LIGHT-EMITTING DEVICE INCLUDING ORGANOMETALLIC COMPOUND, ELECTRONIC APPARATUS INCLUDING THE LIGHT-EMITTING DEVICE, AND THE ORGANOMETALLIC COMPOUND

A light-emitting device including an organometallic compound represented by Formula 1, an electronic apparatus including the light-emitting device, and the organometallic compound represented by Formula 1 are provided.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to and the benefit of Korean Patent Application No. 10-2022-0003628, filed on Jan. 10, 2022, in the Korean Intellectual Property Office, the entire content of which is hereby incorporated by reference.

BACKGROUND

Aspects of one or more embodiments of the present disclosure relate to a light-emitting device including an organometallic compound, an electronic apparatus including the light-emitting device, and the organometallic compound.

2. Description of the Related Art

Self-emissive devices among light-emitting devices have relatively wide viewing angles, high contrast ratios, short response times, and excellent or suitable characteristics in terms of luminance, driving voltage, and response speed.

SUMMARY

Aspects of one or more embodiments of the present disclosure are directed toward a light-emitting device including an organometallic compound, an electronic apparatus including the light-emitting device, and the organometallic compound.

According to one or more embodiments,

provided is a light-emitting device including a first electrode,

a second electrode facing the first electrode,

an interlayer between the first electrode and the second electrode and including an emission layer, and

an organometallic compound represented by Formula 1.

In Formula 1,

rings CY11, CY12, CY2, CY3, and CY4may each independently be a C5-C60carbocyclic group or a C1-C60heterocyclic group,

Y1, Y2, Y3, Y4, X11, and X12may each independently be selected from a carbon atom (C) and a nitrogen atom (N),

Y1and X12may directly be linked to each other via a chemical bond,

X11and X12may directly be linked to each other via a chemical bond,

X12may be a bridgehead atom,

B1to B4may each independently be a single bond, an oxygen atom (O), a sulfur atom (S), N(R11a), or C(R11a)(R12a),

R13and R14may be optionally linked to each other to form a C5-C60carbocyclic group that is unsubstituted or substituted with R10aor a C1-C60heterocyclic group that is unsubstituted or substituted with R10a,

a1 and a2 may each independently be an integer from 0 to 3,

when a1 is 0, a group represented by *-(L1)a1-*′ may be a single bond,

when a2 is 0, a group represented by *-(L2)a2-*′ may be a single bond,

b11, b12, b2, b3, and b4 may each independently be an integer from 0 to 8, and

* and *′ may each indicate a binding site to a neighboring atom.

According to one or more embodiments, provided is an electronic apparatus including the light-emitting device.

According to one or more embodiments, provided is the organometallic compound represented by Formula 1.

DETAILED DESCRIPTION

In an embodiment,

provided is a light-emitting device including: a first electrode;

a second electrode facing the first electrode;

an interlayer between the first electrode and the second electrode and including an emission layer; and

an organometallic compound represented by Formula 1.

In Formula 1,

rings CY11, CY12, CY2, CY3, and CY4may each independently be a C5-C60carbocyclic group or a C1-C60heterocyclic group,

Y1, Y2, Y3, Y4, X11, and X12may each independently be selected from a carbon atom (C) and a nitrogen atom (N),

Y1and X12may directly be linked to each other via a chemical bond,

X11and X12may directly be linked to each other via a chemical bond,

X12may be a bridgehead atom,

B1to B4may each independently be a single bond, an oxygen atom (O), a sulfur atom (S), N(R11a), or C(R11a)(R12a),

R13and R14may be optionally linked to each other to form a C5-C60carbocyclic group that is unsubstituted or substituted with R10aor a C1-C60heterocyclic group that is unsubstituted or substituted with R10a,

a1 and a2 may each independently be an integer from 0 to 3,

when a1 is 0, a group represented by *-(L1)a1-*′ may be a single bond,

when a2 is 0, a group represented by *-(L2)a2-*′ may be a single bond,

b11, b12, b2, b3, and b4 may each independently be an integer from 0 to 8, and

* and *′ may each indicate a binding site to a neighboring atom.

In the light-emitting device according to an embodiment, the interlayer may include the organometallic compound represented by Formula 1.

In the light-emitting device according to an embodiment, the emission layer may include the organometallic compound represented by Formula 1.

In the light-emitting device according to an embodiment, the percentage of the metal-to-ligand charge-transfer triplet state (3MLCT) of the organometallic compound may be greater than or equal to about 15%.

In the light-emitting device according to an embodiment,

the emission layer may further include a second compound and a third compound,

the second compound is a hole transporting host, and

the third compound is an electron transporting host.

In the light-emitting device according to an embodiment,

the second compound may include at least one π electron-rich C3-C60cyclic group, and for example, the π electron-rich C3-C60cyclic group may include at least one selected from a carbazole group, a dibenzofuran group, and a fluorene group.

The third compound may include at least one π electron-deficient nitrogen-containing C1-C60cyclic group, and for example, the π electron-deficient nitrogen-containing C1-C60cyclic group may include at least one selected from a pyridine group, a pyrimidine group, and a triazine group.

In the light-emitting device according to an embodiment, the organometallic compound, the second compound, and the third compound may be different from one another.

Also, in the light-emitting device according to an embodiment, the second compound and the third compound may form an exciplex, and the organometallic compound, the second compound, and/or the third compound may not form an exciplex.

In the light-emitting device according to an embodiment, the second compound may be at least one of compounds represented by Formulae HTH1 to HTH52.

In the light-emitting device according to an embodiment, the third compound may be at least one of compounds represented by Formulae ETH1 to ETH82.

In the light-emitting device according to an embodiment, a ratio of an amount of the second compound may be greater than or equal to a ratio of an amount of the third compound, with respect to a total weight of the emission layer.

A ratio of an amount of the second compound to an amount of the third compound may be in a range of about 7:3 to about 6:4.

In the light-emitting device according to an embodiment, the emission layer may further include a fourth compound, and the fourth compound may emit delayed fluorescence.

In the light-emitting device according to an embodiment, the second compound, the third compound, and the fourth compound may be different from one another.

In the light-emitting device according to an embodiment, the emission layer may emit blue light, and the blue light may emit light having a maximum emission wavelength of about 400 nm to about 500 nm.

In the light-emitting device according to an embodiment,

the first electrode may be an anode,

the second electrode may be a cathode,

the interlayer may further include a hole transport region between the first electrode and the emission layer and an electron transport region between the emission layer and the second electrode,

the electron transport region may include a hole blocking layer, an electron transport layer, an electron injection layer, or one or more combinations thereof.

The light-emitting device according to an embodiment may further include

a first capping layer or a second capping layer,

the first capping layer may be on one surface of the first electrode, and

the second capping layer may be on one surface of the second electrode.

In the light-emitting device according to an embodiment, at least one of the first capping layer or the second capping layer may include the organometallic compound represented by Formula 1.

According to one or more embodiments of the disclosure, provided is an electronic apparatus including the light-emitting device according to one of embodiments.

The electronic apparatus according to an embodiment may further include

wherein the thin-film transistor may include a source electrode and a drain electrode, and

the first electrode of the light-emitting device may be electrically connected to the source electrode or the drain electrode of the thin-film transistor.

The electronic apparatus according to an embodiment may further include

a color filter, a quantum dot color conversion layer, a touch screen layer, a polarizing layer, or one or more combinations thereof.

According to one or more embodiments of the disclosure,

provided is an organometallic compound represented by Formula 1.

In Formula 1,

rings CY11, CY12, CY2, CY3, and CY4may each independently be a C5-C60carbocyclic group or a C1-C60heterocyclic group,

Y1, Y2, Y3, Y4, X11, and X12may each independently be selected from a carbon atom (C) and a nitrogen atom (N),

Y1and X12may directly be linked to each other via a chemical bond,

X11and X12may directly be linked to each other via a chemical bond,

X12may be a bridgehead atom,

B1to B4may each independently be a single bond, an oxygen atom (O), a sulfur atom (S), N(R11a), or C(R11a)(R12a),

R13and R14may be optionally linked to each other to form a C5-C60carbocyclic group that is unsubstituted or substituted with R10aor a C1-C60heterocyclic group that is unsubstituted or substituted with R10a,

a1 and a2 may each independently be an integer from 0 to 3,

when a1 is 0, a group represented by *-(L1)a1-*′ may be a single bond,

when a2 is 0, a group represented by *-(L2)a2-*′ may be a single bond,

b11, b12, b2, b3, and b4 may each independently be an integer from 0 to 8, and

* and *′ may each indicate a binding site to a neighboring atom.

