HETEROCYCLIC COMPOUND, LIGHT-EMITTING DEVICE INCLUDING HETEROCYCLIC COMPOUND, AND ELECTRONIC APPARATUS INCLUDING LIGHT-EMITTING DEVICE

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

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to and the benefit of Korean Patent Application No. 10-2021-0158041, filed on Nov. 16, 2021, in the Korean Intellectual Property Office, the entire disclosure of which is hereby incorporated by reference.

BACKGROUND

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

2. Description of the Related Art

From among light-emitting devices, organic light-emitting devices are self-emissive devices that, as compared with devices of the related art, have wide viewing angles, high contrast ratios, short response times, and excellent or suitable characteristics in terms of luminance, driving voltage, and response speed, and produce full-color images.

Organic light-emitting devices may include a first electrode located on a substrate, and a hole transport region, an emission layer, an electron transport region, and a second electrode sequentially stacked on the first electrode. Holes provided from the first electrode move toward the emission layer through the hole transport region, and electrons provided from the second electrode move toward the emission layer through the electron transport region. Carriers, such as holes and electrons, recombine in the emission layer to produce excitons. The excitons may transition from an excited state to a ground state, thus generating light.

SUMMARY

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

Additional aspects of embodiments of the present disclosure will be set forth in part in the description which follows and, in part, will be apparent from the disclosure, or may be learned by practice of the presented embodiments of the disclosure.

According to one or more embodiments, a heterocyclic compound may be represented by Formula 1:

A1is a C3-C60carbocyclic group or a C1-C60heterocyclic group,

a1 to a3 may each independently be an integer from 0 to 3,

n1 and n2 may each independently be an integer from 1 to 10,

at least one of R1in the number of n1, and R2in the number of n2, or R3in Formula 1 may be a group represented by Formula 2,

* indicates a binding site to a neighboring atom,

R10amay be

a nitro group; or a C1-C60alkyl group, a C2-C60alkenyl group, a C2-C60alkynyl group, a C1-C60alkoxy group, a C3-C60carbocyclic group, a C1-C60heterocyclic group, a C7-C60aryl alkyl group, or a C2-C60heteroaryl alkyl group, each unsubstituted or substituted with deuterium, —F, a cyano group, a C1-C60alkyl group, a C1-C60alkoxy group, a phenyl group, a biphenyl group, a C1-C60heterocyclic group, or one or more combinations thereof.

According to one or more embodiments, a light-emitting device includes 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 (in the interlayer), and

at least one heterocyclic compound.

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

DETAILED DESCRIPTION

An aspect of an embodiment of the present disclosure is directed toward a heterocyclic compound represented by Formula 1:

A1is a C3-C60carbocyclic group or a C1-C60heterocyclic group, and A2is a C1-C60heterocyclic group.

In an embodiment, A2may be a C1-C60heterocyclic group which including at least one Nitrogen atom.

In an embodiment, L1to L3may each independently be represented by one of Formulae 3-1 to 3-41:

X1may be N or C(Z3),

X2may be N or C(Z4),

X3may be N or C(Z5),

X4may be N or C(Z6),

e4 may be an integer from 1 to 4,

e6 may be an integer from 1 to 6,

e7 may be an integer from 1 to 7,

e8 may be an integer from 1 to 8, and

a1 to a3 may each independently be an integer from 0 to 3.

When a1 is 0, L1may not be present, and R1and A1may be directly linked to each other via a single bond. When a1 is 0, L1may be present as a single bond.

When a2 is 0, L2may not be present, and R2and A2may be directly linked to each other via a single bond. When a2 is 0, L2may be present as a single bond.

When a3 is 0, L3may not be present, and R3may be directly linked to the core via a single bond. For example, when a3 is 0, L3may be present as a single bond.

In an embodiment, at least one of a1 in the number of n1, a2 in the number of n2, or a3 in Formula 1 may be an integer of 1 or more. For example, a3 may be an integer of 1 or more.

In an embodiment, the sum of a1 in the number of n1, a2 in the number of n2, and a3 in Formula 1 may be 2 or more.

n1 and n2 may each independently be an integer from 1 to 10.

*-(L1)a1-R1in the number of n1 may be identical to or different from each other, and *-(L2)a2-R2in the number of n2 may be identical to or different from each other.

