Patent Application
20230363256
This application claims priority under 35 U.S.C. § 119 to Korean Patent Application Nos. 10-2022-0055749, filed on May 4, 2022, 10-2023-0046327, filed on Apr. 7, 2023, and 10-2023-0057362, filed on May 2, 2023, in the Korean Intellectual Property Office, the contents of which are incorporated by reference herein in their entirety.
The disclosure relates to a composition, a light-emitting device including the composition, and an electronic apparatus including the light-emitting device.
From among light-emitting devices, organic light-emitting devices are self-emissive devices that, as compared with conventional devices, have wide viewing angles, high contrast ratios, short response times, and excellent characteristics in terms of luminance, driving voltage, and response speed, and produce full-color images.
In an example, an organic light-emitting device may include an anode, a cathode, and an organic layer that is located between the anode and the cathode and includes an emission layer. A hole transport region may be arranged between the anode and the emission layer, and an electron transport region may be arranged between the emission layer and the cathode. Holes provided from the anode move toward the emission layer through the hole transport region, and electrons provided from the cathode move toward the emission layer through the electron transport region. The holes and the electrons recombine in the emission layer to produce excitons. The excitons may transition from an excited state to a ground state, thus generating light.
Provided are a composition including certain compounds. A light-emitting device including the composition has excellent lifespan characteristics, and thus, a high-quality electronic apparatus may be implemented by using the light-emitting device.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.
According to an aspect of the disclosure, a composition includes
A triplet (T1) energy level of the first compound may be greater than about 2.8 eV.
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 organic layer arranged between the first electrode and the second electrode and including an emission layer, and the organic layer may include the composition.
The emission layer of the light-emitting device may include the composition.
According to another aspect of the disclosure, an electronic apparatus includes the light-emitting device.
The above and other aspects, features, and advantages of certain embodiments of the disclosure will be more apparent from the following description taken in conjunction with the accompanying drawings, in which:
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 the specification. 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.
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. 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.
“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.
A composition according to an embodiment of the disclosure may include:
In an embodiment, a triplet (T1) energy level of the first compound may be greater than about 2.8 eV, for example, about 2.8 eV to about 3.5 eV.
In an embodiment, a triplet (T1) energy level of the second compound may be about 2.3 eV to about 3.5 eV, for example, about 2.4 eV to about 3.0 eV.
The triplet T1 energy level may be evaluated by the density functional theory (DFT), for example, a DFT method of a Gaussian program. For example, the triplet T1 energy level evaluation method may refer to Evaluation Example 1.
When the triplet T1 energy level of the first compound satisfies the range as described above, a light-emitting device including the composition may have excellent characteristics in terms of color purity, luminescence efficiency, and/or lifespan. For example, the light-emitting device may have excellent characteristics in terms of luminescence efficiency and/or lifespan, and simultaneously may emit blue light of excellent color purity.
Examples of the pyrrole-containing condensed cyclic group included in the first compound may include a carbazole group, a benzofurocarbazole group, a benzothienocarbazole group, an indolocarbazole group, an indenocarbazole group, and a benzosilolocarbazole group.
In an embodiment, the first compound may include a carbazole group, a benzofurocarbazole group, a benzothienocarbazole group, an indolocarbazole group, an indenocarbazole group, a benzosilolocarbazole group, or any combination thereof.
The silicon-containing group included in the first compound may be a group represented by Formula S-1:
may be a single bond,
Formula S-1 is the same as described in the present specification.
The term “π electron-rich C5-C60 cyclic group” as used herein 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 iso-indole group, an indole group, an indene group, a benzofuran group, a benzothiophene group, a benzosilole group, a naphthopyrrole group, a naphthofuran group, a naphthothiophene group, a naphthosilole group, a benzocarbazole group, a dibenzocarbazole group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, a triindolobenzene group, a pyrrolophenanthrene group, a furanophenanthrene group, a thienophenanthrene group, a benzonaphthofuran group, a benzonaphthothiophene group, an (indolo)phenanthrene group, a (benzofurano)phenanthrene group, or a (benzothieno)phenanthrene group.
The electron-transporting moiety not included in the first compound may be, for example, a π electron-deficient nitrogen-containing cyclic group (for example, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, or an imidazole group), a cyano group, or a group represented by one of the following formulae:
wherein, in the Formulae above, *, *′, and *″ each indicate a binding site to an atom.
The azine group included in the second compound may be a triazine group. In other words, the second compound may include a triazine group.
The silicon-containing group not included in the second compound may be, for example, a group represented by Formula S-1 described in the present specification.
In an embodiment, the first compound and the second compound may form an exciplex, and the maximum emission wavelength of the emission spectrum of the exciplex may be about 450 nm to about 490 nm, about 460 nm to about 490 nm, about 470 nm to about 490 nm, or about 480 nm to about 490 nm.
The emission spectrum of the exciplex formed from the first compound and the second compound is obtained by evaluating the emission spectrum of a film including the first compound and the second compound.
The first compound and the second compound may form an exciplex having a maximum emission wavelength within the range as described above, and for example, a light-emitting device including, as a host in an emission layer, the composition including the first compound and the second compound may have improved lifespan as the movement path of a host exciton in the emission layer is improved.
In an embodiment,
When the first compound and/or the second compound further includes at least one deuterium as described above, lifespan characteristics of a light-emitting device including the composition may be improved.
A weight ratio of the first compound to the second compound in the composition may be 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 a weight ratio of the first compound to the second compound satisfies the range as described above, balance between holes and electrons in an emission layer including the composition is effectively achieved, and thus, a light-emitting device having excellent luminescence efficiency and/or excellent lifespan characteristics may be implemented.
In an embodiment, the first compound may be a compound represented by Formula 1-1, a compound represented by Formula 1-2, a compound represented by Formula 1-3, or a combination thereof. Formulae 1-1, 1-2, and 1-3 are respectively the same as those described below.
In an embodiment, the second compound may be a compound represented by Formula 2. Formula 2 is the same as described below.
In an embodiment, the composition may further include an emitter. The emitter is a material capable of emitting light by receiving excitons from the first compound, the second compound, and/or a sensitizer and transitioning therefrom to a ground state.
When the composition further includes an emitter, an amount (weight) of the emitter may be about 0.5 wt % to about 30 wt % based on 100 wt % 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 capable of emitting phosphorescence or fluorescence.
For example, the emitter may be a phosphorescent compound, a fluorescent compound (for example, delayed fluorescence compound or a prompt fluorescent compound), or any combination thereof.
The emitter may emit blue light.
For example, the emitter may emit blue light having a maximum emission wavelength of about 400 nm to about 490 nm (for example, about 450 nm to about 490 nm), about 410 nm to about 470 nm, or about 420 nm to about 450 nm.
In an embodiment, the emitter may be an organometallic compound, the organometallic compound may include a transition metal and n ligands bonded to the transition metal, and n may be an integer from 1 to 4. In other words, the emitter may be a phosphorescent dopant.
In an embodiment, a transition metal in the organometallic compound may be platinum (Pt) or palladium (Pd), n may be 1, and the ligand may be a tetradentate ligand. The tetradentate ligand may include, for example, a carbene moiety bonded to the transition metal.
In an embodiment, the transition metal in the organometallic compound may be iridium (Ir) or osmium (Os), n may be 3, and at least one of the n ligands may be a bidentate ligand including —F, a cyano group, or a combination thereof or a bidentate ligand including a carbene moiety bonded to the transition metal. For example, the bidentate ligand may further include an imidazole group or a triazole group.
