compound, a rare earth metal compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or a combination thereof, as described above. In one or more embodiments, the electron injection layer may further include an organic material. When the electron injection layer further includes an organic material, an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal compound, an alkaline earth-metal compound, a rare earth metal compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or a combination thereof may be homogeneously or non-homogeneously dispersed in a matrix including the organic material.
A thickness of the electron injection layer may be about 1 Å to about 100 Å, and, for example, about 3 Å to about 90 Å. 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 may be on the 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 (AI), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), ITO, IZO, or a combination thereof. The second electrode 19 may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode.
The second electrode 19 may have a single-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-C10 alkyl group are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, or a tert-decyl group, each unsubstituted or substituted with a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, or a combination thereof.
The term “C1-C60 alkoxy group” used herein refers to a monovalent group represented by —OA101 (wherein A101 is the C1-C60 alkyl group), and examples thereof are a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.
The term “C2-C60 alkenyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof 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 may include 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-C1 heterocycloalkyl group.
Examples of the C1-C1 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 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 include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a chrysenyl group. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the rings may be fused to each other.
The term “C1-C60 heteroaryl group” as used herein refers to a monovalent group having a heterocyclic aromatic system having 1 to 60 carbon atoms and including at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom, and the term “C1-C60 heteroarylene group” as used herein refers to a divalent group having a heterocyclic aromatic system having 1 to 60 carbon atoms and including at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom. Examples of the C1-C60 heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, and an isoquinolinyl group. When the 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” used herein refers to a monovalent group in which two or more rings are condensed with each other, only carbon is used as a ring-forming atom (for example, the number of carbon atoms may be 8 to 60) and the whole molecule is a non-aromaticity group. 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 a neighboring atom) as a ring-forming moiety. For example, the π electron-depleted nitrogen-containing C1-C60 cyclic group may be a) a first ring, b) a condensed ring in which at least two first rings are condensed, or c) a condensed ring in which at least one first ring and at least one second ring are condensed.
The term “π electron-rich C3-C60 cyclic group” as used herein refers to a cyclic group having 3 to 60 carbon atoms and not including at least one *—N═*′ (wherein * and *′ each indicate a binding site to a neighboring atom) as a ring-forming moiety. For example, the π electron-rich C3-C60 cyclic group may be a) a second ring or b) a condensed ring in which at least two second rings are condensed.
The term “C5-C60 cyclic group” as used herein refers to a monocyclic or polycyclic group having 5 to 60 carbon atoms, 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” as used herein refers to a monocyclic or polycyclic group that has 1 to 60 carbon atoms and includes at least one heteroatom, 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, an isobenzothiazole group, a benzoxazole group, an isobenzoxazole group, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, a thiadiazole group, an imidazopyridine group, an imidazopyrimidine group, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, an acridine group, or a pyridopyrazine group.
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, a benzofuran group, a benzothiophene group, a benzosilole group, a naphthopyrrole group, a naphthofuran group, a naphthothiophene group, a naphthosilole group, a benzocarbazole group, a dibenzocarbazole group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, a triindolobenzene group, a pyrrolophenanthrene group, a furanophenanthrene group, a thienophenanthrene group, a benzonaphthofuran group, a benzonapthothiophene group, an (indolo)phenanthrene group, a (benzofurano)phenanthrene group, or a (benzothieno)phenanthrene group.
For example, the C5-C60 carbocyclic group may be a cyclopentane group, a cyclohexane group, a cyclohexene group, a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a 1,2,3,4-tetrahydronaphthalene group, a cyclopentadiene group, an indene group, a fluorene group, an adamantane group, a norbornane group, or a norbornene group.
For example, the C1-C60 heterocyclic group may be a thiophene group, a furan group, a pyrrole group, a cyclopentadiene group, a silole group, a borole group, a phosphole group, a selenophene group, a germole group, a benzothiophene group, a benzofuran group, an indole group, 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 term “a π electron-deficient nitrogen-containing C1-C60 cyclic group, a rr electron-rich C3-C60 cyclic group, a C5-C60 cyclic group, and a C1-C60 heterocyclic group” may be part of a condensed cycle or may be a monovalent, a divalent, a trivalent, a tetravalent, a pentavalent, or a hexavalent group, depending on the formula structure.