At least one of R1in the number of n1, R2in the number of n2, or R3in Formula 1 may be a group represented by Formula 2.

* indicates a binding site to a neighboring atom.

In an embodiment, the heterocyclic compound represented by Formula 1 may be represented by Formula 1-1:

X11may be N or C(E11),

X12may be N or C(E12),

X13may be N or C(E13),

X14may be N or C(E14),

X21may be N or C(E21),

X22may be N or C(E22),

X23may be N or C(E23),

X24may be N or C(E24),

L11to L14may each independently be the same as in the description of L1,

a11 to a14 may each independently be the same as in the description of a1,

R11to R14may each independently be the same as in the description of R1,

L21to L24may each independently be the same as in the description of L2,

a21 to a24 may each independently be the same as in the description of a2,

R21to R24may each independently be the same as in the description of R2,

L3, a3, and R3may respectively the same as L3, a3, or R3as described herein,

at least one of R11to R14, R21to R24, or R3may be a group represented by Formula 2, and

* indicates a binding site to a neighboring atom.

In an embodiment, two or more neighboring groups of E11to E14and E21to E24may optionally be bonded to each other to form a C5-C30carbocyclic group unsubstituted or substituted with at least one R10aor a C2-C30heterocyclic group unsubstituted or substituted with at least one R10a.

In an embodiment, in Formula 1-1,

R3may be a group represented by Formula 2; or

X24may be C(E24), and R24may be a group represented by Formula 2.

In an embodiment, the heterocyclic compound represented by Formula 1-1 may be represented by Formula 1-1(a):

at least one of R11to R14, R21to R24, or R3may be a group represented by Formula 2.

In an embodiment, in Formula 1-1(a), R3may be the group represented by Formula 2, or R24may be a group represented by Formula 2.

In an embodiment, the heterocyclic compound represented by Formula 1-1 may be represented by Formula 1-2:

X31may be N or C(E31),

X32may be N or C(E32),

X33may be N or C(E33),

X34may be N or C(E34),

X35may be N or C(E35),

X11to X14and X21to X24are each the same as described herein,

L31to L35may each independently be the same as in the description of L3,

a31 to a35 may each independently be an integer from 0 to 2,

R31to R35may each independently be the same as in the description of R3,

at least one of R11to R14, R21to R24, or R31to R35may be a group represented by Formula 2, and

* indicates a binding site to a neighboring atom.

In an embodiment, in Formula 1-2, at least one of X31to X35may be N.

a group represented by Formula 2,

In one or more embodiments, R1to R3may each independently be:

a group represented by Formula 2,

a group represented by one of Formulae 4-1 to 4-36:

e2 may be 1 or 2,

e3 may be an integer from 1 to 3,

e4 may be an integer from 1 to 4,

e5 may be an integer from 1 to 5,

e6 may be an integer from 1 to 6,

e7 may be an integer from 1 to 7,

e9 may be an integer from 1 to 9,

* indicates a binding site to a neighboring atom.

In one or more embodiments, the heterocyclic compound represented by Formula 1 may be selected from Compounds 1 to 8, but embodiments of the present disclosure are not limited thereto:

The heterocyclic compound represented by Formula 1 may have a structure in which at least one silole group is included in the core of the condensed heterocyclic core (for example, the core of the pyrido-indole moiety) in which rings A1and A2are condensed with the pyrrole group.

Because the heterocyclic compound includes a heterocyclic core in which rings A1and A2are condensed with the pyrrole group, a molecule may be more rigid in view of a bond dissociation energy (BDE), thereby having thermal stability and being suitable in transferring energy.

In some embodiments, the heterocyclic compound may include at least one silole group, thereby improving electron injection and transport characteristics, and thus improving (increasing) efficiency and lifespan characteristics of the light-emitting device.

Therefore, an electronic device, e.g., an organic light-emitting device, employing the heterocyclic compound represented by Formula 1, may have a low driving voltage, high maximum quantum yield, high efficiency, and a long lifespan.

Methods of synthesizing the heterocyclic compound represented by Formula 1 should be readily apparent to those of ordinary skill in the art by referring to Examples described herein.

At least one heterocyclic compound represented by Formula 1 may be utilized in a light-emitting device (for example, an organic light-emitting device).

Another aspect of an embodiment of the present disclosure is directed toward 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 at least one the heterocyclic compound.