In an embodiment, the organometallic compound may be an organometallic compound represented by Formula 3 and/or an organometallic compound represented by Formula 5 described in the present specification. Formulae 3 and 5 will be described below.
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.
For example, an absolute value of a difference between singlet (S1) energy and triplet (T1) energy of the delayed fluorescence material may be about 0 eV to about 0.3 eV.
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 together. In this regard, at least two C3-C60 cyclic groups in the core may be condensed together 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 below.
In an embodiment, the composition may further include a sensitizer.
An amount (weight) of the sensitizer may be about 0.01 wt % to about 10 wt % based on 100 wt % of the composition.
For example, the sensitizer may be an organometallic compound including a transition metal and a tetradentate ligand bonded to the transition metal, wherein the transition metal may be platinum (Pt) or palladium (Pd), and the tetradentate ligand may include a carbene moiety bonded 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 as described in the present specification. The sensitizer may serve to effectively transfer excitons from the first compound and second compound to the emitter.
In an embodiment, the emitter may be a delayed fluorescence material as described in the present specification, and the sensitizer may be an organometallic compound as described in the present specification. 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.
Hereinafter, each Formula will be described.
The first compound may be a compound represented by Formula 1-1, a compound represented by Formula 1-2, a compound represented by Formula 1-3, or a combination thereof:
is a single bond, and ii) when m2 is 0, a group represented by
is a single bond,
For example, R1 to R7 in Formulae 1-1, 1-2, and 1-3 may each independently:
In an embodiment, R1 to R7 in Formulae 1-1, 1-2, and 1-3 may each independently be:
In an embodiment, in Formula 1-1, i) R1, ii) R3, iii) R4, or iv) each of R3 and R4 may be a group represented by Formula S-1.
In an embodiment, R6 in Formula 1-2 may be a group represented by Formula S-1.
In an embodiment, ring A1 to ring A7 and ring B1 to ring B4 in Formulae 1-1, 1-2, 1-3, and S-1 may each independently be a benzene group, a naphthalene group, a furan group, a thiophene group, a pyrrole group, a cyclopentadiene group, a silole group, a benzofuran group, a benzothiophene group, an indole group, an indene group, a benzosilole group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a fluorene group, a dibenzosilole group, a benzofurocarbazole group, a benzothienocarbazole group, an indolocarbazole group, an indenocarbazole group, or a benzosilolocarbazole group.
In an embodiment, rings A1, A2, A4 and A5 may each independently be a benzene group, a benzofuran group, a benzothiophene group, or an indole group.
In an embodiment, rings A3, A6, A7, and B1 to ring B4 may each independently be a benzene group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a benzofurocarbazole group, a benzothienocarbazole group, or an indolocarbazole group.
W1 to W4 in Formula S-1 may each independently be:
The first compound may be, for example, one of Compounds H1 to H29, a compound from which deuterium is replaced with hydrogen among Compounds H2 to H5 and H29, a compound in which the substitution position and/or the number of deuterium is changed among Compounds H2 to H5 and H29, a compound in which at least one hydrogen of Compounds H1 and H6 and H28 is replaced with deuterium, or any combination thereof:
The second compound may be a compound represented by Formula 2:
For example, at least two of X4 to X6 in Formula 2 may be N. In an embodiment, X4 to X6 in Formula 2 may each be N.
In an embodiment, each of Z1 to Z3 may be a benzene group that is unsubstituted or substituted with at least one R0.
In an embodiment, Z1 to Z3 may each independently be a group represented by one of Formulae 2(1) to 2(3):
In an embodiment, Z1 to Z3 may each independently be a group represented by one of Formulae 2(2) and 2(3).
In an embodiment, in Formula 2,
In an embodiment, each of Z11 to Z13 may be a benzene group, a carbazole group, a benzofurocarbazole group, or a benzothienocarbazole group, each unsubstituted or substituted with at least one R0.
In an embodiment, each of Z11 to Z13 may be a carbazole group, a benzofurocarbazole group, or a benzothienocarbazole group, each unsubstituted or substituted with at least one R0.
In an embodiment, each of Z11 to Z13 may be a group represented by Formula 2-CZ:
In an embodiment, in Formula 2,
In an embodiment, R0 and Z14 to Z16 may each independently be:
In an embodiment, the second compound may include a carbazole group, and the number of carbazole groups included in the second compound may be 5 or less (for example, 3, 4, or 5).
The second compound may be one of Compounds E1 to E41, a compound from which deuterium is replaced with hydrogen among Compounds E2, E3, E4, E7, E8, E9, E10, and E13, a compound in which the substitution position of a deuterium and/or the number of deuterium atoms is changed among Compounds E2, E3, E4, E7, E8, E9, E10, E12 and E13, a compound in which at least one hydrogen of Compounds E1, E5, E6, E11, and E14 to E16 is replaced with deuterium, or any combination thereof:
Description of Formula 3
The emitter and the sensitizer in the present specification may be an organometallic compound represented by Formula 3:
In an embodiment, M31 in Formula 3 may be Pt, Pd, or Au.
In an embodiment, M31 in Formula 3 may be Pt or Pd.
In an embodiment, a bond between X11 and M31 in Formula 3 may be a coordinate bond.
In an embodiment, in Formula 3, X11 may be C, and a bond between X11 and M31 may be a coordinate bond. In other words, X11 in Formula 3 may be C in a carbene moiety.
In an embodiment, 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:
wherein a bond between carbon of an imidazole group and M31 in Formula 3-1 is a coordinate bond. In other words, the imidazole group in Formula 3-1 includes a carbene moiety bonded to M31.
A bond between carbon of a benzimidazole group and M31 in Formula 3-2 may be a coordinate bond. In other words, the benzimidazole group in Formula 3-2 includes a carbene moiety bonded to M31.
In Formulae 3-1 and 3-2,
In an embodiment, in Formulae 3-1 and 3-2,
For example, in Formulae 3-1 and 3-2, at least one of R311 to R317 may include a C1-C20 alkyl group, a C6-C60 aryl group, or a C7-C60 arylakyl group, each unsubstituted or substituted with at least one of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a phenyl group, a cumyl group, or a combination thereof.
The emitter may be an organometallic compound represented by Formula 5:
M51(L51)n51(L52)n52 Formula 5
For example, M51 may be a first-row transition metal, a second-row transition metal, or a third-row transition metal.
As another example, M51 may be iridium (Ir), platinum (Pt), osmium (Os), titanium (Ti), zirconium (Zr), hafnium (Hf), europium (Eu), terbium (Tb), thulium (Tm), or rhodium (Rh).
In an embodiment, M51 may be Ir, Pt, Os, or Rh.
In an embodiment, 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 the same as described in the present specification.
n51 in Formula 5 may be 1, 2, or 3, wherein, when n51 is 2 or more, two or more L51 may be identical to or different from each other.
n52 in Formula 5 may be 0, 1, or 2, wherein, when n52 is 2, two L52 may be identical to or different from each other.
The sum of n51 and n52 in Formula 5 may be 2 or 3. For example, the sum of n51 and n52 may be 3.
In an embodiment, in Formula 5, i) M may be Ir, and n51+n52=3; or ii) M may be Pt, and n51+n52=2.