In the organometallic compound according to an embodiment, ring CY3and ring CY4may be the same group.

In the organometallic compound according to an embodiment, ring CY3and ring CY4may be different groups.

In the organometallic compound according to an embodiment, ring CY3and CY4may each independently be a benzene group, a pyridine group, a pyridazine group, a pyrimidine group, a pyrazine group, a triazine group, a cyclopentadiene group, a pyrrole group, a pyrazole group, an imidazole group, or a triazole group.

In formula 1, a moiety represented by

may be a moiety represented by

In formula 1, a moiety represented by

may be a moiety represented by

In the organometallic compound according to an embodiment,

in Formula 1, a moiety represented by

or a moiety represented by

may each independently be one of groups represented by Formulae 1-2-1 to 1-2-35.

In Formulae 1-2-1 to 1-2-35,

In the organometallic compound according to an embodiment,

In the organometallic compound according to an embodiment,

in Formula 1, a moiety represented by

may be a group represented by Formula 1-1.

In Formula 1-1,

rings CY21and CY22may each independently be a C5-C60carbocyclic group or a C1-C60heterocyclic group,

X21and X22may each independently be selected from a carbon atom (C) and a nitrogen atom (N),

Y2and X22may directly be linked to each other via a chemical bond,

X21and X22may directly be linked to each other via a chemical bond,

X22may be a bridgehead atom,

* indicates a binding site to L2,

*′ indicates a binding site to Z1,

R21and R22are respectively the same as described in connection with R2in Formula 1, and

b21 and b22 are respectively the same as described in connection with b2 in Formula 1.

In the organometallic compound according to an embodiment,

ring CY11and ring CY21may be the same group.

In the organometallic compound according to an embodiment, ring CY11and ring CY21may be different groups.

In the organometallic compound according to an embodiment, ring CY12and ring CY22may be the same group.

In the organometallic compound according to an embodiment, ring CY12and ring CY22may be different groups.

In the organometallic compound according to an embodiment,

In the organometallic compound according to an embodiment,

a moiety represented by

in Formula 1 or a moiety represented by

in Formula 1-1 may each independently be one of groups represented by Formulae 1-1-1 to 1-1-12.

In Formulae 1-1-1 to 1-1-12,

In the organometallic compound according to an embodiment,

two of Y1to Y4may each be a nitrogen atom (N) and may satisfy one of conditions of 1) to 4).

In the organometallic compound according to an embodiment,

a1 and a2 may each be 0, and

B1to B4may each be a single bond.

In the organometallic compound according to an embodiment,

Z1may be C(R11)(R12), and

C(R11)(R12) may be C(CH3)2or a group represented by 1-3-1.

In Formula 1-3-1,

In the organometallic compound according to an embodiment,

In the organometallic compound according to an embodiment,

The organometallic compound according to an embodiment may be represented by Formulae BD1 to BD105.

The organometallic compound represented by Formula 1 includes metal nuclei and a tetradentate ligand, and the tetradentate ligand includes at least one fused bicyclic compound. Also, the fused bicyclic compound may be a group in which one non-aromatic ring and one aromatic ring are condensed with each other.

The organometallic compound has a structure in which a ligand of a tetracoordinate organometallic compound is fixed with an additional linking group, and thus the formation of an exciplex with an organic compound is suppressed or reduced, and as a result, color purity and luminescence efficiency of the organometallic compound may be improved (increased).

Also, a highest occupied molecular orbital (HOMO) energy level of the organometallic compound may be determined by the fused bicyclic compound. Accordingly, by diversifying the fused bicyclic compound, energy levels of HOMO, lowest unoccupied molecular orbital (LUMO), T1, S1, and/or the like of the organometallic compound may be finely adjusted, and versatility may increase.

Furthermore, due to the non-aromatic ring included in the fused bicyclic compound, structural instability such as steric hindrance occurring between aromatic rings or steric hindrance between metal-ligand bonding sites and/or the like can be resolved (reduced). In an organometallic compound according to an embodiment, a metal nucleus may bond with a tetradentate ligand to form at least one 6-membered ring and up to three 6-membered rings.

Accordingly, the organometallic compound according to an embodiment may provide improved planarity, and may have an easier-to-laminate structure. Furthermore, the horizontal orientation and efficiency characteristics may be improved.

As a result, an electronic device, for example an organometallic compound, including the organometallic compound according to an embodiment may have a low driving voltage, a high efficiency, and a long lifespan.

Methods of synthesizing the organometallic compound represented by Formula 1 may be understood by those of ordinary skill in the art by referring to Synthesis Examples and Examples described herein.

At least one organometallic compound represented by Formula 1 may be utilized in a light-emitting device (for example, an organic light-emitting device). Thus, provided is a light-emitting device including: a first electrode; a second electrode facing the first electrode; an interlayer between the first electrode and the second electrode and including an emission layer; and the organometallic compound represented by Formula 1 as described in the present disclosure.

In an embodiment,

the first electrode of the light-emitting device may be an anode,

the second electrode of the light-emitting device may be a cathode,

the interlayer may further include a hole transport region between the first electrode and the emission layer and an electron transport region between the emission layer and the second electrode,

the electron transport region may include a buffer layer, a hole blocking layer, an electron control layer, an electron transport layer, an electron injection layer, or one or more combinations thereof.

In an embodiment, the organometallic compound may be included between the first electrode and the second electrode of the light-emitting device. Therefore, the organometallic compound may be included in the interlayer of the light-emitting device, for example, the emission layer of the interlayer.

In an embodiment, the emission layer in the interlayer of the light-emitting device may include a dopant and a host, and the host may include the organometallic compound. For example, the organometallic compound may act as a host. The emission layer may emit red light, green light, blue light, and/or white light. In an embodiment, the emission layer may emit blue light. The blue light may have a maximum emission wavelength of, for example, about 400 nm to about 490 nm.

In an embodiment, the emission layer in the interlayer of the light-emitting device may include a dopant and a host, the host may include the organometallic compound, and the dopant may emit blue light. In an embodiment, the dopant may include a transition metal and ligand(s) in the number of m, m may be an integer from 1 to 6, the ligand(s) in the number of m may be identical to or different from each other, at least one of the ligand(s) in the number of m may be bound to the transition metal via a carbon-transition metal bond, and the carbon-transition metal bond may be a coordinate bond. For example, at least one of the ligand(s) in the number of m may be a carbene ligand (e.g., Ir(pmp)3and/or the like). The transition metal may be, for example, iridium, platinum, osmium, palladium, rhodium, and/or gold. The emission layer and the dopant may be the same as described in the present disclosure.

In an embodiment, the light-emitting device may include a capping layer located outside the first electrode or located outside the second electrode.

In an embodiment, the light-emitting device may further include at least one of a first capping layer outside the first electrode or a second capping layer outside the second electrode, and the at least one of the first capping layer or the second capping layer may include the organometallic compound represented by Formula 1. More details for the first capping layer and/or second capping layer may each independently be the same as described in the present disclosure.

In an embodiment, the light-emitting device may include:

a first capping layer outside the first electrode and including the organometallic compound represented by Formula 1;

a second capping layer outside the second electrode and including the organometallic compound represented by Formula 1; or

the first capping layer and the second capping layer.

The wording “(interlayer and/or capping layer) includes an organometallic compound” as utilized herein may be to refer to that the (interlayer and/or capping layer) may include one kind of organometallic compound represented by Formula 1 or two or more different kinds of organometallic compounds, each represented by Formula 1″.

In an embodiment, the interlayer and/or capping layer may include Compound 1 only as the organometallic compound. In this regard, Compound 1 may be present in the emission layer of the light-emitting device. In an embodiment, the interlayer may include, as the organometallic compound, Compound 1 and Compound 2. In this regard, Compound 1 and Compound 2 may be present in substantially the same layer (for example, all of Compound 1 and Compound 2 may be present in the emission layer), or may be present in different layers (for example, Compound 1 may be present in the emission layer, and Compound 2 may be present in the electron transport region).

The term “interlayer” as utilized herein refers to a single layer and/or all of a plurality of layers located between the first electrode and the second electrode of the light-emitting device.

According to one or more embodiments, provided is an electronic apparatus including the light-emitting device. The electronic apparatus may further include a thin-film transistor. In an embodiment, the electronic apparatus may further include a thin-film transistor including a source electrode and a drain electrode, wherein the first electrode of the light-emitting device may be electrically connected to the source electrode or the drain electrode. In an embodiment, the electronic apparatus may further include a color filter, a color conversion layer, a touch screen layer, a polarizing layer, or one or more combinations thereof. More details for the electronic apparatus are as described in the present disclosure.

