Patent Application
20230219988
This application claims priority to and benefits of Korean Patent Application No. 10-2021-0156046 under 35 U.S.C. §119, filed on Nov. 12, 2021 in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.
Embodiments relate to an organometallic compound, a light-emitting device including the same, and an electronic apparatus including the light-emitting device.
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 characteristics in terms of luminance, driving voltage, and response speed, and produce full-color images.
In a light-emitting device, a first electrode is located on a substrate, and a hole transport region, an emission layer, an electron transport region, and a second electrode are sequentially formed 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. These excitons transition from an excited state to a ground state, thereby generating light.
It is to be understood that this background of the technology section is, in part, intended to provide useful background for understanding the technology. However, this background of the technology section may also include ideas, concepts, or recognitions that were not part of what was known or appreciated by those skilled in the pertinent art prior to a corresponding effective filing date of the subject matter disclosed herein.
Embodiments include an organometallic compound having high efficiency and a long lifespan, a light-emitting device including the organometallic compound, and an electronic apparatus including the light-emitting device.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the embodiments of the disclosure.
According to embodiments, an organometallic compound may be represented by Formula 1.
[0009] In Formula 1,
In an embodiment, CY1 may be a 5-membered ring, or a condensed ring of a 5-membered ring and a 6-membered ring; CY2, CY3, and CY5 may each independently be a 6-membered ring, or a condensed ring of a 5-membered ring and a 6-membered ring; and CY4 may be a 5-membered ring, a 6-membered ring, or a condensed ring of a 5-membered ring and a 6-membered ring.
In an embodiment, the 5-membered ring may be a cyclopentadiene group, a furan group, a pyrrole group, a thiophene group, an imidazole group, an oxazole group, an isoxazole group, a pyrazole group, a thiazole group, an isothiazole group, a triazole group, an oxadiazole group, a thiadiazole group, or a tetrazole group; and the 6-membered ring may be a benzene group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, or a tetrazine group.
In an embodiment, CY1 to CY5 may each independently be a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a cyclopentadiene group, a 1,2,3,4-tetrahydronaphthalene group, a thiophene group, a furan group, an indole group, a benzoborole group, a benzophosphole group, an indene group, a benzosilole group, a benzogermole group, a benzothiophene group, a benzoselenophene group, a benzofuran group, a carbazole group, a dibenzoborole group, a dibenzophosphole group, a fluorene group, a dibenzosilole group, a dibenzogermole group, a dibenzothiophene group, a dibenzoselenophene group, a dibenzofuran group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a tetrazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a tetrazole, a benzopyrazole group, a benzimidazole group, a benzotriazole, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, or a 5,6,7,8-tetrahydroquinoline group; and when Z1 is Se, at least one of CY3 and CY5 may each independently be an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a tetrazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, a tetrazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzotriazole, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, or a 5,6,7,8-tetrahydroquinoline group.
In an embodiment, a moiety represented by
in Formula 1 may be a moiety represented by Formula CY3-1, which is explained below.
In an embodiment, a moiety represented by
in Formula 1 may be a moiety represented by one of Formulae CY1-1 to CY1-70; a moiety represented by
in Formula 1 may be a moiety represented by one of Formulae CY2-1 to CY2-14; and a moiety represented by
in Formula 1 may be a moiety represented by one of Formulae CY4-1 to CY4-70, wherein Formulae CY1-1 to CY1-70, Formulae CY2-1 to CY2-14, and Formulae CY4-1 to CY4-70 are explained below.
In an embodiment, Y1 may be C, Y2 may be C, Y3 may be C, and Y4 may be N.
In an embodiment, Y1 may be N, and A1 may be a coordinate bond.
In an embodiment, at least one of R1(s) in the number of d1 and R4(s) in the number of d4 may each independently be a C1-C60 alkyl group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In an embodiment, the organometallic compound represented by Formula 1 may be represented by Formula 1-11 or Formula 1-12, which are explained below.
In an embodiment, the organometallic compound may be selected from Compounds 1 to 140, which are explained below.
According to embodiments, a light-emitting device may include a first electrode, a second electrode facing the first electrode, and an interlayer between the first electrode and the second electrode, and including an emission layer wherein the emission layer may include at least one organometallic compound represented by Formula 1.
In an embodiment, the first electrode may be an anode, the second electrode may be a cathode, and the interlayer may further include a hole transport region between the first electrode and the emission layer and an electron transport region between the emission layer and the second electrode. The hole transport region may include a hole injection layer, a hole transport layer, an emission auxiliary layer, an electron blocking layer, or any combination thereof. The electron transport region may include a hole blocking layer, an electron transport layer, an electron injection layer, or any combination thereof.
In an embodiment, the emission layer may further include a compound represented by Formula 1A, Formula 301-1, or Formula 301-2, which are explained below.
In an embodiment, the emission layer may further include a fluorescent compound, a thermally activated delayed fluorescence (TADF) compound satisfying Equation 1, or any combination thereof, wherein Equation 1 is explained below.