In 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 emission layer and the first electrode, and the interlayer may further include 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 emission layer may include the at least one heterocyclic compound.

In an embodiment, the emission layer may further include a transition metal-containing compound.

In an embodiment, the emission layer may emit blue light or blue-green light.

In an embodiment, the emission layer may emit blue light or blue-green light having a maximum emission wavelength range of about 400 nm to about 500 nm.

As used herein, the expression the “(the interlayer) includes a heterocyclic compound” may be construed as meaning the “(the interlayer) may include one heterocyclic compound of Formula 1 or two different heterocyclic compounds of Formula 1”.

In an embodiment, the interlayer may include only Compound 1 as the heterocyclic compound. In this regard, Compound 1 may be present in the emission layer of the light-emitting device. In one or more embodiments, the interlayer may include, as the heterocyclic 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 used 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.

Another aspect of an embodiment of the present disclosure is directed toward an electronic apparatus including the light-emitting device. The electronic apparatus may further include a thin-film transistor.

For example, 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. For example, the electronic apparatus may be a flat panel display apparatus, but embodiments of the present disclosure are not limited thereto.

For more details on the electronic apparatus, related descriptions provided herein may be referred to.

Description of FIG.1

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

Hereinafter, the structure of the light-emitting device10according to an embodiment and a method of manufacturing the light-emitting device10will be described with reference toFIG.1.

First Electrode110

InFIG.1, a substrate may be additionally located under the first electrode110or on the second electrode150. As the substrate, a glass substrate and/or a plastic substrate may be utilized. In one or more embodiments, the substrate may be a flexible substrate, and may include plastics with excellent or suitable heat resistance and durability, such as polyimide (PI), 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 multi-layered structure including a plurality of layers. For example, the first electrode110may have a three-layered structure of ITO/Ag/ITO.

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

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

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

In one or more embodiments, the interlayer130may include, i) two or more emitting units sequentially stacked between the first electrode110and the second electrode150, and ii) a charge generation layer located between the two or more 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.

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

xa5 may be an integer from 1 to 10,

R201and R202may optionally be linked to each other via a single bond, a C1-C5alkylene group unsubstituted or substituted with at least one R10a, or a C2-C5alkenylene group unsubstituted or substituted with at least one R10a, to 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 unsubstituted or substituted with at least one R10a, or a C2-C5alkenylene group unsubstituted or substituted with at least one R10a, to form a C8-C60polycyclic group unsubstituted or substituted with at least one R10a, and

na1 may be an integer from 1 to 4.

For example, each of Formulae 201 and 202 may include at least one of the groups represented by Formulae CY201 to CY217:

R10band R10cin Formulae CY201 to CY217 are each the same as in the description of R10a, ring CY201 to ring CY204 may each independently be a C3-C2ocarbocyclic group or a C1-C20heterocyclic group, and at least one hydrogen in Formulae CY201 to CY217 may be unsubstituted or substituted with R10a.

In one or more embodiments, ring CY201 to ring CY204 in Formulae CY201 to CY217 may each independently be a benzene group, a naphthalene group, a phenanthrene group, or an anthracene group.

In one or more embodiments, each of Formulae 201 and 202 may include at least one of the groups represented by Formulae CY201 to CY203.

In one or more embodiments, Formula 201 may include at least one of the groups represented by Formulae CY201 to CY203 and at least one of the groups represented by Formulae CY204 to CY217.

In one or more embodiments, in Formula 201, xa1 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 one or more embodiments, each of Formulae 201 and 202 may not include (e.g., may exclude) a group represented by one of Formulae CY201 to CY203.

In one or more embodiments, each of Formulae 201 and 202 may not include (e.g., may exclude) a group represented by one of Formulae CY201 to CY203, and may include at least one of the groups represented by Formulae CY204 to CY217.

In one or more embodiments, each of Formulae 201 and 202 may not include (e.g., may exclude) a group represented by one of 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 flow of electrons from an electron transport region. The emission auxiliary layer and the electron blocking layer may include the materials as described above.

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 consisting of a charge-generation material).

The charge generation material may be, for example, a p-dopant.

For example, the lowest unoccupied molecular orbital (LUMO) energy level of the p-dopant may be −3.5 eV or less.

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

Examples of the quinone derivative are TCNQ, F4-TCNQ, etc.