Description of FIG.1

FIG.1is a schematic cross-sectional view of a light-emitting device10according to an embodiment of the disclosure. The light-emitting device10includes a first electrode110, an interlayer130, and a second electrode150.

Hereinafter, a structure of the light-emitting device10according to an embodiment and a method of manufacturing the light-emitting device10will be described in connection withFIG.1.

First Electrode110

InFIG.1, a substrate may be additionally located under the first electrode110or above the second electrode150. As the substrate, a glass substrate and/or a plastic substrate may be utilized. In an embodiment, the substrate may be a flexible substrate, and may include plastics with excellent or suitable heat resistance and durability, such as polyimide, polyethylene terephthalate (PET), polycarbonate, polyethylene napthalate, polyarylate (PAR), polyetherimide, or one or more combinations thereof.

The first electrode110may be formed by, for example, depositing or sputtering a material for forming the first electrode110on the substrate. When the first electrode110is an anode, a material for forming the first electrode110may be a high work function material that facilitates injection of holes.

The first electrode110may have a single-layered structure including (e.g., consisting of) a single layer or a multilayer structure including a plurality of layers. In an embodiment, the first electrode110may have a three-layered structure of ITO/Ag/ITO.

The interlayer130may be on the first electrode110. The interlayer130may include an emission layer.

The interlayer130may further include a hole transport region between the first electrode110and the emission layer and an electron transport region between the emission layer and the second electrode150.

The interlayer130may further include metal-containing compounds such as organometallic compounds, inorganic materials such as quantum dots, and/or the like, in addition to one or more suitable organic materials.

In an embodiment, the interlayer130may include, i) two or more emitting units sequentially stacked between the first electrode110and the second electrode150, and ii) a charge generation layer between the two emitting units. When the interlayer130includes emitting units and a charge generation layer as described above, the light-emitting device10may be a tandem light-emitting device.

Hole Transport Region in Interlayer130

For example, the hole transport region may have a multi-layered structure including a hole injection layer/hole transport layer structure, a hole injection layer/hole transport layer/emission auxiliary layer structure, a hole injection layer/emission auxiliary layer structure, a hole transport layer/emission auxiliary layer structure, or a hole injection layer/hole transport layer/electron blocking layer structure, the layers of each structure being stacked sequentially from the first electrode110.

The hole transport region may include a compound represented by Formula 201, a compound represented by Formula 202, or a combination thereof:

L201to L204may each independently be a C3-C60carbocyclic group that is unsubstituted or substituted with at least one R10aor a C1-C60heterocyclic group that is unsubstituted or substituted with at least one R10a,

L205may be *—O—*′, *—S—*′, *—N(Q201)-*′, a C1-C20alkylene group that is unsubstituted or substituted with at least one R10a, a C2-C20alkenylene group that is unsubstituted or substituted with at least one R10a, a C3-C60carbocyclic group that is unsubstituted or substituted with at least one R10a, or a C1-C60heterocyclic group that is unsubstituted or substituted with at least one R10a,

xa5 may be an integer from 1 to 10,

R201to R204and Q201may each independently be a C3-C60carbocyclic group that is unsubstituted or substituted with at least one R10a, or a C1-C60heterocyclic group that is unsubstituted or substituted with at least one R10a,

R201and R202may optionally be linked to each other via a single bond, a C1-C5alkylene group that is unsubstituted or substituted with at least one R10a, or a C2-C5alkenylene group that is unsubstituted or substituted with at least one R10ato form a C8-C60polycyclic group (for example, a carbazole group and/or the like) unsubstituted or substituted with at least one R10a(for example, Compound HT16),

R203and R204may optionally be linked to each other via a single bond, a C1-C5alkylene group that is unsubstituted or substituted with at least one R10a, or a C2-C5alkenylene group that is unsubstituted or substituted with at least one R10ato form a C8-C60polycyclic group that is unsubstituted or substituted with at least one R10a, and

na1 may be an integer from 1 to 4.

In an embodiment, each of Formulae 201 and 202 may include at least one of groups represented by Formulae CY201 to CY217.

In an embodiment, ring CY201to ring CY204in Formulae CY201 to CY217 may each independently be a benzene group, a naphthalene group, a phenanthrene group, or an anthracene group.

In an embodiment, each of Formulae 201 and 202 may include at least one of groups represented by Formulae CY201 to CY203.

In an embodiment, Formula 201 may include at least one of groups represented by Formulae CY201 to CY203 and at least one of groups represented by Formulae CY204 to CY217.

In an embodiment, xa1 in Formula 201 may be 1, R201may be a group represented by one of Formulae CY201 to CY203, xa2 may be 0, and R202may be a group represented by one of Formulae CY204 to CY207.

In an embodiment, each of Formulae 201 and 202 may not include (e.g., may exclude) groups represented by Formulae CY201 to CY203.

In an embodiment, each of Formulae 201 and 202 may not include (e.g., may exclude) groups represented by Formulae CY201 to CY203, and may include at least one of groups represented by Formulae CY204 to CY217.

In an embodiment, each of Formulae 201 and 202 may not include (e.g., may exclude) groups represented by Formulae CY201 to CY217.

The emission auxiliary layer may increase light-emission efficiency by compensating for an optical resonance distance according to the wavelength of light emitted by an emission layer, and the electron blocking layer may block or reduce the leakage of electrons from an emission layer to a hole transport region. Materials that may be included in the hole transport region may also be included in the emission auxiliary layer and the electron blocking layer.

The hole transport region may further include, in addition to these materials, a charge-generation material for the improvement of conductive properties. The charge-generation material may be substantially uniformly or non-uniformly dispersed in the hole transport region (for example, in the form of a single layer including (e.g., consisting of) a charge-generation material).

In an embodiment, a LUMO energy level of the p-dopant may be about −3.5 eV or less.

In an embodiment, the p-dopant may include a quinone derivative, a cyano group-containing compound, a compound containing an element EL1 and an element EL2, or one or more combinations thereof.

Examples of the quinone derivative may include TCNQ, F4-TCNQ, and/or the like.

Examples of the cyano group-containing compound may include HAT-CN, a compound represented by Formula 221, and/or the like.

In Formula 221,

R221to R223may each independently be a C3-C60carbocyclic group that is unsubstituted or substituted with at least one R10aor a C1-C60heterocyclic group that is unsubstituted or substituted with at least one R10a, and

at least one of R221to R223may each independently be a C3-C60carbocyclic group or a C1-C60heterocyclic group, each substituted with: a cyano group; —F; —Cl; —Br; —I; a C1-C20alkyl group substituted with a cyano group, —F, —Cl, —Br, —I, or one or more combinations thereof.

In the compound containing the element EL1 and the element EL2, the element EL1 may be metal, metalloid, or a combination thereof, and the element EL2 may be non-metal, metalloid, or a combination thereof.

Examples of the metalloid may include silicon (Si), antimony (Sb), and/or tellurium (Te).

In an embodiment, examples of the compound containing the element EL1 and the element EL2 may include metal oxide, metal halide (for example, metal fluoride, metal chloride, metal bromide, or metal iodide), metalloid halide (for example, metalloid fluoride, metalloid chloride, metalloid bromide, or metalloid iodide), metal telluride, or one or more combinations thereof.

Examples of the metal halide may include alkali metal halide, alkaline earth metal halide, transition metal halide, post-transition metal halide, and/or lanthanide metal halide.

Examples of the metalloid halide may include antimony halide (for example, SbCl5, etc.).

Emission Layer in Interlayer130

The emission layer may include a host and a dopant. The dopant may include a phosphorescent dopant, a fluorescent dopant, or a combination thereof.

An amount of the dopant in the emission layer may be from about 0.01 parts by weight to about 15 parts by weight based on 100 parts by weight of the host.

In an embodiment, the emission layer may include a quantum dot.

In an embodiment, the emission layer may include a delayed fluorescence material. The delayed fluorescence material may act as a host or a dopant in the emission layer.

The host may include a compound represented by Formula 301:

Ar301and L301may each independently be a C3-C60carbocyclic group that is unsubstituted or substituted with at least one R10aor a C1-C60heterocyclic group that is unsubstituted or substituted with at least one R10a,

xb1 may be an integer from 0 to 5,

R301may be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C60alkyl group that is unsubstituted or substituted with at least one R10a, a C2-C60alkenyl group that is unsubstituted or substituted with at least one R10a, a C2-C60alkynyl group that is unsubstituted or substituted with at least one R10a, a C1-C60alkoxy group that is unsubstituted or substituted with at least one R10a, a C3-C60carbocyclic group that is unsubstituted or substituted with at least one R10a, a C1-C60heterocyclic group that is unsubstituted or substituted with at least one R10a, —Si(Q301)(Q302)(Q303), —N(Q301)(Q302), —B(Q301)(Q302), —C(═O)(Q301), —S(═O)2(Q301), or —P(═O)(Q301)(Q302),

xb21 may be an integer from 1 to 5, and

Q301to Q303are respectively the same as described in connection with Q1.