In an embodiment, an amount of the at least one organometallic compound may be in a range of about 0.01 parts by weight to about 49.99 parts by weight, based on total 100 parts by weight of the emission layer.
In an embodiment, the emission layer may emit light having a ClEy equal to or less than about 0.20.
According to embodiments, an electronic apparatus may include the light-emitting device.
In an embodiment, the electronic apparatus may further include a thin-film transistor, 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 at least one of the source electrode and the drain electrode of the thin-film transistor.
In an embodiment, the electronic apparatus may further include a color filter, a color conversion layer, a touch screen layer, a polarizing layer, or any combination thereof.
The above and other aspects, features, and advantages of the embodiments of the disclosure will be more apparent from the following description taken in conjunction with the accompanying drawings, in which:
The disclosure will now be described more fully hereinafter with reference to the accompanying drawings, in which embodiments are shown. This disclosure may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
In the drawings, the sizes, thicknesses, ratios, and dimensions of the elements may be exaggerated for ease of description and for clarity. Like numbers refer to like elements throughout.
In the description, it will be understood that when an element (or region, layer, part, etc.) is referred to as being “on”, “connected to”, or “coupled to” another element, it can be directly on, connected to, or coupled to the other element, or one or more intervening elements may be present therebetween. In a similar sense, when an element (or region, layer, part, etc.) is described as “covering” another element, it can directly cover the other element, or one or more intervening elements may be present therebetween.
In the description, when an element is “directly on,” “directly connected to,” or “directly coupled to” another element, there are no intervening elements present. For example, “directly on” may mean that two layers or two elements are disposed without an additional element such as an adhesion element therebetween.
As used herein, the expressions used in the singular such as “a,” “an,” and “the,” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. For example, “A and/or B” may be understood to mean “A, B, or A and B.” The terms “and” and “or” may be used in the conjunctive or disjunctive sense and may be understood to be equivalent to “and/or”.
In the specification and the claims, the term “at least one of” is intended to include the meaning of “at least one selected from the group of” for the purpose of its meaning and interpretation. For example, “at least one of A and B” may be understood to mean “A, B, or A and B.” When preceding a list of elements, the term, “at least one of,” modifies the entire list of elements and does not modify the individual elements of the list.
It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element. Thus, a first element could be termed a second element without departing from the teachings of the disclosure. Similarly, a second element could be termed a first element, without departing from the scope of the disclosure.
The spatially relative terms “below”, “beneath”, “lower”, “above”, “upper”, or the like, may be used herein for ease of description to describe the relations between one element or component and another element or component as illustrated in the drawings. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation, in addition to the orientation depicted in the drawings. For example, in the case where a device illustrated in the drawing is turned over, the device positioned “below” or “beneath” another device may be placed “above” another device. Accordingly, the illustrative term “below” may include both the lower and upper positions. The device may also be oriented in other directions and thus the spatially relative terms may be interpreted differently depending on the orientations.
The terms “about” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the recited value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the recited quantity (i.e., the limitations of the measurement system). For example, “about” may mean within one or more standard deviations, or within ±20%, ±10%, or ±5% of the stated value.
It should be understood that the terms “comprises,” “comprising,” “includes,” “including,” “have,” “having,” “contains,” “containing,” and the like are intended to specify the presence of stated features, integers, steps, operations, elements, components, or combinations thereof in the disclosure, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.
Unless otherwise defined or implied herein, all terms (including technical and scientific terms) used have the same meaning as commonly understood by those skilled in the art to which this disclosure pertains. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and should not be interpreted in an ideal or excessively formal sense unless clearly defined in the specification.
An organometallic compound may be represented by Formula 1:
In Formula 1, M may be a transition metal.
In an embodiment, M may be platinum (Pt), palladium (Pd), copper (Cu), silver (Ag), gold (Au), rhodium (Rh), iridium (Ir), ruthenium (Ru), or osmium (Os).
In Formula 1, CY1 to CY5 may each independently be a C3-C60 carbocyclic group or a C1-C60 heterocyclic group.
In an embodiment, CY1 may be a 5-membered ring, or a condensed ring of a 5-membered ring and a 6-membered ring; CY2, CY3, and CY5 may each independently be a 6-membered ring, or a condensed ring of a 5-membered ring and a 6-membered ring; and CY4 may be a 5-membered ring, a 6-membered ring, or a condensed ring of a 5-membered ring and a 6-membered ring.
In an embodiment, the 5-membered ring may be a cyclopentadiene group, a furan group, a pyrrole group, a thiophene group, an imidazole group, an oxazole group, an isoxazole group, a pyrazole group, a thiazole group, an isothiazole group, a triazole group, an oxadiazole group, a thiadiazole group, or a tetrazole group; and the 6-membered ring may be a benzene group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, or a tetrazine group.
In Formula 1, Y1 to Y4 may each independently be C or N.
In an embodiment, Y1 may be C, Y2 may be C, Y3 may be C, and Y4 may be N.
In Formula 1, A1 to A4 may each independently be a chemical bond, O, or S.
The chemical bond may be a covalent bond, a metal bond, or a coordinate bond, but is not limited thereto.