In an embodiment, 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,
As another example, in Formulae 5A and 5B, ring CY1 to ring CY4 may each independently be a cyclopentane group, a cyclohexane group, a cyclohexene group, a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a 1,2,3,4-tetrahydronaphthalene group, a cyclopentadiene group, a pyrrole group, a furan group, a thiophene group, a silole group, a borole group, a phosphole group, a germole group, a selenophene group, an indene group, an indole group, a benzofuran group, a benzothiophene group, a benzosilole group, a benzoborole group, a benzophosphole group, a benzogermole group, a benzoselenophene group, a fluorene group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, a dibenzosilole group, a dibenzoborole group, a dibenzophosphole group, a dibenzogermole group, a dibenzoselenophene group, a benzofluorene group, a benzocarbazole group, a naphthobenzofuran group, a naphthobenzothiophene group, a naphthobenzosilole group, a naphthobenzoborole group, a naphthobenzophosphole group, a naphthobenzogermole group, a naphthobenzoselenophene group, a dibenzofluorene group, a dibenzocarbazole group, a dinaphthofuran group, a dinaphthothiophene group, a dinaphthosilole group, a dinaphthoborole group, a dinaphthophosphole group, a dinaphthogermole group, a dinaphthoselenophene group, an indenophenanthrene group, an indolophenanthrene group, a phenanthrobenzofuran group, a phenanthrobenzothiophene group, a phenanthrobenzosilole group, a phenanthrobenzoborole group, a phenanthrobenzophosphole group, a phenanthrobenzogermole group, a phenanthrobenzoselenophene group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azaindene group, an azaindole group, an azabenzofuran group, an azabenzothiophene group, an azabenzosilole group, an azabenzoborole group, an azabenzophosphole group, an azabenzogermole group, an azabenzoselenophene group, an azafluorene group, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, an azadibenzoborole group, an azadibenzophosphole group, an azadibenzogermole group, an azadibenzoselenophene group, an azabenzofluorene group, an azabenzocarbazole group, an azanaphthobenzofuran group, an azanaphthobenzothiophene group, an azanaphthobenzosilole group, an azanaphthobenzoborole group, an azanaphthobenzophosphole group, an azanaphthobenzogermole group, an azanaphthobenzoselenophene group, an azadibenzofluorene group, an azadibenzocarbazole group, an azadinaphthofuran group, an azadinaphthothiophene group, an azadinaphthosilole group, an azadinaphthoborole group, an azadinaphthophosphole group, an azadinaphthogermole group, an azadinaphthoselenophene group, an azaindenophenanthrene group, an azaindolophenanthrene group, an azaphenanthrobenzofuran group, an azaphenanthrobenzothiophene group, an azaphenanthrobenzosilole group, an azaphenanthrobenzoborole group, an azaphenanthrobenzophosphole group, an azaphenanthrobenzogermole group, an azaphenanthrobenzoselenophene group, an azadibenzothiophene 5-oxide group, an aza9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a benzoquinoline group, a benzoisoquinoline group, a benzoquinoxaline group, a benzoquinazoline group, a phenanthroline group, a phenanthridine group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isooxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, an azasilole group, an azaborole group, an azaphosphole group, an azagermole group, an azaselenophene group, a benzopyrrole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzisoxazole group, a benzothiazole group, a benzisothiazole group, a benzoxadiazole group, a benzothiadiazole group, a pyridinopyrrole group, a pyridinopyrazole group, a pyridinoimidazole group, a pyridinooxazole group, a pyridinoisoxazole group, a pyridinothiazole group, a pyridinoisothiazole group, a pyridinooxadiazole group, a pyridinothiadiazole group, a pyrimidinopyrrole group, a pyrimidinopyrazole group, a pyrimidinoimidazole group, a pyrimidinooxazole group, a pyrimidinoisoxazole group, a pyrimidinothiazole group, a pyrimidinoisothiazole group, a pyrimidinooxadiazole group, a pyrimidinothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, a 5,6,7,8-tetrahydroquinoline group, an adamantane group, a norbornane group, a norbornene group, a benzene group condensed with a cyclohexane group, a benzene group condensed with a norbornane group, a pyridine group condensed with a cyclohexane group, or a pyridine group condensed with a norbornane group.
For example, ring CY51 and ring CY53 in Formulae 5A and 5B may be different from each other.
In an embodiment, ring CY52 and ring CY54 in Formulae 5A and 5B may be different from each other.
In an embodiment, 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)(Q55), —Ge(Q53)(Q54)(Q55), —B(Q56)(Q57), —P(═O)(Q58)(Q59), or —P(Q58)(Q59). Q51 to Q59 are each the same as described in the present specification.
In an embodiment, R51 to R54 in Formulae 5A and 5B may each independently be:
In an embodiment, R51 to R54 may each independently be:
b51 to b54 in Formulae 5A and 5B indicate the numbers of R51 to R54, respectively, and may each independently be an integer from 0 to 20. When b51 is 2 or more, two or more R51 may be identical to or different from each other, when b52 is 2 or more, two or more R52 may be identical to or different from each other, when b53 is 2 or more, two or more R53 may be identical to or different from each other, and when b54 is 2 or more, two or more R54 may be identical to or different from each other. For example, b51 to b54 may each independently be an integer from 0 to 8.
In an embodiment, in Formula 5A, Y52 may be C, a bond between Y52 and M51 may be a covalent bond, and at least one R52 may be a cyano group, —F, or a combination thereof.
In an embodiment, in Formula 5A, Y51 may be N, a bond between Y51 and M51 may be a coordinate bond, CY51 may be an imidazole group, a triazole group, a benzimidazole group, or a triazolopyridine group, and at least one R52 may be a cyano group, —F, or a combination thereof.
In an embodiment, in Formula 5A, Y51 may be C, and a bond between Y51 and M51 may be a coordinate bond.
In an embodiment, in Formula 5A, Y51 may be C, a bond between Y51 and M51 may be a coordinate bond, and CY51 may be a benzimidazole group or an imidazopyrazine group.
Examples of organometallic compounds represented by Formula 3 and organometallic compounds represented by Formula 5
For example, each of 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 may be, a polycyclic compound represented by 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 together. At least two C3-C60 cyclic groups in the polycyclic group may be condensed together while sharing boron (B) or nitrogen (N).
In an embodiment, 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 one may be 0.
In an embodiment, R41 to R49 may each independently be:
In an embodiment, the polycyclic compound represented by Formula 4 may be a polycyclic compound represented by one of Formulae 4-1 to 4-9:
The polycyclic compound represented by Formula 4 may be selected from among Compounds D1 to D30:
According to another aspect of the disclosure, a layer includes the composition as described in the present specification.
For example, when the composition further includes an emitter, the layer may be an emission layer.
According to another aspect of the disclosure, a light-emitting device, for example, an organic light-emitting device, includes: a first electrode; a second electrode; and an organic layer arranged between the first electrode and the second electrode and including an emission layer, wherein the organic layer includes the composition as described in the present specification.
In an embodiment, the composition may be included in an emission layer in 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 of about 400 nm to about 490 nm (for example, about 450 nm to 490 nm), about 410 nm to about 470 nm, or about 420 nm to about 450 nm.
Since the organic light-emitting device includes the composition as described above, the organic light-emitting device may have excellent luminescence efficiency and excellent 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 organic layer may further include a hole transport region between the first electrode and the emission layer and an electron transport region between the emission layer and the second electrode, wherein the hole transport region may include a hole injection layer, a hole transport layer, an electron blocking layer, an auxiliary layer, or a combination thereof, and the electron transport region may include a buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof.