In an embodiment, when xb11 in Formula 301 is 2 or more, two or more of Ar301(s) may be linked to each other via a single bond.

In an embodiment, the host may include a compound represented by Formula 301-1, a compound represented by Formula 301-2, or a combination thereof:

ring A301to ring A304may each independently be a C3-C60carbocyclic group that is unsubstituted or substituted with at least one R10aor a C1-C60heterocyclic group that is unsubstituted or substituted with at least one R10a,

xb22 and xb23 may each independently be 0, 1, or 2,

L301, xb1, and R301are respectively the same as described in the present disclosure,

L302to L304may each independently be the same as described in connection with L301,

xb2 to xb4 may each independently be the same as described in connection with xb1, and

R302to R305and R311to R314are respectively the same as described in connection with R301.

In an embodiment, the host may include an alkali earth metal complex, a post-transition metal complex, or a combination thereof. In an embodiment, the host may include a Be complex (for example, Compound H55), an Mg complex, a Zn complex, or one or more combinations thereof.

The phosphorescent dopant may include at least one transition metal as a central metal.

The phosphorescent dopant may be electrically neutral.

In an embodiment, the phosphorescent dopant may include an organometallic compound represented by Formula 401:

L401may be a ligand represented by Formula 402, and xc1 may be 1, 2, or 3, wherein, when xc1 is two or more, two or more of L401(s) may be identical to or different from each other,

L402may be an organic ligand, and xc2 may be 0, 1, 2, 3, or 4, wherein, when xc2 is 2 or more, two or more of L402(s) may be identical to or different from each other,

X401and X402may each independently be nitrogen or carbon,

ring A401and ring A402may each independently be a C3-C60carbocyclic group or a C1-C60heterocyclic group,

Q411to Q414are respectively the same as described in connection with Q1,

R401and R402may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C20alkyl group that is unsubstituted or substituted with at least one R10a, a C1-C20alkoxy group that is unsubstituted or substituted with at least one R10a, a C3-C60carbocyclic group that is unsubstituted or substituted with at least one R10a, a C1-C60heterocyclic group that is unsubstituted or substituted with at least one R10a, —Si(Q401)(Q402)(Q403), —N(Q401)(Q402), —B(Q401)(Q402), —C(═O)(Q401), —S(═O)2(Q401), or —P(═O)(Q401)(Q402),

Q401to Q403are respectively the same as described in connection with Q1,

In an embodiment, in Formula 402, i) X401may be nitrogen, and X402may be carbon, or ii) each of X401and X402may be nitrogen.

In an embodiment, when xc1 in Formula 402 is 2 or more, two ring A401in two or more of L401(s) may be optionally linked to each other via T402, which is a linking group, and two ring A402may optionally be linked to each other via T403, which is a linking group (see Compounds PD1 to PD4 and PD7). T402and T403are respectively the same as described in connection with T401.

L402in Formula 401 may be an organic ligand. In an embodiment, L402may include a halogen group, a diketone group (for example, an acetylacetonate group), a carboxylic acid group (for example, a picolinate group), —C(═O), an isonitrile group, —CN group, a phosphorus group (for example, a phosphine group, a phosphite group, etc.), or one or more combinations thereof.

The phosphorescent dopant may include, for example, at least one of compounds PD1 to PD39, or one or more combinations thereof:

Fluorescent Dopant

The fluorescent dopant may include an amine group-containing compound, a styryl group-containing compound, or a combination thereof.

In an embodiment, the fluorescent dopant may include a compound represented by Formula 501:

Ar501, L501to L503, R501, and R502may each independently be a C3-C60carbocyclic group that is unsubstituted or substituted with at least one R10aor a C1-C60heterocyclic group that is unsubstituted or substituted with at least one R10a,

xd1 to xd3 may each independently be 0, 1, 2, or 3, and

In an embodiment, Ar501in Formula 501 may be a condensed cyclic group (for example, an anthracene group, a chrysene group, or a pyrene group) in which three or more monocyclic groups are condensed together.

In an embodiment, xd4 in Formula 501 may be 2.

In an embodiment, the fluorescent dopant may include: at least one of Compounds FD1 to FD36; DPVBi; DPAVBi; or one or more combinations thereof:

Delayed Fluorescence Material

The emission layer may include a delayed fluorescence material.

In the present disclosure, the delayed fluorescence material may be selected from compounds capable of emitting delayed fluorescence based on a delayed fluorescence emission mechanism.

The delayed fluorescence material included in the emission layer may act as a host or a dopant depending on the type or kind of other materials included in the emission layer.

In an embodiment, the difference between the triplet energy level (eV) of the delayed fluorescence material and the singlet energy level (eV) of the delayed fluorescence material may be greater than or equal to 0 eV and less than or equal to 0.5 eV. When the difference between the triplet energy level (eV) of the delayed fluorescence material and the singlet energy level (eV) of the delayed fluorescence material satisfies the above-described range, up-conversion from the triplet state to the singlet state of the delayed fluorescence materials may effectively occur, and thus, the luminescence efficiency of the light-emitting device10may be improved (increased).

In an embodiment, the delayed fluorescence material may include i) a material including at least one electron donor (for example, a π electron-rich C3-C60cyclic group, such as a carbazole group) and at least one electron acceptor (for example, a sulfoxide group, a cyano group, or a π electron-deficient nitrogen-containing C1-C60cyclic group), and ii) a material including a C8-C60polycyclic group in which two or more cyclic groups are condensed while sharing boron (B).

Examples of the delayed fluorescence material may include at least one of the following Compounds DF1 to DF9:

Quantum Dot

The emission layer may include a quantum dot.

In the present disclosure, a quantum dot refers to a crystal of a semiconductor compound, and may include any suitable material capable of emitting light of one or more suitable emission wavelengths according to the size of the crystal.

The quantum dot may be synthesized by a wet chemical process, a metal organic chemical vapor deposition process, a molecular beam epitaxy process, or any suitable process similar thereto.

According to the wet chemical process, a precursor material is mixed with an organic solvent to grow a quantum dot particle crystal. When the crystal grows, the organic solvent naturally acts as a dispersant coordinated on the surface of the quantum dot crystal and controls the growth of the crystal so that the growth of quantum dot particles may be controlled or selected through a process which is more easily performed than vapor deposition methods, such as metal organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE), and which requires lower costs.

The quantum dot may include: a Group II-VI semiconductor compound; a Group III-V semiconductor compound; a Group III-VI semiconductor compound; a Group I-III-VI semiconductor compound; a Group IV-VI semiconductor compound; a Group IV element or compound; or one or more combinations thereof.

Examples of the Group III-VI semiconductor compound may include: a binary compound, such as GaS, GaSe, Ga2Se3, GaTe, InS, InSe, In2S3, In2Se3, or InTe; a ternary compound, such as InGaS3, or InGaSe3; or one or more combinations thereof.

Examples of the Group I-III-VI semiconductor compound may include: a ternary compound, such as AgInS, AgInS2, CuInS, CuInS2, CuGaO2, AgGaO2, or AgAlO2; or one or more combinations thereof.

The Group IV element or compound may include: a single element compound, such as Si or Ge; a binary compound, such as SiC or SiGe; or one or more combinations thereof.

Each element included in a multi-element compound such as the binary compound, ternary compound and quaternary compound, may exist in a particle with a substantially uniform concentration or non-uniform concentration.

In an embodiment, the quantum dot may have a single structure or a dual core-shell structure. In the case of the quantum dot having a single structure, the concentration of each element included in the corresponding quantum dot is substantially uniform. In an embodiment, the material contained in the core and the material contained in the shell may be different from each other.

The shell of the quantum dot may act as a protective layer to prevent or reduce chemical degeneration of the core to maintain semiconductor characteristics and/or as a charging layer to impart electrophoretic characteristics to the quantum dot. The shell may be a single layer or a multi-layer. The element presented in the interface between the core and the shell of the quantum dot may have a concentration gradient that decreases toward the center of the quantum dot.