Examples of the cyano group-containing compound are HAT-CN and a compound represented by Formula 221:

In Formula 221,

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 any combination thereof; or one or more combinations thereof.

In the compound including element EL1 and element EL2, element EL1 may be metal, metalloid, or one or more combinations thereof, and element EL2 may be non-metal, metalloid, or one or more combinations thereof.

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

An example of the metalloid halide is 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 any combination thereof.

The host may include the at least one heterocyclic compound represented by Formula 1.

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

In one or more embodiments, the emission layer may include a quantum dot.

In some embodiments, 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 the at least one heterocyclic compound represented by Formula 1.

The host may further include a compound represented by Formula 301:

In Formula 301,

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 unsubstituted or substituted with at least one R10a, a C2-C60alkenyl group unsubstituted or substituted with at least one R10a, a C2-C60alkynyl group unsubstituted or substituted with at least one R10a, a C1-C60alkoxy group unsubstituted or substituted with at least one R10a, a C3-C60carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60heterocyclic group 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 each the same as in the description of Q1.

For example, 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 one or more embodiments, the host may include a compound represented by Formula 301-1, a compound represented by Formula 301-2, or one or more combinations thereof:

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

L301, xb1, and R301may respectively be the same as L301, xb1, and R301as described herein,

L302to L304may each independently be the same as in the description of L301,

xb2 to xb4 may each independently be the same as in the description of xb1 and

R302to R305and R311to R314may respectively be the same as in the description of R301.

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

In one or more embodiments, the phosphorescent dopant may include at least one transition metal as a central metal.

The phosphorescent dopant may be electrically neutral.

For example, 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, and 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 Q414may each be the same as in the description of 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 unsubstituted or substituted with at least one R10a, a C1-C20alkoxy group unsubstituted or substituted with at least one R10a, a C3-C60carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60heterocyclic group 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 Q403may each be the same as in the description of Q1,

For example, in Formula 402, i) X401may be nitrogen, and X402may be carbon, or ii) each of X401and X402may be nitrogen.

In one or more embodiments, when xc1 in Formula 402 is 2 or more, two ring A401(s) in two or more of L401(s) may be optionally linked to each other via T402, which is a linking group, and two ring A402(s) may be optionally linked to each other via T403, which is a linking group (see Compounds PD1 to PD4 and PD7). T402and T403are each the same as in the description of T401.

L402in Formula 401 may be an organic ligand. For example, 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, 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 one or more combinations thereof.

For example, the fluorescent dopant may include a compound represented by Formula 501:

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

For example, 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 one or more embodiments, xd4 in Formula 501 may be 2.

For example, the fluorescent dopant may include: 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 fluorescent light 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 one or more embodiments, 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).

For example, 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.

The term “quantum dots” as used herein refers to crystals of a semiconductor compound, and may include any material capable of emitting light of one or more suitable emission wavelengths according to the size of the crystals.

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 process similar (suitable) thereto that should be apparent to one of ordinary skill in the art upon reviewing the disclosure.

The wet chemical process is a method including mixing a precursor material with an organic solvent and then growing 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 can be controlled or selected through a process which lowers costs, and is easier than vapor deposition methods, such as metal organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE).

The quantum dot may include a Group III-VI semiconductor compound; 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 In2S3; a ternary compound, such as AgInS, AgInS2, CuInS, or CuInS2; or one or more combinations thereof.

Examples of the Group III-VI semiconductor compound may be: a binary compound, such as GaS, GaSe, Ga2Se3, GaTe, InS, InSe, In2Se3, or InTe; a ternary compound, such as InGaS3or InGaSe3; or one or more combinations thereof.

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

Examples of the Group IV-VI semiconductor compound may be: a binary compound, such as SnS, SnSe, SnTe, PbS, PbSe, or PbTe; a ternary compound, such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, or SnPbTe; a quaternary compound, such as SnPbSSe, SnPbSeTe, or SnPbSTe; 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, the ternary compound, and the quaternary compound may be present at a substantially uniform concentration or non-uniform concentration in a particle form.

In some embodiments, the quantum dot may have a single structure in which the concentration of each element in the quantum dot is substantially uniform, or a core-shell dual structure. For example, the material included in the core and the material included in the shell may be different from each other.