As used herein, the number of carbons in each group that is substituted (e.g., C1-C60) excludes the number of carbons in the substituent. For example, a C1-C60 alkyl group can be substituted with a C1-C60 alkyl group. The total number of carbons included in the C1-C60 alkyl group substituted with the C1-C60 alkyl group is not limited to 60 carbons. In addition, more than one C1-C60 alkyl substituent may be present on the C1-C60 alkyl group. This definition is not limited to the C1-C60 alkyl group and applies to all substituted groups that recite a carbon range.
Substituents of the substituted π electron-deficient nitrogen-containing C1-C60 cyclic group, the substituted π electron-rich C3-C60 cyclic group, the substituted C5-C60 cyclic group, the substituted C1-C60 heterocyclic group, the substituted C1-C60 alkylene group, the substituted C2-C60 alkenylene group, the substituted C2-C60 alkynylene group, the substituted C3-C10 cycloalkylene group, the substituted C1-C10 heterocycloalkylene group, the substituted C3-C10 cycloalkenylene group, the substituted C1-C10 heterocycloalkenylene group, the substituted C6-C60 arylene group, the substituted C1-C60 heteroarylene group, the substituted divalent non-aromatic condensed polycyclic group, the substituted divalent non-aromatic condensed heteropolycyclic group, the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C1-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted 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:
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 tetraphenyl group (quaterphenyl)” 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 an organic light-emitting device according to embodiments are described in detail with reference to Synthesis Examples and Examples.
However, the organic light-emitting device is not limited thereto. The wording “‘B’ was used instead of ‘ A″’ used in describing Synthesis Examples means that an amount of ‘A’ used was identical to an amount of ‘B’ used, in terms of a molar equivalent.
3-bromo-1,1′-biphenyl (5.3 g, 23.1 mmol), 9H-9,3′:6′,9″-tercarbazole (12.6 grams (g), 25.4 millimoles (mmol)), Pd(dba)2 (bis(dibenzylideneacetone)palladium (0)) (1.3 g, 2.3 mmol), sodium tert-butoxide (NaOtBu) (4.4 g, 46.2 mmol), and tri-tert-butylphosphine (P(tBu)3) (50 weight percent (wt %) toluene solution, 1.8 g, 4.6 mmol) were mixed with 58 milliliters (ml) of xylene, heated to 115° C., and then stirred for 3 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, the reaction product was added to 800 ml of methanol, stirred for 1 hour, and then filtered under reduced pressure. A solid obtained therefrom was dried and then purified by silica gel column chromatography to provide 2.7 g (yield of 18%) of Compound H1.
LC-Mass (calculated: 649.25 g/mol, found: M+1=650 g/mol).
9H-3,9′-bicarbazole (11.5 g, 34.7 mmol), 3,5-dibromo-1,1′-biphenyl (12.99 g, 41.6 mmol), Cul (3.3 g, 17.3 mmol), K3PO4 (14.7 g, 69.4 mmol), and 1,2-diaminocyclohexane (4.0 g, 34.7 mmol) were mixed with dioxane (173 ml), heated to 110° C., and then stirred while refluxing for 4 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and an insoluble substance was filtered with a celite pad, subjected to evaporative concentration, and then filtered by silica gel column chromatography to provide 12.4 g (yield of 62%) of Compound H4-1.
LC-Mass (calculated: 562.10 g/mol, found: M+1=563 g/mol).
Compound H4-1 (12.4 g, 21.6 mmol), 9H-carbazole (3.8 g, 22.7 mmol), Pd2(dba)3 (1.0 g, 1.1 mmol), NaOtBu (3.1 g, 32.4 mmol), and P(tBu)3 (50 wt % toluene solution, 1.5 ml, 3.2 mmol) were mixed with 108 ml of xylene, heated to 130° C., and then stirred for 5 hours. After completion of the reaction, without cooling, the reaction product was filtered with a silica pad, subjected to evaporative concentration, and then purified by silica gel column chromatography to provide 9.7 g (yield of 69%) of Compound H4.
LC-Mass (calculated: 649.25 g/mol, found: M+1=650 g/mol).