Examples of the shell of the quantum dot may be an oxide of metal, metalloid, or non-metal, a semiconductor compound, and one or more combinations thereof. Examples of the oxide of metal, metalloid, or non-metal may include: a binary compound, such as SiO2, Al2O3, TiO2, ZnO, MnO, Mn2O3, Mn3O4, CuO, FeO, Fe2O3, Fe3O4, CoO, Co3O4, or NiO; a ternary compound, such as MgAl2O4, CoFe2O4, NiFe2O4, or CoMn2O4; or one or more combinations thereof. Examples of the semiconductor compound may include, as described herein, a Group II-VI semiconductor compound, a Group III-V semiconductor compound, a Group III-VI semiconductor compound, a Group I-III-VI semiconductor compound, a Group IV-VI semiconductor compound, or one or more combinations thereof. In some embodiments, the semiconductor compound may include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnSeS, ZnTeS, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InGaP, InSb, AlAs, AlP, AlSb, or one or more combinations thereof.

A full width at half maximum (FWHM) of an emission wavelength spectrum of the quantum dot may be about 45 nm or less, for example, about 40 nm or less, for example, about 30 nm or less, and within these ranges, color purity or color reproducibility may be increased. In some embodiments, because the light emitted through the quantum dot is emitted in all directions, the wide viewing angle can be improved (increased).

In some embodiments, the quantum dot may be a substantially spherical particle, a pyramidal particle, a multi-arm particle, a cubic nanoparticle, a nanotube particle, a nanowire particle, a nanofiber particle, or a nanoplate particle.

Because the energy band gap can be adjusted by controlling the size of the quantum dot, light having one or more suitable wavelength bands can be obtained from the quantum dot emission layer. Therefore, by utilizing quantum dots of different sizes, a light-emitting device that emits light of one or more suitable wavelengths may be implemented. In an embodiment, the size of the quantum dot may be selected to emit red, green and/or blue light. In some embodiments, the size of the quantum dot may be configured to emit white light by combining light of one or more suitable colors.

Electron Transport Region in Interlayer130

The electron transport region may include a buffer layer, a hole blocking layer, an electron control layer, an electron transport layer, an electron injection layer, or one or more combinations thereof.

For example, the electron transport region may have an electron transport layer/electron injection layer structure, a hole blocking layer/electron transport layer/electron injection layer structure, an electron control layer/electron transport layer/electron injection layer structure, or a buffer layer/electron transport layer/electron injection layer structure, the constituting layers of each structure being sequentially stacked from an emission layer.

In an embodiment, the electron transport region (for example, the buffer layer, the hole blocking layer, the electron control layer, or the electron transport layer in the electron transport region) may include a metal-free compound including at least one π electron-deficient nitrogen-containing C1-C60cyclic group.

Ar601and L601may each independently be a C3-C60carbocyclic group that is unsubstituted or substituted with at least one R10aor a C1-C60heterocyclic group that is unsubstituted or substituted with at least one R10a,

R601may be a C3-C60carbocyclic group that is unsubstituted or substituted with at least one R10a, a C1-C60heterocyclic group that is unsubstituted or substituted with at least one R10a, —Si(Q601)(Q602)(Q603), —C(═O)(Q601), —S(═O)2(Q601), or —P(═O)(Q601)(Q602),

Q601to Q603may each independently be the same as described in connection with Q1,

at least one of Ar601, L601, and R601may each independently be a π electron-deficient nitrogen-containing C1-C60cyclic group that is unsubstituted or substituted with at least one R10a.

In an embodiment, when xe11 in Formula 601 is 2 or more, two or more of Ar601(s) may be linked via a single bond.

In an embodiment, Ar601in Formula 601 may be a substituted or unsubstituted anthracene group.

X614may be N or C(R614), X615may be N or C(R615), X616may be N or C(R616), at least one of X614to X616may be N,

L611to L613are respectively the same as those described in connection with L601,

xe611 to xe613 are respectively the same as those described in connection with xe1,

R611to R613are respectively the same as those described in connection with R601, and

R614to R616may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, a C1-C20alkyl group, a C1-C20alkoxy group, a C3-C60carbocyclic group that is unsubstituted or substituted with at least one R10a, or a C1-C60heterocyclic group that is unsubstituted or substituted with at least one R10a.

The electron transport region may include an electron injection layer that facilitates the injection of electrons from the second electrode150. The electron injection layer may be in direct contact with the second electrode150.

The alkali metal may include Li, Na, K, Rb, Cs, or one or more combinations thereof. The alkaline earth metal may include Mg, Ca, Sr, Ba, or one or more combinations thereof. The rare earth metal may include Sc, Y, Ce, Tb, Yb, Gd, or one or more combinations thereof.

The alkali metal-containing compound, the alkaline earth metal-containing compound, and the rare earth metal-containing compound may include oxides, halides (for example, fluorides, chlorides, bromides, or iodides), or tellurides of the alkali metal, the alkaline earth metal, and the rare earth metal, or one or more combinations thereof.

The alkali metal complex, the alkaline earth-metal complex, and the rare earth metal complex may include i) one of ions of the alkali metal, the alkaline earth metal, and the rare earth metal and ii), as a ligand bonded to the metal ion, for example, a hydroxyquinoline, a hydroxyisoquinoline, a hydroxybenzoquinoline, a hydroxyacridine, a hydroxyphenanthridine, a hydroxyphenyloxazole, a hydroxyphenylthiazole, a hydroxyphenyloxadiazole, a hydroxyphenylthiadiazole, a hydroxyphenylpyridine, a hydroxyphenyl benzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or one or more combinations thereof.

The electron injection layer may include (e.g., consist of) an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal-containing compound, an alkaline earth metal-containing compound, a rare earth metal-containing compound, an alkali metal complex, an alkaline earth metal complex, a rare earth metal complex, or one or more combinations thereof, as described above. In an embodiment, the electron injection layer may further include an organic material (for example, a compound represented by Formula 601).

In an embodiment, the electron injection layer may include (e.g., consist of) i) an alkali metal-containing compound (for example, an alkali metal halide); or ii) a) an alkali metal-containing compound (for example, an alkali metal halide) and b) an alkali metal, an alkaline earth metal, a rare earth metal, or one or more combinations thereof. In an embodiment, the electron injection layer may be a KI:Yb co-deposited layer, an RbI:Yb co-deposited layer, and/or the like.

When the electron injection layer further includes an organic material, the alkali metal, the alkaline earth metal, the rare earth metal, the alkali metal-containing compound, the alkaline earth metal-containing compound, the rare earth metal-containing compound, the alkali metal complex, the alkaline earth-metal complex, the rare earth metal complex, or one or more combinations thereof may be substantially homogeneously or non-homogeneously dispersed in a matrix including (with) the organic material.

The second electrode150may be on the interlayer130having such a structure. The second electrode150may be a cathode, which is an electron injection electrode, and as the material for the second electrode150, a metal, an alloy, an electrically conductive compound, or one or more combinations thereof, each having a low work function, may be utilized.

The second electrode150may have a single-layered structure or a multi-layered structure including two or more layers.

Capping Layer

A first capping layer may be outside the first electrode110, and/or a second capping layer may be outside the second electrode150. In more detail, the light-emitting device10may have a structure in which the first capping layer, the first electrode110, the interlayer130, and the second electrode150are sequentially stacked in this stated order, a structure in which the first electrode110, the interlayer130, the second electrode150, and the second capping layer are sequentially stacked in this stated order, or a structure in which the first capping layer, the first electrode110, the interlayer130, the second electrode150, and the second capping layer are sequentially stacked in this stated order.

Light generated in an emission layer of the interlayer130of the light-emitting device10may be extracted toward the outside through the first electrode110, which is a semi-transmissive electrode or a transmissive electrode, and the first capping layer or light generated in an emission layer of the interlayer130of the light-emitting device10may be extracted toward the outside through the second electrode150, which is a semi-transmissive electrode or a transmissive electrode, and the second capping layer.

The first capping layer and the second capping layer may increase external emission efficiency according to the principle of constructive interference. Accordingly, the light extraction efficiency of the light-emitting device10is increased, so that the emission efficiency of the light-emitting device10may be improved.

Each of the first capping layer and second capping layer may include a material having a refractive index (at 589 nm) of 1.6 or more.

At least one of the first capping layer or the second capping layer may each independently include carbocyclic compounds, heterocyclic compounds, amine group-containing compounds, porphyrin derivatives, phthalocyanine derivatives, naphthalocyanine derivatives, alkali metal complexes, alkaline earth metal complexes, or one or more combinations thereof. The carbocyclic compound, the heterocyclic compound, and the amine group-containing compound may be optionally substituted with a substituent containing O, N, S, Se, Si, F, Cl, Br, I, or one or more combinations thereof. In an embodiment, at least one of the first capping layer or the second capping layer may each independently include an amine group-containing compound.