The term “organic layer” used herein refers to a single layer and/or a plurality of layers between the first electrode and the second electrode of the organic light-emitting device. The “organic layer” may include, in addition to an organic compound, an organometallic complex including metal.
In
In
A substrate may be additionally disposed under the first electrode 11 or above the second electrode 19. For use as the substrate, any substrate that is used in organic light-emitting devices available in the art may be used, and the substrate may be a glass substrate or a transparent plastic substrate, each having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance.
The first electrode 11 may be, for example, formed by depositing or sputtering a material for forming the first electrode 11 on the substrate. The first electrode 11 may be an anode. The material for forming the first electrode 11 may include materials with a high work function to facilitate hole injection.
The first electrode 11 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. When the first electrode 11 is a transmissive electrode, the material for forming the first electrode 11 may include indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), or any combination thereof. In an embodiment, when the first electrode 110 is a semi-transmissive electrode or a reflective electrode, a material for forming the first electrode 11 may include magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), or any combination thereof.
The first electrode 11 may have a single layered structure or a multilayer structure including a plurality of layers.
The thickness of the emission layer 15 may be in a range of about 100 Å to about 1,000 Λ, for example, about 200 Å to about 600 Λ. When the thickness of the emission layer is within the range, 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 in the present specification.
The hole transport region 12 may be located between the first electrode 11 and the emission layer 15 of the organic light-emitting device 10.
The hole transport region 12 may have a single-layered structure or a multi-layered structure.
For example, the hole transport region 12 may have a hole injection layer, a hole transport layer, a hole injection layer/hole transport layer structure, a hole injection layer/first hole transport layer/second hole transport layer structure, a hole injection layer/first hole transport layer/second hole transport layer/electron blocking layer structure, a hole transport layer/organic layer structure, a hole injection layer/hole transport layer/organic layer structure, a hole transport layer/electron blocking layer structure, or a hole injection layer/hole transport layer/electron blocking layer structure.
The hole transport region 12 may include any compound having hole-transporting properties.
For example, the hole transport region 12 may include an amine-based compound.
In an embodiment, the hole transport region 12 may include, for example, m-MTDATA, TDATA, 2-TNATA, NPB, 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 any combination thereof:
wherein, in Formulae 201 to 205,
In an embodiment,
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 an embodiment, 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, a compound represented by Formula 201 including a carbazole group and further including at least one of a dibenzofuran group, a dibenzothiophene group, a fluorene group, a spiro-bifluorene group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, or a combination thereof.
The carbazole-free amine-based compound may include, for example, a compound represented by Formula 201 not including a carbazole group and including at least one of a dibenzofuran group, a dibenzothiophene group, a fluorene group, a spiro-bifluorene group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, or a combination thereof.
In an embodiment, the hole transport region 12 may include a compound represented by Formula 201, a compound represented by Formula 202, or any combination thereof.
In an embodiment, the hole transport region 12 may include a compound represented by Formula 201-1, 202-1, or 201-2, or any combination thereof:
wherein, in Formulae 201-1, 202-1, and 201-2, L201 to L203, L205, xa1 to xa3, xa5, R201, and R202 are the same as described herein, 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 hydrazine group, a hydrazone 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 that is 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 at least one of Compounds HT1 to HT39:
In an embodiment, hole transport region 12 of the organic light-emitting device 10 may further include a p-dopant. When the hole transport region 12 further includes a p-dopant, the hole transport region 12 may have a matrix (for example, at least one of compounds represented by Formulae 201 to 205) and a p-dopant included in the matrix. The p-dopant may be uniformly or non-uniformly doped in the hole transport region 12.
In an embodiment, the LUMO energy level of the p-dopant may be about −3.5 eV or less.
The p-dopant may include a quinone derivative, a metal oxide, a cyano group-containing compound, or any combination thereof.
For example, the p-dopant may include:
In Formula 221,
R221 to R223 may each independently be 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 C1-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, wherein at least one substituent of R221 to R223 may be: a cyano group; —F; —Cl; —Br; —I; a C1-C20 alkyl group substituted with —F; a C1-C20 alkyl group substituted with —Cl; a C1-C20 alkyl group substituted with —Br; a C1-C20 alkyl group substituted with —I; or any combination thereof.
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 Λ, 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.
The buffer layer may compensate for an optical resonance distance according to a wavelength of light emitted from the emission layer, and thus, efficiency may be increased.
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 arranged between the emission layer 15 and the second electrode 19 of the organic light-emitting device 10.
The electron transport region 17 may have a single-layered structure or a multilayer structure.
For example, the electron transport region 17 may have an electron transport layer, an electron transport layer/electron injection layer structure, a buffer layer/electron transport layer structure, hole blocking layer/electron transport layer structure, a buffer layer/electron transport layer/electron injection layer structure, or a hole blocking layer/electron transport layer/electron injection layer structure. The electron transport region 17 may further include an electron control layer.
The electron transport region 17 may include known electron-transporting materials.
The electron transport region 17 (for example, a buffer layer, a hole blocking layer, an electron control layer, or an electron transport layer in the electron transport region) may include a metal-free compound containing at least one π electron-deficient nitrogen-containing C1-C60 cyclic group. The π electron-deficient nitrogen-containing C1-C60 cyclic group is the same as described above.
For example, the electron transport region 17 may include a compound represented by Formula 601.
[Ar601]xe11-[(L601)xe1-R601]xe21 Formula 601
In Formula 601,
In an embodiment, at least one of xe11 Ar601 and xe21 R601 may include the π electron-deficient nitrogen-containing C1-C60 cyclic group.
In an embodiment, Ar601 and L601 in Formula 601 may each independently be a benzene group, a naphthalene group, a fluorene group, a spiro-bifluorene group, a benzofluorene group, a dibenzofluorene group, a phenalene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a naphthacene group, a picene group, a perylene group, a pentaphene group, an indenoanthracene group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, an imidazole group, a pyrazole group, a thiazole group, an isothiazole group, an oxazole group, an isoxazole group, a pyridine group, a pyrazine group, a pyrimidine group, a pyridazine group, an indazole group, a purine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a phthalazine group, a naphthyridine group, a quinoxaline group, a quinazoline group, a cinnoline group, a phenanthridine group, an acridine group, a phenanthroline group, a phenazine group, a benzimidazole group, an isobenzothiazole group, a benzoxazole group, an isobenzoxazole group, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, a thiadiazole group, an imidazopyridine group, an imidazopyrimidine group, or an azacarbazole group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, —Si(Q31)(Q32)(Q33), —S(═O)2(Q31), —P(═O)(Q31)(Q32), or any combination thereof, and
When xe11 in Formula 601 is 2 or more, two or more Ar601 may be linked to each other via a single bond.
In an embodiment, Ar601 in Formula 601 may be an anthracene group.
In an embodiment, the compound represented by Formula 601 may be represented by Formula 601-1:
In an embodiment, xe1 and xe611 to xe613 in Formulae 601 and 601-1 may each independently be 0, 1, or 2.