(4-chloro-2-fluorophenyl)boronic acid (10.0 g, 57.4 mmol), iodobenzene (14.0 g, 68.8 mmol), tetrakis(triphenylphosphino)palladium (0) (3.3 g, 2.9 mmol), and K2CO3 (23.8 g, 172.1 mmol) were mixed with tetrahydrofuran (THF) (200 ml) and H2O (90 ml), heated to 80° C., and then stirred while refluxing for 3 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and an organic layer was extracted with ethyl acetate. A filtrate obtained by filtering the organic layer under reduced pressure after removing water therefrom by using MgSO4 was subjected to evaporative concentration and then purified with a silica gel column chromatography to provide 11.5 g (yield of 97%) of Compound H16-1.
LC-Mass (calculated: 206.03 g/mol, found M+1=207 g/mol).
Compound H16-1 (11.0 g, 53.2 mmol), 9H-carbazole (10.7 g, 63.9 mmol), and Cs2CO3 (26.0 g, 79.9 mmol) were mixed with 135 ml of N,N-dimethylformamide (DMF), heated to 165° C., and then stirred for 24 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and the reaction product was added to 300 ml of methanol and 400 ml of H2O, stirred for 1 hour, and then filtered under reduced pressure. A solid obtained therefrom was dried and purified by silica gel column chromatography to provide 15.1 g (yield of 79.9%) of Compound H16-2.
LC-Mass (calculated: 353.10 g/mol, found: M+1=354 g/mol).
Compound H16-2 (8.0 g, 22.6 mmol), 9H-3,9′-bicarbazole (7.5 g, 22.6 mmol), Pd2(dba)3 (2.1 g, 2.3 mmol), NaOtBu (4.3 g, 45.2 mmol), and P(tBu)3 (50 wt % toluene solution, 3.7 g, 9.0 mmol) were mixed with 57 ml of xylene, heated to 160° C., and then stirred for 24 hours. After completion of the reaction, without cooling, the reaction product was filtered through a silica pad, subjected to evaporative concentration, and then purified by silica gel column chromatography to provide 9.0 g (yield of 61%) of Compound H16.
LC-Mass (calculated: 649.25 g/mol, found: M+1=650 g/mol).
3.11 g (yield of 21%) of Compound H27 was synthesized in the same manner as in Synthesis Example 1, except that Compound H27-1 (3-bromo-1,1′-biphenyl-2′, 3′, 4′, 5′, 6′-d5) was used instead of 3-bromo-1,1′-biphenyl and Compound H27-2(9H-9,3′: 6′, 9″-tercarbazole-1,1′, 1″, 2,2′, 2″, 3,3″, 4,4′, 4″, 5,5′, 5″, 6,6″, 7,7′, 7″, 8,8′, 8″-d22) was used instead of 9H-9,3′: 6′, 9″-tercarbazole.
LC-Mass (calculated: 676.42 g/mol, found: M+1=677 g/mol).
13.20 g (yield of 66%) of Compound H36-1 was synthesized in the same manner as used to synthesize Compound H4-1 of Synthesis Example 2, except that Compound H36-3(3,5-dibromo-1,1′-biphenyl-2′, 3′, 4′, 5′, 6′-d5) was used instead of 3,5-dibromo-1,1′-biphenyl, and Compound H36-4(9H-3,9′-bicarbazole-1,1′, 2,2′, 3,3′, 4,4′, 5,5′, 6,6′, 7,7′, 8,8′-d15) was used instead of 9H-3,9′-bicarbazole.
LC-Mass (calculated: 582.23 g/mol, found: M+1=583 g/mol).
9.32 g (yield of 62%) of Compound H36 was synthesized in the same manner as used to synthesize Compound H4 of Synthesis Example 2, except that Compounds H36-1 and H36-2(9H-carbazole-1,2,3,4,5,6,7,8-d8) were used instead of Compound H4-1 and 9H-carbazole, respectively.
LC-Mass (calculated: 677.43 g/mol, found: M+1=678 g/mol).