In an embodiment, at least one of the first capping layer or the second capping layer may each independently include at least one of Compounds HT28 to HT33, at least one of Compounds CP1 to CP6, β-NPB, or one or more combinations thereof:

The organometallic compound represented by Formula 1 may be included in one or more suitable films. According to an embodiment, a film including an organometallic compound represented by Formula 1 may be provided. The film may be, for example, an optical member (or a light control member) (for example, a color filter, a color conversion member, a capping layer, a light extraction efficiency enhancement layer, a selective light absorbing layer, a polarizing layer, a quantum dot-containing layer, and/or the like), a light-blocking member (for example, a light reflective layer, a light absorbing layer, and/or the like), and/or a protective member (for example, an insulating layer, a dielectric layer, and/or the like).

Electronic Apparatus

The light-emitting device may be included in one or more suitable electronic apparatuses. In an embodiment, the electronic apparatus including the light-emitting device may be a light-emitting apparatus, an authentication apparatus, and/or the like.

The electronic apparatus (for example, light-emitting apparatus) may further include, in addition to the light-emitting device, i) a color filter, ii) a quantum dot color conversion layer, or iii) a color filter and a quantum dot color conversion layer. The color filter and/or the quantum dot color conversion layer may be located in at least one traveling direction of light emitted from the light-emitting device. For example, the light emitted from the light-emitting device may be blue light or white light. The light-emitting device may be the same as described above. In an embodiment, the quantum dot color conversion layer may include quantum dots. The quantum dot may be, for example, a quantum dot as described herein.

The electronic apparatus may include a first substrate. The first substrate may include a plurality of subpixel areas, the color filter may include a plurality of color filter areas respectively corresponding to the subpixel areas, and the quantum dot color conversion layer may include a plurality of color conversion areas respectively corresponding to the subpixel areas.

A pixel-defining layer may be located or arranged among the subpixel areas to define each of the subpixel areas.

The color filter may further include a plurality of color filter areas and light-shielding patterns located among the color filter areas, and the quantum dot color conversion layer may include a plurality of color conversion areas and light-shielding patterns located among the color conversion areas.

The color filter areas (or the color conversion areas) may include a first area emitting first color light, a second area emitting second color light, and/or a third area emitting third color light, and the first color light, the second color light, and/or the third color light may have different maximum emission wavelengths from one another. In an embodiment, the first color light may be red light, the second color light may be green light, and the third color light may be blue light. In an embodiment, the color filter areas (or the color conversion areas) may include quantum dots. In more detail, the first area may include a red quantum dot, the second area may include a green quantum dot, and the third area may not include (e.g., may exclude) a quantum dot. The quantum dot is substantially the same as described in the present disclosure. The first area, the second area, and/or the third area may each further include a scatterer.

In an embodiment, the light-emitting device may emit first light, the first area may absorb the first light to emit first first-color light, the second area may absorb the first light to emit second first-color light, and the third area may absorb the first light to emit third first-color light. In this regard, the first first-color light, the second first-color light, and the third first-color light may have different maximum emission wavelengths. In more detail, the first light may be blue light, the first first-color light may be red light, the second first-color light may be green light, and the third first-color light may be blue light.

The thin-film transistor may further include a gate electrode, a gate insulating film, etc.

The activation layer may include crystalline silicon, amorphous silicon, organic semiconductor, oxide semiconductor, and/or the like.

The authentication apparatus may further include, in addition to the light-emitting device, a biometric information collector.

Description of FIGS.2and3

FIG.2is a cross-sectional view of a light-emitting apparatus according to an embodiment of the disclosure.

The light-emitting apparatus ofFIG.2includes a substrate100, a thin-film transistor (TFT), a light-emitting device, and an encapsulation portion300that seals the light-emitting device.

A TFT may be on the buffer layer210. The TFT may include an activation layer220, a gate electrode240, a source electrode260, and a drain electrode270.

The activation layer220may include an inorganic semiconductor such as silicon or polysilicon, an organic semiconductor, or an oxide semiconductor, and may include a source region, a drain region and a channel region.

A gate insulating film230for insulating the activation layer220from the gate electrode240may be on the activation layer220, and the gate electrode240may be on the gate insulating film230.

The TFT is electrically connected to a light-emitting device to drive the light-emitting device, and is covered by a passivation layer280. The passivation layer280may include an inorganic insulating film, an organic insulating film, or a combination thereof. A light-emitting device is provided on the passivation layer280. The light-emitting device may include a first electrode110, an interlayer130, and a second electrode150.

The first electrode110may be formed on the passivation layer280. The passivation layer280may not completely cover the drain electrode270and exposes a portion of the drain electrode270, and the first electrode110is connected to the exposed portion of the drain electrode270.

A pixel-defining layer290containing an insulating material may be on the first electrode110. The pixel-defining layer290exposes a region of the first electrode110, and an interlayer130may be formed in the exposed region of the first electrode110. The pixel-defining layer290may be a polyimide and/or polyacrylic organic film. At least some layers of the interlayer130may extend beyond the upper portion of the pixel-defining layer290to be located in the form of a common layer (i.e., may be provided as a common layer).

The second electrode150may be on the interlayer130, and a capping layer170may be additionally formed on the second electrode150. The capping layer170may be formed to cover the second electrode150.

FIG.3is a cross-sectional view of a light-emitting apparatus according to another embodiment of the disclosure.

The light-emitting apparatus ofFIG.3is substantially the same as the light-emitting apparatus ofFIG.2, except that a light-shielding pattern500and a functional region400are additionally located on the encapsulation portion300. The functional region400may be a combination of i) a color filter area, ii) a color conversion area, or iii) a combination of the color filter area and the color conversion area. In an embodiment, the light-emitting device included in the light-emitting apparatus ofFIG.3may be a tandem light-emitting device.

Manufacture Method

Respective layers included in the hole transport region, the emission layer, and respective layers included in the electron transport region may be formed in a certain region by utilizing one or more suitable methods selected from vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) deposition, ink-jet printing, laser-printing, and laser-induced thermal imaging.

Definition of Terms

The “cyclic group” as utilized herein may include the C3-C60carbocyclic group and the C1-C60heterocyclic group.

The term “π electron-rich C3-C60cyclic group” as utilized herein refers to a cyclic group that has three to sixty carbon atoms and does not include *—N═*′ as a ring-forming moiety, and the term “π electron-deficient nitrogen-containing C1-C60cyclic group” as utilized herein refers to a heterocyclic group that has one to sixty carbon atoms and includes *—N═*′ as a ring-forming moiety.

In an embodiment,

the π electron-rich C3-C60cyclic group may be i) a group T1, ii) a condensed cyclic group in which two or more groups T1 are condensed with each other, iii) a group T3, iv) a condensed cyclic group in which two or more groups T3 are condensed with each other, or v) a condensed cyclic group in which at least one group T3 and at least one group T1 are condensed with each other (for example, the C3-C60carbocyclic group, a 1H-pyrrole group, a silole group, a borole group, a 2H-pyrrole group, a 3H-pyrrole group, a thiophene group, a furan group, an indole group, a benzoindole group, a naphthoindole group, an isoindole group, a benzoisoindole group, a naphthoisoindole group, a benzosilole group, a benzothiophene group, a benzofuran group, a carbazole group, a dibenzosilole group, a dibenzothiophene group, a dibenzofuran group, an indenocarbazole group, an indolocarbazole group, a benzofurocarbazole group, a benzothienocarbazole group, a benzosilolocarbazole group, a benzoindolocarbazole group, a benzocarbazole group, a benzonaphthofuran group, a benzonaphthothiophene group, a benzonaphthosilole group, a benzofurodibenzofuran group, a benzofurodibenzothiophene group, a benzothienodibenzothiophene group, etc.), and

the π electron-deficient nitrogen-containing C1-C60cyclic group may be i) a group T4, ii) a condensed cyclic group in which two or more group T4 are condensed with each other, iii) a condensed cyclic group in which at least one group T4 and at least one group T1 are condensed with each other, iv) a condensed cyclic group in which at least one group T4 and at least one group T3 are condensed with each other, or v) a condensed cyclic group in which at least one group T4, at least one group T1, and at least one group T3 are condensed with one another (for example, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, an oxadiazole group, a thiazole group, an isothiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzoisoxazole group, a benzothiazole group, a benzoisothiazole group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a benzoisoquinoline group, a quinoxaline group, a benzoquinoxaline group, a quinazoline group, a benzoquinazoline group, a phenanthroline group, a cinnoline group, a phthalazine group, a naphthyridine group, an imidazopyridine group, an imidazopyrimidine group, an imidazotriazine group, an imidazopyrazine group, an imidazopyridazine group, an azacarbazole group, an azafluorene group, an azadibenzosilole group, an azadibenzothiophene group, an azadibenzofuran group, etc.),

The term “cyclic group”, “C3-C60carbocyclic group”, “C1-C60heterocyclic group”, “π electron-rich C3-C60cyclic group”, or “π electron-deficient nitrogen-containing C1-C60cyclic group” as utilized herein refers to a group condensed to any cyclic group or a polyvalent group (for example, a divalent group, a trivalent group, a tetravalent group, etc.), depending on the structure of a formula in connection with which the terms are utilized. In an embodiment, “a benzene group” may be a benzo group, a phenyl group, a phenylene group, and/or the like, which may be understood by one of ordinary skill in the art according to the structure of a formula including the “benzene group.”