In an embodiment, R601 and R611 to R613 in Formulae 601 and 601-1 may each independently be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, a pyridinyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a thiadiazolyl group, an oxadiazolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a benzimidazolyl group, an isobenzothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, or an azacarbazolyl group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a pentaphenyl group, a hexacenyl group, a pentacenyl group, a thiophenyl group, a furanyl group, a carbazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a dibenzosilolyl group, a pyridinyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a thiadiazolyl group, an oxadiazolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a benzimidazolyl group, an isobenzothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an azacarbazolyl group, or any combination thereof; or
The electron transport region 17 may include at least one of Compounds ET1 to ET36:
In an embodiment, the electron transport region 17 may include 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-dphenyl-1,10-phenanthroline (Bphen), Alq3, BAlq, 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), NTAZ, DBFPO, or any combination thereof. For example, when the electron transport region 17 includes a hole blocking layer, the hole blocking layer may include BCP or Bphen:
Thicknesses of the buffer layer, the hole blocking layer, and the electron control layer may each independently be 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.
The thickness of the electron transport layer may be in a range of about 100 Å to about 1,000 Å, for example, about 150 Å to about 500 Å. When the thickness of the electron transport layer is within the range as described above, satisfactory electron transport characteristics may be obtained without a substantial increase in driving voltage.
The electron transport region 17 (for example, the electron transport layer in the electron transport region 17) may further include, in addition to the materials described above, a metal-containing material.
The metal-containing material may include an alkali metal complex, an alkaline earth metal complex, or any combination thereof. A metal ion of the alkali metal complex may include a Li ion, a Na ion, a K ion, a Rb ion, a Cs ion, or any combination thereof, and a metal ion of the alkaline earth metal complex may include a Be ion, a Mg ion, a Ca ion, a Sr ion, a Ba ion, or any combination thereof. A ligand coordinated with the metal ion of the alkali metal complex or the alkaline earth-metal complex may include a hydroxyquinoline, a hydroxyisoquinoline, a hydroxybenzoquinoline, a hydroxyacridine, a hydroxyphenanthridine, a hydroxyphenyloxazole, a hydroxyphenylthiazole, a hydroxydiphenyloxadiazole, a hydroxydiphenylthiadiazole, a hydroxyphenylpyridine, a hydroxyphenylbenzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or any combination thereof.
In an embodiment, the metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 (LiQ) or ET-D2:
The electron transport region 17 may include an electron injection layer that facilitates the injection of electrons from the second electrode 19. The electron injection layer may be in direct contact with 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 multilayer structure having a plurality of layers including a plurality of different materials.
The electron injection layer may include an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal compound, an alkaline earth-metal compound, a rare earth metal compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or any combination thereof.
The alkali metal may include Li, Na, K, Rb, Cs, or any combination thereof. In an embodiment, the alkali metal may be Li, Na, or Cs. In an embodiment, the alkali metal may be Li or Cs.
The alkaline earth metal may include Mg, Ca, Sr, Ba, or any combination thereof.
The rare earth metal may include Sc, Y, Ce, Tb, Yb, Gd, or any combination thereof.
The alkali metal compound, the alkaline earth metal compound, and the rare earth metal compound may include oxides and halides (for example, fluorides, chlorides, bromides, or iodides) of the alkali metal, the alkaline earth metal, and the rare earth metal, or any combination thereof.
The alkali metal compound may include: at least one of alkali metal oxides such as Li2O, Cs2O, or K2O; at least one of alkali metal halides such as LiF, NaF, CsF, KF, LiI, NaI, CsI, or KI; or any combination thereof. In an embodiment, the alkali metal compound may include LiF, Li2O, NaF, LiI, NaI, CsI, KI, or any combination thereof.
The alkaline earth-metal compound may include one of alkaline earth-metal compounds, such as BaO, SrO, CaO, BaxSr1-xO (wherein 0<x<1), or BaxCa1-xO (wherein 0<x<1), or any combination thereof. In an embodiment, the alkaline earth metal compound may include BaO, SrO, CaO, or any combination thereof.
The rare earth metal compound may include YbF3, ScF3, ScO3, Y2O3, Ce2O3, GdF3, TbF3, or any combination thereof. In an embodiment, the rare earth metal compound may include YbF3, ScF3, TbF3, YbI3, ScI3, TbI3, or any combination thereof.
The alkali metal complex, the alkaline earth metal complex, and the rare earth metal complex may include an ion of alkali metal, alkaline earth metal, and rare earth metal as described above, and a ligand coordinated with a metal ion of the alkali metal complex, the alkaline earth metal complex, or the rare earth metal complex may include hydroxy quinoline, hydroxy isoquinoline, hydroxy benzoquinoline, hydroxy acridine, hydroxy phenanthridine, hydroxy phenyloxazole, hydroxy phenylthiazole, hydroxy diphenyloxadiazole, hydroxy diphenylthiadiazole, hydroxy phenylpyridine, hydroxy phenylbenzimidazole, hydroxy phenylbenzothiazole, bipyridine, phenanthroline, cyclopentadiene, or any combination thereof.
The electron injection layer may consist of an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal compound, an alkaline earth-metal compound, a rare earth metal compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or any combinations thereof, as described above. In an embodiment, the electron injection layer may further include an organic material. When the electron injection layer further includes an organic material, an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal compound, an alkaline earth-metal compound, a rare earth metal compound, an alkali metal complex, an alkaline earth-metal complex, a rare earth metal complex, or any combination thereof may be homogeneously or non-homogeneously dispersed in a matrix including the organic material.
The thickness of the electron injection layer may be in a range of about 1 Å to about 100 Å, and, for example, about 3 Å to about 90 Λ. When the thickness of the electron injection layer is within the range described above, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.
The second electrode 19 is located on the organic layer 10A having such a structure. The second electrode 19 may be a cathode which is an electron injection electrode, and in this regard, a material for forming the second electrode 19 may be selected from a metal, an alloy, an electrically conductive compound, and a combination thereof, which have a relatively low work function.
The second electrode 19 may include lithium (Li), silver (Ag), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), ITO, IZO, or any combination thereof. The second electrode 19 may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode.
The second electrode 19 may have a single-layered structure having a single layer or a multilayer structure including two or more layers.
The term “C1-C60 alkyl group” as used herein refers to a linear or branched saturated aliphatic hydrocarbon monovalent group having 1 to 60 carbon atoms, and 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 may include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, or a tert-decyl group, each unsubstituted or substituted with a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, or any combination thereof.
The term “C1-C60 alkoxy group” 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, or a pentoxy group.
The term “C2-C60 alkenyl group” as used herein has a structure including 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 has a structure including 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, B, or any combination thereof as a ring-forming atom and 1 to 10 carbon atoms, and the term “the C1-C10 heterocycloalkylene group” as used herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkyl group.
Examples of the C1-C10 heterocycloalkyl group may include a silolanyl group, a silinanyl group, a 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 hetero atom selected from N, O, P, Si, S, Se, Ge, B, or any combination thereof 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 include a 2,3-dihydrofuranyl group and a 2,3-dihydrothiophenyl group. The term “C1-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 two or more rings may be fused to each other.
The term “C1-C60 heteroaryl group” as used herein refers to a monovalent group that includes at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and a heterocyclic aromatic system having 1 to 60 carbon atoms, and the term “C1-C60 heteroarylene group” as used herein refers to a divalent group that includes at least one heteroatom selected from N, O, P, Si, S, Se, Ge, B, or any combination thereof as a ring-forming atom and a heterocyclic aromatic system having 1 to 60 carbon atoms. 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 C6-C60 heteroaryl group and the C6-C60 heteroarylene group each include two or more rings, the two or more 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 having two or more rings condensed together, only carbon atoms (for example, 8 to 60 carbon atoms) as ring-forming atoms, and non-aromaticity in its molecular structure when considered as a whole. 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 a monovalent non-aromatic condensed polycyclic group.