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

Examples of the shell of the quantum dot may be an oxide of metal, or non-metal, a semiconductor compound, and one or more combinations thereof. Examples of the oxide of metal or non-metal may be 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; and one or more combinations thereof. Examples of the semiconductor compound may be, as described herein, Group III-VI semiconductor compounds; Group II-VI semiconductor compounds; Group III-V semiconductor compounds; Group III-VI semiconductor compounds; Group I-III-VI semiconductor compounds; Group IV-VI semiconductor compounds; and one or more combinations thereof. For example, 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 the 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 may be improved (increased).

In some embodiments, the quantum dot may be in the form of 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 may be adjusted by controlling the size of the quantum dot, light having one or more suitable wavelength bands may be obtained from the quantum dot emission layer. Accordingly, by utilizing quantum dots of different sizes, a light-emitting device that emits light of one or more suitable wavelengths may be implemented. In one or more embodiments, 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 combination of 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.

For example, the electron transport region may include a compound represented by Formula 601:

R601may be a C3-C60carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60heterocyclic group 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 be the same as in the description of Q1,

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

For example, when xe11 in Formula 601 is 2 or more, two or more of Ar601(s) may be linked to each other via a single bond.

In other embodiments, Ar601in Formula 601 may be a substituted or unsubstituted anthracene group.

In other embodiments, the electron transport region may include a compound represented by Formula 601-1:

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

L611to L613may each be the same as in the description of L601,

xe611 to xe613 may each be the same as in the description of xe1,

R611to R613may each be the same as in the description of 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 unsubstituted or substituted with at least one R10a, or a C1-C60heterocyclic group unsubstituted or substituted with at least one R10a.

For example, xe1 and xe611 to xe613 in Formulae 601 and 601-1 may each independently be 0, 1, or 2.

The electron transport region may include one of Compounds ET1 to ET45, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), diphenyl(4-(triphenylsilyl)phenyl)-phosphine oxide (TSPO1), Alq3, BAlq, TAZ, NTAZ, DPEPO, or one or more combinations thereof:

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 directly contact the second electrode150.

The alkali metal may include Li, a 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 be oxides, halides (for example, fluorides, chlorides, bromides, or iodides), or tellurides of the alkali metal, the alkaline earth metal, and/or 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 or more of ions of the alkali metals, the alkaline earth metals, and/or the rare earth metals 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 hydroxydiphenyloxadiazole, a hydroxydiphenylthiadiazole, a hydroxyphenylpyridine, a hydroxyphenyl benzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or one or more combinations thereof.

In one or more embodiments, 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. For example, 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, alkali metal, alkaline earth metal, rare earth metal, an alkali metal-containing compound, an alkaline earth metal-containing compound, a rare earth metal-containing compound, alkali metal complex, alkaline earth-metal complex, rare earth metal complex, or one or more combinations thereof may be substantially uniformly or non-uniformly dispersed in a matrix including the organic material.

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

The second electrode150may have a single-layered structure or a multi-layered structure including a plurality of layers.

Capping Layer

A first capping layer may be located outside the first electrode110, and/or a second capping layer may be located outside the second electrode150. In particular, 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 the stated order, a structure in which the first electrode110, the interlayer130, the second electrode150, and the second capping layer are sequentially stacked in the 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 the stated order.

Light generated in an emission layer of the interlayer130of the light-emitting device10may be extracted toward the outside through the first electrode110which is a semi-transmissive electrode or a transmissive electrode, and the first capping layer. Light generated in an emission layer of the interlayer130of the light-emitting device10may be extracted toward the outside through the second electrode150which 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 luminescence efficiency of the light-emitting device10may be improved.

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

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. Optionally, the carbocyclic compound, the heterocyclic compound, and the amine group-containing compound may be substituted with a substituent including O, N, S, Se, Si, F, Cl, Br, I, or one or more combinations thereof. In one or more embodiments, at least one of the first capping layer or the second capping layer may each independently include an amine group-containing compound.

For example, at least one of the first capping layer or the second capping layer may each independently include a compound represented by Formula 201, a compound represented by Formula 202, or one or more combinations thereof.