The term “C1-C60heteroaryl group” as utilized herein refers to a monovalent group having a heterocyclic aromatic system that has, in addition to a carbon atom, at least one heteroatom as a ring-forming atom, and 1 to 60 carbon atoms. The term “C1-C60heteroarylene group” as utilized herein refers to a divalent group having a heterocyclic aromatic system that has, in addition to a carbon atom, at least one heteroatom as a ring-forming atom, and 1 to 60 carbon atoms. Examples of the C1-C60heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, a benzoquinolinyl group, an isoquinolinyl group, a benzoisoquinolinyl group, a quinoxalinyl group, a benzoquinoxalinyl group, a quinazolinyl group, a benzoquinazolinyl group, a cinnolinyl group, a phenanthrolinyl group, a phthalazinyl group, a naphthyridinyl group, an azafluorenyl group, a carbazolyl group, an azacarbazolyl group, an indeno carbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzosilolocarbazolyl group, a benzoindolocarbazolyl group, and a benzocarbazolyl group. When the C1-C60heteroaryl group and the C1-C60heteroarylene group each include two or more rings, the rings may be condensed with each other.

The term “monovalent non-aromatic condensed polycyclic group” as utilized herein refers to a monovalent group having two or more rings condensed to each other, only carbon atoms (for example, having 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 an indenyl group, an indenophenanthrenyl group, and an indeno anthracenyl group. The term “divalent non-aromatic condensed polycyclic group” as utilized herein refers to a divalent group having the same structure as a monovalent non-aromatic condensed polycyclic group.

The term “C6-C60aryloxy group” as utilized herein indicates —OA102(wherein A102is the C6-C60aryl group), and the term “C6-C60arylthio group” as utilized herein indicates —SA103(wherein A103is the C6-C60aryl group).

The term “C7-C60aryl alkyl group” utilized herein refers to -A104A105(where A104may be a C1-C54alkylene group, and A105may be a C6-C59aryl group), and the term “C2-C60heteroaryl alkyl group” utilized herein refers to -A106A107(where A106may be a C1-C59alkylene group, and A107may be a C1-C59heteroaryl group).

The term “hetero atom” as utilized herein refers to any atom other than a carbon atom. Examples of the heteroatom include O, S, N, P, Si, B, Ge, Se, or one or more combinations thereof.

“Ph” as utilized herein refers to a phenyl group, “Me” as utilized herein refers to a methyl group, “Et” as utilized herein refers to an ethyl group, “tert-Bu” or “But” as utilized herein refers to a tert-butyl group, and “OMe” as utilized herein refers to a methoxy group.

The term “terphenyl group” as utilized herein refers to “a phenyl group substituted with a biphenyl group”. The “terphenyl group” is a substituted phenyl group having, as a substituent, a C6-C60aryl group substituted with a C6-C60aryl group.

* and *′ as utilized herein, unless defined otherwise, each refer to a binding site to a neighboring atom in a corresponding formula or moiety.

Hereinafter, compounds according to embodiments and light-emitting devices according to embodiments will be described in more detail with reference to the following synthesis examples and examples. The wording “B was utilized instead of A” utilized in describing Synthesis Examples refers to that an identical molar equivalent of B was utilized in place of A.

EXAMPLES

The organometallic compound according to an embodiment may be synthesized, for example, as follows. However, synthesis methods of the organometallic compound according to an embodiment are not limited thereto.

Source of Reagent Utilized

Synthesis Example 1. Synthesis of BD1

1) Synthesis of Intermediate BD1-1

7-methoxy-1,2,3,4-tetrahydroquinoline (1 eq), 2-bromo-4-(tert-butyl)pyridine (1.2 eq), SPhos (0.07 eq), Pd2(dba)3(0.05 eq), and sodium tert-butoxide (2.0 eq) were suspended in a toluene solvent, and the temperature was raised to 100° C., followed by stirring for 12 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an organic layer was extracted by utilizing methylene chloride and distilled water. The extracted organic layer was washed with a saturated aqueous sodium chloride solution and dried by utilizing magnesium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain Intermediate BD1-1 at a yield of 80%.

2) Synthesis of Intermediate BD1-2

Intermediate BD1-1 (1.0 eq) was dissolved in methylene chloride, and 1M BBr3(1.2 eq) was added dropwise thereto at 0° C. After stirring the resultant at room temperature for an hour, the mixture was neutralized with a NaOH aqueous solution, and an organic layer was extracted by utilizing methylene chloride and distilled water. The extracted organic layer was dried by utilizing magnesium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain Intermediate BD1-2 at a yield of 64%.

3) Synthesis of Intermediate BD1-3

4) Synthesis of Intermediate BD1-4

Intermediate BD1-2 (1.0 eq), Intermediate BD1-3 (1.2 eq), CuI (0.01 eq), K2CO3(2.0 eq), and L-Proline (0.02 eq) were dissolved in DMSO (0.1M), followed by stirring at 130° C. for 24 hours. The reaction mixture was cooled at room temperature, and an extraction process was performed thereon three times by utilizing dichloromethane and water, to thereby obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate and concentrated, and column chromatography was utilized to obtain Intermediate BD1-4 at a yield of 66%.

5) Synthesis of Compound BD1

Synthesis Example 2. Synthesis of BD12

1) Synthesis of Intermediate BD12-1

(6-fluoro-4-methylpyridin-3-yl)boronic acid (1.2 eq), bromobenzene-d5 (1 eq), Pd(PPh3)4 (0.05 eq), and 2M K2CO3(3 eq) were dissolved in toluene, followed by stirring at 110° C. for 12 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an organic layer was extracted by utilizing methylene chloride and distilled water. The extracted organic layer was dried by utilizing magnesium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain Intermediate BD12-1 at a yield of 88%.

2) Synthesis of Intermediate BD12-2

Intermediate BD12-1 (1 eq), 6-bromo-1,2,3,4-tetrahydroquinoline (1.1 eq), and K3PO4(3 eq) were dissolved in DMF, followed by stirring at 160° C. for 10 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an organic layer was extracted by utilizing methylene chloride and distilled water. The extracted organic layer was dried by utilizing magnesium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain Intermediate BD12-2 at a yield of 78%.

3) Synthesis of Intermediate BD12-3

Intermediate BD12-3 was obtained in substantially the same manner as utilized to obtain Intermediate BD1-4 of Synthesis Example 1, except that Intermediate BD12-2 was utilized instead of Intermediate BD1-3.

4) Synthesis of Compound BD12

Intermediate BD12-3 (1.0 eq), dichloro (1,2-dicyclooctadiene)platinum (Pt(COD)Cl2) (1.1 eq), and sodium acetate (2.0 eq) were dissolved in dioxane (0.1 M), followed by stirring at 120° C. for 72 hours. The reaction mixture was cooled at room temperature, and an extraction process was performed thereon three times by utilizing dichloromethane and water, to thereby obtain an organic layer. The obtained organic layer was dried utilizing magnesium sulfate and concentrated, and column chromatography was utilized to synthesize Compound BD12 (yield: 20%).

Synthesis Example 3. Synthesis of BD28

1) Synthesis of Intermediate BD28-1

1,2,3,4-tetrahydroquinoline-7-carbaldehyde (1 eq), 2-bromo-4-methylpyridine (1.2 eq), SPhos (0.07 eq), Pd2(dba)3(0.05 eq), and sodium tert-butoxide (2.0 eq) were suspended in a toluene solvent, and temperature was raised to 100° C., followed by stirring for 12 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an organic layer was extracted by utilizing methylene chloride and distilled water. The extracted organic layer was washed with a saturated aqueous sodium chloride solution and dried by utilizing magnesium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain Intermediate BD28-1 at a yield of 60%.