The term “monovalent non-aromatic condensed heteropolycyclic group” as used herein refers to a monovalent group having two or more rings condensed together, a heteroatom selected from N, O, P, Si, S, Se, Ge, B, or a combination thereof other than carbon atoms (for example, 1 to 60 carbon atoms), as a ring-forming atom, and non-aromaticity in its molecular structure when considered as a whole. The monovalent non-aromatic condensed heteropolycyclic group includes a carbazolyl group. The term “divalent non-aromatic condensed heteropolycyclic group” as used herein refers to a divalent group having the same structure as a monovalent non-aromatic condensed heteropolycyclic group.
The term “π electron-deficient nitrogen-containing C1-C60 cyclic group” as used herein refers to a cyclic group having 1 to 60 carbon atoms and including at least one *—N═*′ (wherein * and *′ each indicate a binding site to an adjacent atom) as a ring-forming moiety. For example, the π electron-deficient nitrogen-containing C1-C60 cyclic group may be a) a first ring, b) a condensed ring in which two or more first rings are condensed together, or c) a condensed ring in which at least one first ring and at least one second ring are condensed together.
The term “π electron-rich C3-C60 cyclic group” as used herein refers to a cyclic group having 3 to 60 carbon atoms and not including at least one *—N═*′ (wherein * and *′ each indicate a binding site to an adjacent atom) as a ring-forming moiety. For example, the π electron-rich C3-C60 cyclic group may be a) a second ring or b) a condensed ring in which two or more second rings are condensed together.
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 together.
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 together, or c) a condensed ring in which at least one third ring and at least one fourth ring are condensed together.
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 an embodiment, the π electron-deficient nitrogen-containing C1-C60 cyclic group may be an imidazole group, a pyrazole group, a thiazole group, an isothiazole group, an oxazole group, an isoxazole group, a pyridine group, a pyrazine group, a pyridazine group, a pyrimidine group, an indazole group, a purine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a benzoisoquinoline group, a phthalazine group, a naphthyridine group, a quinoxaline group, a benzoquinoxaline group, a quinazoline group, a cinnoline group, a phenanthridine group, an acridine group, a phenanthroline group, a phenazine group, a benzimidazole group, an isobenzothiazole group, a benzoxazole group, an isobenzoxazole group, a triazole group, a tetrazole group, an oxadiazole group, a triazine group, a thiadiazole group, an imidazopyridine group, an imidazopyrimidine group, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, an acridine group, or a pyridopyrazine group.
For example, the π electron-rich C3-C60 cyclic group may be a benzene group, a heptalene group, an indene group, a naphthalene group, an azulene group, an indacene group, an acenaphthylene group, a fluorene group, a spiro-bifluorene group, a benzofluorene group, a dibenzofluorene group, a phenalene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a naphthacene group, a picene group, a perylene group, a pentacene group, a hexacene group, a pentaphene group, a rubicene group, a coronene group, an ovalene group, a pyrrole group, a furan group, a thiophene group, an isoindole group, an indole group, an indene group, a benzofuran group, a benzothiophene group, a benzosilole group, a naphthopyrrole group, a naphthofuran group, a naphthothiophene group, a naphthosilole group, a benzocarbazole group, a dibenzocarbazole group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, a dibenzosilole group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, a triindolobenzene group, a pyrrolophenanthrene group, a furanophenanthrene group, a thienophenanthrene group, a benzonaphthofuran group, a benzonapthothiophene group, an (indolo)phenanthrene group, a (benzofurano)phenanthrene group, or a (benzothieno)phenanthrene group.
For example, the C5-C60 carbocyclic group may be a cyclopentane group, a cyclohexane group, a cyclohexene group, a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a 1,2,3,4-tetrahydronaphthalene group, cyclopentadiene group, an indene group, a fluorene group, a 5,6,7,8-tetrahydroisoquinoline group, a 5,6,7,8-tetrahydroquinoline group, an adamantane group, a norbornane group, or a norbornene group.
For example, the C1-C60 heterocyclic group may be a thiophene group, a furan group, a pyrrole group, a cyclopentadiene group, a silole group, a borole group, a phosphole group, a selenophene group, a germole group, a benzothiophene group, a benzofuran group, an indole group, an indene group, a benzosilole group, a benzoborole group, a benzophosphole group, a benzoselenophene group, a benzogermole group, a dibenzothiophene group, a dibenzofuran group, a carbazole group, a dibenzosilole group, a dibenzoborole group, a dibenzophosphole group, a dibenzoselenophene group, a dibenzogermole group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azabenzothiophene group, an azabenzofuran group, an azaindole group, an azaindene group, an azabenzosilole group, an azabenzoborole group, an azabenzophosphole group, an azabenzoselenophene group, an azabenzogermole group, an azadibenzothiophene group, an azadibenzofuran group, an azacarbazole group, an azafluorene group, an azadibenzosilole group, an azadibenzoborole group, an azadibenzophosphole group, an azadibenzoselenophene group, an azadibenzogermole group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, or a benzothiadiazole group.
The term “a π electron-deficient nitrogen-containing C1-C60 cyclic group, a π electron-rich C3-C60 cyclic group, a C5-C60 cyclic group, and a C1-C60 heterocyclic group” 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.
At least one substituent of the substituted π electron-deficient nitrogen-containing C1-C60 cyclic group, the substituted π electron-rich C3-C60 cyclic group, the substituted C5-C60 cyclic group, the substituted C1-C60 heterocyclic group, the substituted C1-C60 alkylene group, the substituted C2-C60 alkenylene group, the substituted C2-C60 alkynylene group, the substituted C3-C10 cycloalkylene group, the substituted C1-C10 heterocycloalkylene group, the substituted C3-C10 cycloalkenylene group, the substituted C1-C10 heterocycloalkenylene group, the substituted C6-C60 arylene group, the substituted C1-C60 heteroarylene group, the substituted divalent non-aromatic condensed polycyclic group, the substituted divalent non-aromatic condensed heteropolycyclic group, the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C2-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may each independently be:
—N(Q31)(Q32), —S1(Q33)(Q34)(Q35), —Ge(Q33)(Q34)(Q35), —B(Q36)(Q37), —P(═O)(Q38)(Q39), or —P(Q38)(Q39); or
Q1 to Q9, Q11 to Q19, Q21 to Q29, and Q31 to Q39 used herein may each independently be: hydrogen; deuterium; —F; —Cl; —Br; —I; a hydroxyl group; a cyano group; a nitro group; an amidino group; a hydrazine group; a hydrazone group; a carboxylic acid or a salt thereof; a sulfonic acid or a salt thereof; a phosphoric acid or a salt thereof; a C1-C60 alkyl group which is unsubstituted or substituted with deuterium, a C1-C6 alkyl group, a C6-C60 aryl group, or any combination thereof; a C2-C60 alkenyl group; a C2-C60 alkynyl group; a C1-C60 alkoxy group; a C3-C10 cycloalkyl group; a C1-C10 heterocycloalkyl group; a C3-C10 cycloalkenyl group; a C1-C10 heterocycloalkenyl group; a C6-C60 aryl group which is unsubstituted or substituted with deuterium, a C1-C60 alkyl group, a C6-C60 aryl group, or any combination thereof; a C6-C60 aryloxy group; a C6-C60 arylthio group; a C1-C60 heteroaryl group; a monovalent non-aromatic condensed polycyclic group; or a monovalent non-aromatic condensed heteropolycyclic group.