9,9′-(6-chloro-1,3,5-triazine-2,4-diyl)bis(9H-carbazole) (9.56 g, 21.5 mmol), triphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (10.91 g, 23.6 mmol), Pd(PPh3)4 (2.48 g, 2.1 mmol), and K2CO3 (5.93 g, 42.9 mmol) were mixed with 54 ml of tetrahydrofuran and 22 ml of H2O, heated to 85° C., and stirred while refluxing for 12 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and then 1,000 ml of methanol was added to the reaction mixture to obtain a solid. Then, the reaction product was purified by silica gel column chromatography to provide 8.5 g (yield of 53%) of Compound E1.
LC-Mass (calculated: 745.27 g/mol, found: M+1=746 g/mol).
9H-carbazole-1,2,3,4,5,6,7,8-d8 (8.21 g, 46.7 mmol) and 80 ml of tetrahydrofuran were mixed and then cooled to −78° C. in a nitrogen atmosphere. Then, n-BuLi (2.5M, 24.4 ml) was slowly added dropwise to the mixture at −78° C. and stirred for 1 hour, and then 2,4,6-trichloro-1,3,5-triazine (4.50 g, 24.4 mmol) was further added thereto, and after the reaction mixture was allowed to warm to room temperature, the mixture was stirred for 4 hours. After completion of the reaction, distilled water was slowly added dropwise thereto to terminate the reaction. Then, an organic layer was extracted with ethyl acetate, dried with MgSO4 and concentrated, and then purified by silica gel column chromatography to provide 8.23 g (yield of 38%) of Compound E20-1.
LC-Mass (calculated: 461.21 g/mol, found: M+1=462 g/mol).
9H-carbazole-1,2,3,4,5,6,7,8-d8 (12.48 g, 71.2 mmol), 1-bromo-2-fluorobenzene-3,4,5,6-d4 (10.20 g, 57.0 mmol), and K3PO4 (30.53 g, 143.8 mmol) were mixed with 280 ml of N,N-dimethylformamide and then stirred for 20 hours at 165° C. After completion of the reaction, the temperature was cooled to room temperature, and an organic layer was extracted with ethyl acetate, dried with MgSO4, and concentrated, and then purified by silica gel column chromatography to provide 7.20 g (yield of 30%) of Compound E20-2.
LC-Mass (calculated: 333.09 g/mol, found: M+1=334 g/mol).
Compound E-2 (13.52 g, 40.4 mmol), bis(pinacolato)diboron (13.91 g, 54.6 mmol) [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium (II) (Pd(dppf)Cl2) (1.71 g, 2.4 mmol), and potassium acetate (KOAc) (10.3 g, 105.1 mmol) were mixed with 160 ml of xylene and then refluxed while heating for 16 hours. Then, after the reaction mixture was allowed to cool to room temperature, the mixture was purified by silica gel column chromatography to provide 6.85 g (yield of 44%) of Compound E20-3.
LC-Mass (calculated: 381.27 g/mol, found: M+1=382 g/mol).
Compound E20-1 (7.12 g, 15.42 mmol), Compound E20-3 (10.14 g, 26.5 mmol), Pd(PPh3)4 (1.16 g, 1.0 mmol), and K2CO3 (6.55 g, 47.5 mmol) were mixed with 60 ml of tetrahydrofuran and 30 ml of H2O and then refluxed while heating in a nitrogen atmosphere. The reaction mixture was cooled to room temperature after the mixture was reacted for 18 hours, and an organic layer extracted therefrom with ethyl acetate. The organic layer was dried with MgSO4 and concentrated under vacuum to provide the crude product which was purified by silica gel column chromatography to provide Compound E20 (9.21 g, yield of 88%).
LC-Mass (calculated: 680.41 g/mol, found: M+1=681 g/mol).
1-bromo-2,6-difluorobenzene-3,4,5-d3 (5.03 g, 25.7 mmol), 9H-carbazole-1,2,3,4,5,6,7,8-d8 (9.90 g, 56.5 mmol), and Cs2CO3 (20.91 g, 64.2 mmol) were combined with 85 ml of N-methyl-2-pyrrolidone, heated to 180° C., and then stirred for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and distilled water was added to the reaction mixture to form a precipitate and then the precipitate was filtered. The crude product was purified by silica gel column chromatography to provide 9.9 g (yield of 76%) of Compound E36-2.