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

Electronic Apparatus

The light-emitting device may be included in one or more suitable electronic apparatuses. For example, 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, a light-emitting apparatus) may further include, in addition to the light-emitting device, i) a color filter, ii) a color conversion layer, or iii) a color filter and a color conversion layer. The color filter and/or the 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. For more details on the light-emitting device, the related descriptions provided above may be referred to. In one or more embodiments, the color conversion layer may include a quantum dot. The quantum dot may be, for example, a quantum dot as described herein.

A pixel-defining film may be located 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 color conversion layer may further include a plurality of color conversion areas and light-shielding patterns located among the color conversion areas.

The plurality of color filter areas (or the plurality of 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, wherein the first color light, the second color light, and/or the third color light may have different maximum emission wavelengths from one another. For example, 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. For example, the plurality of color filter areas (or the plurality of color conversion areas) may include quantum dots. For example, 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. For more details on the quantum dot, related descriptions provided herein may be referred to. The first area, the second area, and/or the third area may each include a scatterer.

For example, 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. For example, 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, and/or the like.

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

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

Description of FIGS.2and3

FIG.2is a cross-sectional view showing a light-emitting apparatus according to an embodiment of the present 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 located on the buffer layer210. The TFT may include an activation layer220, a gate electrode240, a source electrode260, and/or 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/or a channel region.

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

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

The first electrode110may be located on the passivation layer280. The passivation layer280may be located such that it may expose a portion of the drain electrode270, not fully covering the drain electrode270, and the first electrode110may be located such that it may be connected to the exposed portion of the drain electrode270.

A pixel defining layer290including an insulating material may be located on the first electrode110. The pixel defining layer290may expose a certain 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 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.

The second electrode150may be located 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.3shows a cross-sectional view showing a light-emitting apparatus according to an embodiment of the present disclosure.

The light-emitting apparatus ofFIG.3is 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 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.

Manufacturing Method

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

Definition of Terms

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

The term “π electron-rich C3-C60cyclic group” as used 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 used herein refers to a heterocyclic group that has one to sixty carbon atoms and includes *—N=*′ as a ring-forming moiety.

For example,

the π electron-rich C3-C60cyclic group may be i) a T1 group, ii) a condensed cyclic group in which two or more T1 groups are condensed with each other, iii) a T3 group, iv) a condensed cyclic group in which two or more T3 groups are condensed with each other, or v) a condensed cyclic group in which at least one T3 group and at least one T1 group are condensed with each other (for example, the C3-C60carbocyclic group, a 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, and/or the like),

the π electron-deficient nitrogen-containing C1-C60cyclic group may be i) a T4 group, ii) a condensed cyclic group in which two or more T4 groups are condensed with each other, iii) a condensed cyclic group in which at least one T4 group and at least one T1 group are condensed with each other, iv) a condensed cyclic group in which at least one T4 group and at least one T3 group are condensed with each other, or v) a condensed cyclic group in which at least one T4 group, at least one T1 group, and at least one T3 group 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 terms “the cyclic group, the C3-C60carbocyclic group, the C1-C60heterocyclic group, the π electron-rich C3-C60cyclic group, or the π electron-deficient nitrogen-containing C1-C60cyclic group” as used herein refer to a group condensed to any cyclic group, a monovalent group, or a polyvalent group (for example, a divalent group, a trivalent group, a tetravalent group, etc.) according to the structure of a formula for which the corresponding term issued. For example, the “benzene group” may be a benzo group, a phenyl group, a phenylene group, and/or the like, which may be easily 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 used herein refers to a monovalent group having a heterocyclic aromatic system of 1 to 60 carbon atoms, further including, in addition to carbon atoms, at least one heteroatom, as ring-forming atoms. The term “C1-C60heteroarylene group” as used herein refers to a divalent group having a heterocyclic aromatic system of 1 to 60 carbon atoms, further including, in addition to carbon atoms, at least one heteroatom, as ring-forming atoms. Examples of the C1-C60heteroaryl group are 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/or 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 (for example, having 8 to 60 carbon atoms) having two or more rings condensed to each other, only carbon atoms as ring-forming atoms, and no aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic condensed polycyclic group are an indenyl group, an indenophenanthrenyl group, and/or an indeno anthracenyl group. The term “divalent non-aromatic condensed polycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed polycyclic group described above.

The term “R10a” as used herein refers to:

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

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

The term “biphenyl group” as used herein refers to “a phenyl group substituted with a phenyl group.” For example, the “biphenyl group” may be a substituted phenyl group having a C6-C60aryl group as a substituent.