For example, Q1 to Q, 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” 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 disclosure is not limited thereto. The wording “‘B’ was used instead of ‘A’” used in describing Synthesis Examples means that an amount of ‘A’ used was identical to an amount of ‘B’ used, in terms of a molar equivalent.
Compound H1 was synthesized according to the following reaction scheme.
9H-3,9′-bicarbazole (7.48 g, 22.49 mmol), (3-bromophenyl)triphenylsilane (11.21 g, 26.99 mmol), Pd(dba)2 (1.29 g, 2.25 mmol), tri-tert-butylphosphine (50 wt % of toluene solution, 1.82 g, 4.50 mmol), and sodium tert-butoxide (4.32 g, 44.98 mmol) were dissolved in o-xylene (56 ml). The mixture was heated and then stirred under reflux for 12 hours. After completion of the reaction, the temperature was lowered to room temperature, and then, methanol (1,000 ml) was added to the mixture. The resulting solid was filtered and then purified by silica column chromatography to obtain 10 g (yield of 67%) of Compound H1.
LC-Mass (calculated: 666.25 g/mol, found: M+1=667 g/mol)
1-iodo-2-nitrobenzene (27 g, 108 mmol), (phenyl-d5)boronic acid (15.1 g, 119 mmol), tetrakis(triphenylphosphine)palladium (0) (5 g, 4.32 mmol), and potassium carbonate (37.6 g, 272 mmol) were combined with a mixture of 540 ml of tetrahydrofuran and 135 ml of distilled water, followed by heating at 90° C. for 16 hours. After the reaction was completed, the mixture was cooled to room temperature, and an organic layer was extracted with ethyl acetate, dried using anhydrous magnesium sulfate (MgSO4), concentrated, and then subjected to silica column, to synthesize Intermediate H2-1. (29.5 g, crude)
LCMS (calculated: 204.09, found(M+1): 205.10 m/z)
Intermediate H2-1 (29.5 g, 144 mmol) and triphenylphosphine (71 g, 271 mmol) were combined with 1,2-dichlorobenzene (500 ml), followed by heating at 200° C. for 16 hours. After the reaction was completed, the mixture was cooled to room temperature, and an organic layer was extracted with ethyl acetate, dried using anhydrous magnesium sulfate (MgSO4), concentrated, and then subjected to silica column chromatography followed by sublimation purification, to synthesize Intermediate H2-2. (9.7 g, 56.6 mmol, yield of 40%)
LCMS (calculated: 171.10, found(M+1): 172.21 m/z)
(3-bromophenyl)triphenylsilane (10 g, 24 mmol), carbazole (4.4 g, 26.3 mmol), sodium tert-butoxide (3.5 g, 39.5 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.88 g, 0.96 mmol), and tri-tert-butylphosphine (0.8 ml, 1.92 mmol) were mixed with 120 ml of toluene, followed by heating at 130° C. for 16 hours. After the reaction was completed, the mixture was cooled to room temperature, and an organic layer was extracted with ethyl acetate, dried using anhydrous magnesium sulfate (MgSO4), concentrated, and then subjected to silica column, to provide Intermediate H2-3. (11 g, 21.9 mmol, yield of 91%)
LCMS (calculated: 501.19, found(M+1): 502.3 m/z)
(4) Synthesis of Intermediate H2-4
Intermediate H2-3 (11 g, 21.9 mmol) and 200 ml of N,N-dimethylformamide (DMF) were stirred at 0° C. While the temperature was maintained at 0° C., N-bromosuccinimide (3.8 g, 21.4 mmol) dissolved in 20 ml of DMF was added dropwise, followed by stirring at room temperature for 16 hours. After the reaction was completed, the mixture was cooled to room temperature, and an organic layer was extracted with ethyl acetate, dried using anhydrous magnesium sulfate (MgSO4), concentrated, and then subjected to silica column chromatography, to provide Intermediate H2-4. (13.2 g, crude)
LCMS (calculated: 579.10, found(M+1): 580.2 m/z)
(5) Synthesis of Compound H2
Intermediate H2-2 (4.7 g, 27.4 mmol), Intermediate H2-4 (13.2 g, 22.7 mmol), sodium tert-butoxide (3.3 g, 34.3 mmol), tris(dibenzylideneacetone)dipalladium (0) (1 g, 1.09 mmol), and tri-tert-butylphosphine (0.9 mL, 2.18 mmol) were combined with 110 ml of toluene, followed by heating at 130° C. for 16 hours. After the reaction was completed, the mixture was cooled to room temperature, the reaction mixture was diluted with water, and an organic layer was extracted with ethyl acetate, dried using anhydrous magnesium sulfate (MgSO4), concentrated, and then subjected to silica column chromatography, to provide Intermediate H2. The column-purified product was further purified by recrystallization and sublimation purification. (6.4 g, 9.53 mmol, yield of 42%)
LCMS (calculated: 670.27, found(M+1): 671.33 m/z)
8.2 g of 9H-carbazole was dissolved in 80 ml of THF, followed by cooling at −78° C. under nitrogen atmosphere. 24.4 ml of 2.5 M n-BuLi was slowly added dropwise at −78° C. and stirred for an hour. 4.5 g of 2,4,6-trichloro-1,3,5-triazine was additionally added thereto, and the temperature was raised to room temperature, followed by stirring for 4 hours. After the reaction was completed, distilled water was slowly added dropwise thereto at room temperature to end the reaction. An organic layer was extracted with ethyl acetate, dried using anhydrous magnesium sulfate (MgSO4), condensed, and then subjected to silica column chromatography, to synthesize Intermediate A-1. (9.25 g, 20.7 mmol, yield of 85%)
LCMS (calculated: 445.11, found(M+1): 446.21 m/z)
[Synthesis of Intermediate B-1]
12.48 g of 9H-carbazole, 10 g of 1-bromo-2-fluorobenzene, and 30.51 g of potassium phosphate tribasic were combined with 280 ml of DMF, followed by stirring at 165° C. for 20 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, and an organic layer was extracted with ethyl acetate, dried using anhydrous magnesium sulfate (MgSO4), concentrated, and then subjected to silica column chromatography, to provide Intermediate B-1. (13.52 g, 41.97 mmol, yield of 73%)
LCMS (calculated: 322.21, found(M+1): 323.25 m/z)
[Synthesis of Intermediate B-2]
13.52 g of Intermediate B-1, 13.91 g of bis(pinacolato)diboron, 1.71 g of Pd(dppf)Cl2, and 10.3 g of potassium acetate were combined with 160 ml of xylene, followed by refluxing while heating for 16 hours. After the mixture was cooled to room temperature, purification was performed by column chromatography to obtain Intermediate B-2 (10.23 g, 27.7 mmol, yield of 66%).
LCMS (calculated: 322.21, found(M+1): 323.25 m/z)
[Synthesis of Compound E1]
7 g of Intermediate A-1, 10.14 g of Intermediate B-1, 1.1 g of Pd(PPh3)4, and 6.55 g of potassium carbonate were combined with 60 ml of THF and 30 ml of distilled water, followed by refluxing while heating under nitrogen atmosphere. After the reaction for 18 hours, the mixture was cooled to room temperature, ethyl acetate was added, an organic layer was separated, and purification was performed by column chromatography to obtain Compound E1 (9.75 g, 15.5 mmol, yield of 82%).