2) Synthesis of Intermediate BD28-2

Magnesium (1 eq) and 2-bromobiphenyl (1 eq) were added to THF and stirred for 30 minutes at 80° C., dried LiCl (1 eq) was added thereto, and then, the mixture was stirred for 10 minutes. Intermediate BD28-1 was dissolved in THF and then slowly added dropwise thereto, followed by stirring for 15 hours. After completion of the reaction, an organic layer was extracted by utilizing an aqueous ammonium chloride solution and ethylacetate. The extracted organic layer was dried by utilizing magnesium sulfate, and a residue obtained by removing the solvent therefrom was separated by utilizing column chromatography to obtain Intermediate BD28-2 at a yield of 58%.

3) Synthesis of Intermediate BD28-3

Intermediate BD28-2 was dissolved in acetone, and potassium phosphate tribasic (2 eq) was added thereto, followed by stirring at 60° C. for 12 hours. After completion of the reaction, an organic layer was extracted by utilizing ethylacetate, the extracted organic layer was dried by utilizing magnesium sulfate, and a residue obtained by removing the solvent therefrom was separated by utilizing column chromatography to obtain Intermediate BD28-3 at a yield of 80%.

4) Synthesis of Intermediate BD28-4

Intermediate BD28-4 was obtained in substantially the same manner as utilized to obtain Intermediate BD28-2 of Synthesis Example 3, except that Intermediate 7-bromo-1-(4-methylpyridin-2-yl)-1,2,3,4-tetrahydroquinoline was utilized instead of 2-bromobiphenyl.

5) Synthesis of Intermediate BD28-5

Intermediate BD28-4 was dissolved in hydrochloric acid and acetic acid (a volume ratio of 1:1), followed by stirring at 60° C. for 12 hours. After completion of the reaction, the mixture was neutralized with an aqueous sodium hydroxide solution, and an organic layer was extracted by utilizing methylene chloride and distilled water. The extracted organic layer was washed with a saturated aqueous sodium chloride solution and dried by utilizing magnesium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain Intermediate BD28-5 at a yield of 70%.

6) Synthesis of Compound BD28

Synthesis Example 4. Synthesis of BD66

1) Synthesis of Intermediate BD66-1

5-bromo-7-methoxy-1,2,3,4-tetrahydroquinoline (1 eq), 2-bromo-4-(tert-butyl) pyridine (1.2 eq), SPhos (0.07 eq), Pd2(dba)3(0.05 eq), and sodium tert-butoxide (2.0 eq) were suspended in a toluene solvent, and the temperature was raised to 100° C., followed by stirring for 12 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an organic layer was extracted by utilizing methylene chloride and distilled water. The extracted organic layer was washed with a saturated aqueous sodium chloride solution and dried by utilizing magnesium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain Intermediate BD66-1 at a yield of 74%.

2) Synthesis of Intermediate BD66-2

Intermediate BD66-1 (1 eq), Copper(I) cyanide (2 eq), and L-proline (1 eq) were added to DMF, followed by stirring at 160° C. for 24 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an organic layer was extracted by utilizing ethylacetate and distilled water. The extracted organic layer was washed with a saturated aqueous sodium chloride solution and dried by utilizing magnesium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain Intermediate BD66-2 at a yield of 80%.

3) Synthesis of Intermediate BD66-3

Intermediate BD66-3 was obtained in substantially the same manner as utilized to obtain Intermediate BD1-2 of Synthesis Example 1, except that Intermediate BD66-2 was utilized instead of Intermediate BD1-1.

4) Synthesis of Intermediate BD66-4

Intermediate BD66-4 was obtained in substantially the same manner as utilized to obtain Intermediate BD1-4 of Synthesis Example 1, except that Intermediate BD66-3 was utilized instead of Intermediate BD1-2.

5) Synthesis of Compound BD66

Synthesis Example 5. Synthesis of BD91

1) Synthesis of Intermediate BD91-1

Intermediate 66-1 (1 eq) was dissolved in THF, and tert-butylmagnesium bromide (1M in THF, 1.3 eq) was slowly added dropwise thereto, followed by stirring at room temperature for 24 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an organic layer was extracted by utilizing ethylacetate and distilled water. The extracted organic layer was washed with a saturated aqueous sodium chloride solution and dried by utilizing magnesium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain Intermediate BD91-1 at a yield of 67%.

2) Synthesis of Intermediate BD91-2

Intermediate BD91-2 was obtained in substantially the same manner as utilized to obtain Intermediate BD1-2 of Synthesis Example 1, except that Intermediate BD91-1 was utilized instead of Intermediate BD1-1.

3) Synthesis of Intermediate BD91-3

Intermediate BD91-3 was obtained in substantially the same manner as utilized to obtain Intermediate BD1-4 of Synthesis Example 1, except that Intermediate BD91-2 was utilized instead of Intermediate BD1-2.

4) Synthesis of Compound BD91

Evaluation Example 1

LUMO and HOMO values of compounds of Synthesis Examples were measured utilizing methods described in Table 2, and by utilizing the DFT method of the Gaussian 09 program (with the structure optimization at the level of B3LYP, 6-311 G(d,p)), T1(triplet energy), and3MLCT values of Compounds of Synthesis Examples were calculated. The results are shown in Table 3.

Structural formulae of Comparative Compounds 1 and 2 of Table 3 are as follows.

As an anode, a glass substrate with ITO of 15 Ω/cm2and 1,200 Å deposited thereon was cut to a size of 50 mm×50 mm×0.7 mm, sonicated with isopropyl alcohol and pure water each for 5 minutes, and then cleaned by irradiation of ultraviolet rays and exposure of ozone thereto for 30 minutes. The resultant glass substrate was loaded onto a vacuum deposition apparatus.

2-TNATA was vacuum-deposited on the ITO substrate to form a hole injection layer having a thickness of 600 Å, and then, NPB was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 300 Å.

A second compound (HTH29), a third compound (ETH2), and BD1 of Synthesis Example 1 were co-deposited on the hole transport layer at a weight ratio of 65:35:10 to form an emission layer having a third compound of 300 Å.

ETH2 was deposited on the emission layer to form a hole blocking layer having a thickness of 50 Å. Next, Alq3was deposited on the hole blocking layer to form an electron transport layer having a thickness of 300 Å, and LiF, which is a halogenated alkali metal, was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and Al was vacuum-deposited thereon to form a cathode electrode having a thickness of 3,000 Å, to form a LiF/Al electrode, thereby completing the manufacture of a light-emitting device.

Example 2 was carried out in substantially the same manner as in Example 1, except that Compound BD12 was utilized instead of Compound BD1.

Example 3 was carried out in substantially the same manner as in Example 1, except that Compound BD28 was utilized instead of Compound BD1.

Example 4 was carried out in substantially the same manner as in Example 1, except that Compound BD66 was utilized instead of Compound BD1.

Example 5 was carried out in substantially the same manner as in Example 1, except that Compound BD91 was utilized instead of Compound BD1.

Comparative Example 1

Comparative Example 1 was carried out in substantially the same manner as in Example 1, except that Comparative Compound 1 was utilized instead of Compound BD1. A structural formula of Comparative Compound 1 is as follows.

Structural Formula of Comparative Compound 1

Comparative Example 2

Comparative Example 2 was carried out in substantially the same manner as in Example 1, except that Comparative Compound 2 was utilized instead of Compound BD1. A structural formula of Comparative Compound 2 is as follows.

Structural Formula of Comparative Compound 2

A voltage was supplied so that the light-emitting devices manufactured according to Examples 1 to 5 and Comparative Examples 1 and 2 emitted light having a luminance of 1,000 cd/m2. The luminance (cd/m2), driving voltage (V), luminescence efficiency (cd/A), maximum emission wavelength (nm), and device lifespan (hr @ 1,000 cd/m2) were each measured by utilizing the Keithley MU 236 and the luminance meter PR650, and results thereof are shown in Table 4.

From Table 4, it may be confirmed that the light-emitting device including the organometallic compound according to each Example had excellent or suitable driving voltage (V), excellent or suitable luminescence efficiency (cd/A), and excellent or suitable device lifespan (T90), as compared to the light-emitting devices including dopants of Comparative Examples 1 and 2.

A light-emitting device having high efficiency and a long lifespan and a high-quality electronic apparatus including the same may be manufactured by utilizing the organometallic compound.

The use of “may” when describing embodiments of the present disclosure refers to “one or more embodiments of the present disclosure.”