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 used instead of A” used in describing Synthesis Examples indicates that an identical molar equivalent of B was utilized in place of A.

EXAMPLES

Synthesis Example 1: Synthesis of Compound 1

Synthesis of Intermediate A-1

20 g (1.36 mol) of pyrido[1,2-a]indole was dissolved in 200 mL of methylene chloride (MC), and 20 mL of N-Bromosuccinimide (NBS) dissolved in MC was slowly added thereto at room temperature. When the reaction was completed after stirring for 10 hours and adding water thereto, the reaction product was subjected to an extraction process with diethylether and washed with water three times. An organic layer was dried with magnesium sulfate and a solvent was removed therefrom under reduced pressure. In this regard, the obtained reaction product was purified with silica gel column chromatography to obtain 23.4 g of Intermediate A having a yield of 80%. (C12H8BrN: M+1 247.1)

Synthesis of Intermediate A-2

23 g (93.5 mmol) of Intermediate A-1 was dissolved in 30 mL of THF, and 44.0 mL (2.5 M solution in n-hexane, 110 mmol) of n-butyllithium was slowly added thereto at a temperature of −78° C. After 1 hour and 30 minutes, 24.0 mL (120 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added thereto. After the temperature was risen to room temperature, and the reaction product was stirred for 4 hours and the reaction was completed by adding water thereto, the reaction product was extracted with diethylether and washed with water three times. The organic layer was dried with magnesium sulfate and a solvent was removed therefrom under reduced pressure. In this regard, the obtained reaction product was purified with silica gel column chromatography to obtain 21.6 g of Intermediate A-2 having a yield of 79%. (C18H20BNO2: M+1 294.1)

Synthesis of Intermediate A-3

After dissolving 21 g of Intermediate A-2 (71.6 mmol), 18.4 g (81.4 mmol) of 2,4-dichloro-6-phenyl-1,3,5-triazine, 4.80 g (4.15 mmol) of tetrakistriphenylphosphinopalladium, 1.33 g (TATB, 4.15 mmol) of tetrabutylammonium bromide, and 52.9 g (249 mmol) of K3PO4in 830 mL of a mixed solution including toluene/ethanol/water (3/3/1 by volume), the reaction product was stirred by utilizing a reflux condenser at a temperature of 100° C. After 12 hours, the reaction solution was cooled to room temperature and was subjected to an extraction process with diethylether and water. In this regard, the obtained reaction product was purified with silica gel column chromatography to obtain 18.9 g of Intermediate A-3 having a yield of 74%. (C21H13ClN4: M+1 357.8)

Synthesis of Compound 1

18 g (50.4 mmol) of Intermediate A-3, 14 g (30.3 mmol) of Intermediate B-1 was dissolved in 200 mL of THF, and 4.40 mL (2.5 M solution in n-hexane, 11.0 mmol) of n-butyllithium was slowly added thereto at a temperature of −78° C. After 1 hour and 30 minutes, 19.32 g (72.0 mmol) of fluorodimesitylborane was dissolved in 100 mL of THF and added thereto. After the temperature was risen to room temperature, and the reaction product was stirred for 6 hours and the reaction was completed by adding water thereto, the reaction product was extracted with diethylether and washed with water three times. The organic layer was dried with magnesium sulfate and a solvent was removed therefrom under reduced pressure. In this regard, the obtained reaction product was purified with silica gel column chromatography to obtain 19.8 g of Compound 1 having a yield of 60%. (C45H32N4Si: M+1 657.8)

Synthesis Example 2: Synthesis of Compound 2

Compound 2 was synthesized to a yield of 75% in substantially the same manner and molar ratio as in the synthesis process of Compound 1, except that Intermediate B-2 was utilized instead of Intermediate B-1. (C45H32N4Si: M+1 657.8)

Synthesis Example 3: Synthesis of Compound 3

Compound 3 was synthesized to a yield of 60% in substantially the same manner and molar ratio as in the synthesis process of Compound 1, except that Intermediate B-3 was utilized instead of Intermediate B-1. (C45H32N4Si: M+1 657.8)

Synthesis Example 4: Synthesis of Compound 5

Synthesis of Intermediate C-1

Intermediate C-1 was synthesized to a yield of 60% in substantially the same manner as in the synthesis process of Intermediate A-3.