LCMS (calculated: 652.76, found(M+1): 653.1873 m/z)
[Synthesis of Intermediate D-1]
Intermediate D-1 was obtained in the same manner as in the synthesis of Intermediate A-1, except that, during synthesis of Intermediate D-1, 9H-carbazole-1,2,3,4,5,6,7,8-d8 was used instead of 9H-carbazole. (8.23 g, 17.8 mmol)
LCMS (calculated: 462.01, found(M+1): 463.24 m/z)
[Synthesis of Intermediate E-1]
Intermediate E-1 was obtained in the same manner as in the synthesis of Intermediate B-1, except that, during synthesis of Intermediate E-1, 9H-carbazole-1,2,3,4,5,6,7,8-d8 was used instead of 9H-carbazole, and 1-bromo-2-fluorobenzene-3,4,5,6-d4 was used instead of 1-bromo-2-fluorobenzene. (7.2 g, 22.34 mmol) LC/MS [M]+ (calculated: 322.21, found(M+1): 323.46 m/z)
[Synthesis of Intermediate E-2]
Intermediate E-2 was obtained in the same manner as in the synthesis of Intermediate B-2, except that, during synthesis of Intermediate E-2, Intermediate E-1 was used instead of Intermediate B-1. (6.85 g, 18.54 mmol)
LCMS (calculated: 369.27, found(M+1): 370.38 m/z)
[Synthesis of Compound E3]
Compound E3 was obtained in the same manner as used to obtain Compound E1, except that, during synthesis of Compound E2, Intermediate D-1 was used instead of Intermediate A-1, and Intermediate E-2 was used instead of Intermediate B-2. (9.21 g, 13.53 mmol)
LC/MS [M]+ (calculated: 680.93, found(M+1): 682.02 m/z)
Synthesis of Intermediate H29-1
After 3-bromo-9H-carbazole-d7 (1 eq) and KOH (1 eq) were combined with acetone and stirred at room temperature for 20 minutes, p-toluenesulfonyl chloride (1.5 eq) was slowly added dropwise thereto, followed by refluxing overnight to obtain intermediate H29-1.
Intermediate H29-1 was identified by LC/MS.
LCMS (calculated: 406.04, found(M+1): 407.11 m/z)
C19H7D7BrNO2S M+1: 407.02
Synthesis of Intermediate H29-2
Intermediate H29-1 (1 eq), carbazole-d8 (1.1 eq), CuI (0.5 eq), ethylenedimaine (2 eq), and K3PO4 (2 eq) were reacted overnight at 130° C. to obtain Intermediate H29-2. Intermediate H29-2 was identified by LC/MS.
LCMS (calculated: 501.23, found(M+1): 502.31 m/z)
C31H7D15N2O2S M+1: 502.21
Synthesis of Intermediate H29-3
Intermediate H29-2 (1 eq) and NaOH (10 eq) were mixed with a mixed solution of THF, MeOH, and H2O in a volume ratio of 2:1:1 and then reacted at 90° C. to obtain Intermediate H29-3. Intermediate H29-3 was identified by LC/MS.
LCMS (calculated: 347.23, found(M+1): 348.22 m/z)
Synthesis of Intermediate H29-4
1,3-dibromobenzene-2,4,5,6-d4 (1 eq) was reacted with n-BuLi (1.1 eq) at −78° C., and after 60 minutes, chlorotris(phenyl-d5)silane (1.2 eq) was slowly added dropwise thereto. Then, the temperature was slowly raised to room temperature, and the mixture was reacted overnight to obtain Intermediate H29-4. Intermediate H29-4 was identified by LC-MS.
LCMS (calculated: 433.16, found(M+1): 434.21 m/z)
Synthesis of Compound H29
2.8 g of Intermediate H29-3 and 2.9 g of Intermediate H29-4 were placed in a reaction vessel, and 0.25 g of Pd2dba3, 0.14 g of P(tBu)3, 1.2 g of NaOtBu, and 40 mL of toluene were added dropwise thereto. The reaction temperature was raised to 120° C., and then, the mixture was refluxed for 12 hours. After the reaction was completed, water was added, and the reaction solution was extracted with ethyl acetate. An organic layer collected therefrom was dried with magnesium sulfate, and a solvent was evaporated therefrom. A residue thus obtained was then separated and purified by silica gel column chromatography, thereby obtaining 22 g (yield: 42%) of Compound H29. Compound H29 was identified by LC-MS.
LCMS (calculated: 696.44, found(M+1): 697.39 m/z)
T1 energy levels of the compounds of Table 1 were evaluated by using the DFT method (T1 adiabatic) of the Gaussian program, which is structure-optimized at a level of B3LYP/6-31 G(d,p), and results thereof are shown in Table 1.
A quartz substrate washed using chloroform and pure water was prepared, a first compound and a second compound described in Table 2 were co-deposited in a weight ratio of 50:50 at a vacuum pressure of 10−7 torr to prepare Films A and 1 to 4, each having a thickness of 50 nm, the emission spectrum of each of Films A and 1 to 4 was evaluated by using Quantaurus-QY which is an absolute PL quantum yield measurement system manufactured by Hamamatus Corporation, the maximum emission wavelength of an exciplex formed from the first compound and the second compound included in each Film was evaluated therefrom, and results thereof are shown in Table 2. The emission spectrum of each of Films A, 1, and 2 is the same as shown in
From Table 2 and
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.
Compound HT1 and Compound HT-D2 were co-deposited on the ITO electrode on the glass substrate to form a hole injection layer having a thickness of 100 Å, and Compound HT1 was deposited on the hole injection layer to form a hole transport layer having a thickness of 1,300 Å, and mCP was deposited on the hole transport layer to form an electron blocking layer having a thickness of 100 Å to form a hole transport region.
The first compound, the second compound, and the emitter (a weight ratio of the first compound:the second compound:the emitter was 57:30:13) described in Table 3 or the first compound, the second compound, the sensitizer, and the emitter (a weight ratio of the first compound:the second compound:the sensitizer:the emitter was 56:30.2:13:0.8) described in Table 4 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, and Compound ET27 and LiQ were co-deposited on the hole blocking layer to form an electron transport layer having a thickness of 300 Å, and LiQ was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and an Al second electrode (cathode) having a thickness of 1,200 Å was formed on the electron injection layer, thereby completing the manufacture of an organic light-emitting device.
T95 lifespan characteristics of the organic light-emitting devices manufactured in Examples 1 to 5 and 11 to 15 and Comparative Examples 1 to 3 and 11 were measured (at 1,000 nit), wherein T95 is a time taken for initial luminance to reduce to 95%, and results thereof were converted into relative values (%) and are shown in Tables 3 and 4.
From Table 3, it was found that the organic light-emitting devices of Examples 1 to 5 had better lifespan characteristics than those of the organic light-emitting devices of Comparative Examples 1 to 3.
In addition, from Table 4, it was found that the organic light-emitting devices of Examples 11 to 15 had better lifespan characteristics than those of the organic light-emitting device of Comparative Example 1.
Since a light-emitting device including the composition has excellent lifespan characteristics, a high-quality electronic apparatus may be manufactured by using the light-emitting device.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0055749 | May 2022 | KR | national |
| 10-2023-0046327 | Apr 2023 | KR | national |
| 10-2023-0057362 | May 2023 | KR | national |