LC-Mass (calculated: 505.19 g/mol, found: M+1=502 g/mol).
9.5 g of Compound E36-3 (yield of 42%) was provided in the same manner as in synthesizing Compound 20-3 of Synthesis Example 7 except that Compound E36-2 was used instead of Compound E20-2.
LC-Mass (calculated: 553.37 g/mol, found: M+1=554 g/mol).
8.7 g of Compound E36 (yield of 79%) was provided in the same manner as in synthesizing Compound E20 of Synthesis Example 7 except that Compound E36-3 was used instead of Compound E20-3.
LC-Mass (calculated: 852.52 g/mol, found: M+1=853 g/mol).
T1 energy level of the compounds of Table 1 were evaluated using the DFT method (T1 adiabatic) of the Gaussian program, which is structure-optimized at the B3LYP/6-31G(d,p) level, and results thereof are shown in Table 1.
A glass substrate with a 1,500 Å-thick indium tin oxide (ITO) electrode (first electrode, anode) formed thereon was cleaned by distilled water ultrasonication. After the distilled water ultrasonication, ultrasonic cleaning was performed with a solvent such as isopropyl alcohol, acetone, and methanol, and the glass substrate was dried and transferred to a plasma cleaner. The glass substrate was cleaned by using oxygen plasma for 5 minutes, and then transferred to a vacuum laminator.
Compounds HT1 and HT-D2 were co-deposited on the ITO electrode of the glass substrate to form a hole injection layer having a thickness of 100 Å. Subsequently, Compound HT1 was deposited on the hole injection layer to form a hole transport layer having a thickness of 1,300 Å. mCP was next deposited on the hole transport layer to form an electron blocking layer having a thickness of 100 Å, thereby forming a hole transport region.
The first compound, the second compound, and the emitter (the weight ratio of the first compound, the second compound, and the emitter is 57:30:13) were co-deposited on the hole transport region to form an emission layer having a thickness of 400 Å.
BCP was vacuum-deposited on the emission layer to form a hole blocking layer having a thickness of 100 Å. Compound ET27 and 8-hydroxyquinolatolithium (“Liq”) were then co-deposited on the hole blocking layer to form an electron transport layer having a thickness of 300 Å. Next, Liq was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and then, an Al second electrode (a cathode) having a thickness of 1,200 Å was formed on the electron injection layer, thereby completing the manufacture of an organic light-emitting device.
An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compounds in Tables 2 to 4 were used when forming the emission layer.
An organic light-emitting device was manufactured in the same manner as in Example 1-1 except that the first compound, the second compound, the sensitizer, and the emitter (the weight ratio of the first compound, the second compound, the sensitizer, and the emitter is 56:30.2:13:0.8) of Table 5 were co-deposited on the hole transport region to form an emission layer having a thickness of 400 Å instead of forming the emission layer of Example 1-1.
An organic light-emitting device was manufactured in the same manner as in Example 2-1, except that the compounds in Tables 5 to 7 were used when forming the emission layer.
The lifespan (LT95) of the light-emitting device according to the examples and comparative examples were measured, and the results thereof are shown in Tables 2 to 7. A current-voltage meter (Keithley 2400) and a luminance meter (Minolta Cs-1000A) were used as apparatuses for evaluation, and the lifespan (LT95) (at 1,000 nit) was evaluated by measuring the amount of time (hr) taken for luminance to be reduced to 95% of the initial luminance of 100%. The lifespan of the light-emitting devices of Examples 1-1 to 1-10 and Comparative Examples 1-2 to 1-9 were represented as relative values (%) relative to the lifespan of Comparative Example 1-1, and the lifespan of the light-emitting devices of Examples 2-1 to 2-10 and Comparative Examples 2-2 to 2-9 were represented as relative values (%) relative to the lifespan of Comparative Example 2-1.
According to the one or more embodiments, the light-emitting device including the composition has excellent lifespan characteristics, and thus, a high-quality electronic apparatus using the light-emitting device may be manufactured.
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 |
|---|---|---|---|
| 10-2023-0006987 | Jan 2023 | KR | national |