Synthesis of Compound 5

Compound 5 was synthesized to a yield of 55% in substantially the same manner and molar ratio as in the synthesis process of Compound 2, except that Intermediate C-1 was utilized instead of Intermediate A-3. (C51H36N4Si: M+1 733.9)

Table 1 shows1H NMR and MS/FAB of the synthesized compounds. Synthesis methods for other compounds than the compounds shown in Table 1 may be easily recognized by those skilled in the technical field by referring to the synthesis paths and source material materials described above.

As an anode, a Corning 15 Ω/cm2(1,200 Å) ITO glass substrate was cut to a size of 50 mm×50 mm×0.7 mm, sonicated with isopropyl alcohol and pure water each for 15 minutes, and then cleaned by exposure to ultraviolet rays and ozone for 30 minutes. The ITO glass substrate was loaded onto a vacuum deposition apparatus.

2-TNATA was vacuum-deposited on the ITO anode formed on the ITO glass 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.

Compound 1 and BCPDS (weight ratio of 1:1) as a host and PD17 as a dopant were co-deposited to a weight ratio of 90:10 on the hole transport layer to form an emission layer having a thickness of 300 Å.

Subsequently, TSPO1 was deposited on the emission layer to form a hole blocking layer having a thickness of 50 Å, Alq3was deposited on the hole blocking layer to form an electron transport layer having a thickness of 300 Å, LiF 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 LiF/Al electrode having a thickness of 3,000 Å, thereby completing the manufacture of a light-emitting device.

Examples 2 and 3 and Comparative Examples 1 to 3

Light-emitting devices were manufactured in substantially the same manner as in Example 1, except that compounds shown in Table 2 were utilized as a host in forming an emission layer.

As an anode, a glass substrate with 15 Ω/cm2(1,200 Å) ITO thereon, which was manufactured by Corning Inc., 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 exposure to ultraviolet rays and ozone for 30 minutes. Then the resultant glass substrate was loaded onto a vacuum deposition apparatus.

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

Compound 2 as a host and ACRSA as a dopant were co-deposited to a weight ratio of 92:8 on the hole transport layer to form an emission layer having a thickness of 300 Å.

Subsequently, DPEPO was deposited on the emission layer to form an electron transport layer having a thickness of 300 Å, LiF was deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and Al was vacuum-deposited on thereon to form a LiF/Al electrode having a thickness of 3,000 Å, thereby completing the manufacture of a light-emitting device.

Example 5 and Comparative Examples 4 and 5

Light-emitting devices were manufactured in substantially the same manner as in Example 4, except that compounds shown in Table 2 were utilized as a host in forming an emission layer.

Evaluation Example 1

To evaluate characteristics of the light-emitting devices manufactured according to Examples 1 to 5 and Comparative Examples 1 to 5, the driving voltage at a current density of 50 mA/cm2, luminance, luminescence efficiency, and half lifespan at a current density of 100 mA/cm2thereof were measured. The driving voltage of the light-emitting devices was measured utilizing a source meter (Keithley Instrument Inc., 2400 series). The quantum efficiency was measured utilizing quantum efficiency measurement device C9920-2-12 of Hamamatsu Photonics Inc. In the evaluation of quantum efficiency, luminance/current density was measured utilizing a luminance meter of which the wavelength sensitivity is calibrated. The half lifespan is a measure of time (hr) taken for the luminance to reach 50% of the initial luminance. Table 2 shows the evaluation results of the characteristics of the light-emitting devices.

From Table 2, the light-emitting devices of Examples 1 to 5 are each shown to have a lower driving voltage, excellent or suitable luminance, luminescence efficiency, and half lifespan compared to those of the light-emitting devices of Comparative Examples 1 to 5.

Although the present disclosure has been described with reference to the Synthesis Examples and Examples, these examples are provided for illustrative purpose only, and one of ordinary skill in the art may understand that these examples may have one or more suitable modifications and other examples equivalent thereto. Accordingly, the scope of the present disclosure should be determined by, but not limited to, the technical concept of the claims.

The heterocyclic compound may be utilized in manufacturing a light-emitting device having high efficiency and a long lifespan, and the light-emitting device may be utilized in manufacturing a high-quality electronic apparatus having high efficiency and a long lifespan.

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