In an embodiment, Y1 may be N, and A1 may be a coordinate bond.
In an embodiment, Y4 may be N, and A4 may be a metal bond.
In Formula 1, T1 to T3 may each independently be a single bond, a double bond, *-N[(L1)b1—(R1a)]—*’, *—B(R1a)—*’, *—P(R1a)—*’, *—C(R1a)(R1b)—*’, *—Si(R1a)(R1b)—*’, *—Ge(R1a)(R1b)—*’, *—S—*’, *—Se—*’, *—O—*’, *—C(═O)—*’, *—S(═O)—*’, *—S(═O)2—*’, *—C(R1a)═*’, *═C(R1a)—*’, *—C(R1a)═C(R1b)—*’, *—C(═S)—*’, or*—C≡C—*’.
In Formula 1, a1 to a3 may each independently be an integer from 1 to 3.
In an embodiment, T2 may be *—O—*’, and a2 may be 1.
In Formula 1, L1 may be a single bond, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a,
In Formula 1, b1 may be an integer from 0 to 3,
In Formula 1, Z1 may be Se or Te.
In Formula 1, when Z1 is Se, at least one of CY3 and CY5 may each independently be a π electron-deficient nitrogen-containing C1-C60 cyclic group.
In an embodiment, CY1 to CY5 may each independently be a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a cyclopentadiene group, a 1,2,3,4-tetrahydronaphthalene group, a thiophene group, a furan group, an indole group, a benzoborole group, a benzophosphole group, an indene group, a benzosilole group, a benzogermole group, a benzothiophene group, a benzoselenophene group, a benzofuran group, a carbazole group, a dibenzoborole group, a dibenzophosphole group, a fluorene group, a dibenzosilole group, a dibenzogermole group, a dibenzothiophene group, a dibenzoselenophene group, a dibenzofuran group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a tetrazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a tetrazole, a benzopyrazole group, a benzimidazole group, a benzotriazole, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, or a 5,6,7,8-tetrahydroquinoline group, and when Z1 is Se, at least one of CY3 and CY5 may each independently be an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a tetrazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, a tetrazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzotriazole, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, or a 5,6,7,8-tetrahydroquinoline group.
In embodiments, when Z1 is Se, at least one of CY3 and CY5 may each independently be a π electron-deficient nitrogen-containing C1-C60 cyclic group.
In an embodiment, a moiety represented by
in Formula 1 may be a moiety represented by Formula CY3-1:
[0087] In Formula CY3-1,
In an embodiment, a moiety represented by
in Formula 1 may be a moiety represented by one of Formulae CY1-1 to CY1-70,
In Formula 1, R1a, R1b, and R1 to R5 may each independently be hydrogen, deuterium, —F, —Cl, —Br, -l, a hydroxyl group, a cyano group, a nitro group, a C1-C60 alkyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkenyl group unsubstituted or substituted with at least one R10a, a C2-C60 alkynyl group unsubstituted or substituted with at least one R10a, a C1-C60 alkoxy group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a, a C6-C60 aryloxy group unsubstituted or substituted with at least one R10a, a C6-C60 arylthio group unsubstituted or substituted with at least one R10a, —Si(Q1)(Q2)(Q3), —N(Q1)(Q2), —B(Q1)(Q2), —C(═O)(Q1), —S(═O)2(Q1), or —P(═O)(Q1)(Q2).
In Formula 1, d1 to d5 may each independently be an integer from 0 to 10.
In Formula 1, two or more neighboring groups of R1a, R1b, and R1 to R5 may optionally be linked to each other to form a C5-C30 carbocyclic group unsubstituted or substituted with at least one R10a or a C2-C30 heterocyclic group unsubstituted or substituted with at least one R10a.
In an embodiment, at least one of R1(s) in the number of d1 and R4(s) in the number of d4 may each independently be a C1-C60 alkyl group unsubstituted or substituted with at least one R10a, a C3-C60 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C60 heterocyclic group unsubstituted or substituted with at least one R10a.
In an embodiment, in the organometallic compound represented by Formula 1, at least one hydrogen may be substituted with deuterium.
R10a may be:
In an embodiment, the organometallic compound represented by Formula 1 may be represented by Formula 1-11 or Formula 1-12:
[00130] In Formulae 1-11 and 1-12,
In an embodiment, the organometallic compound represented by Formula 1 may be selected from Compounds 1 to 140, but is not limited thereto:
The organometallic compound represented by Formula 1 disclosed herein has a structure that includes ligands linked by a moiety including Se or Te, wherein, when Z1 is Se, at least one of rings linked by the moiety is a π electron-deficient nitrogen-containing C1-C60 cyclic group.
Since the organometallic compound includes the ligands linked by the moiety including Se or Te, a dipole moment in the organometallic compound may be stabilized, and thus, stability of the compound may be increased. Accordingly, a light-emitting device including the organometallic compound may have improved luminescence efficiency and lifespan.
In the organometallic compound, when Z1 is Se, a π electron-deficient nitrogen-containing C1-C60 cyclic group may be included in at least one of the rings linked by the moiety (for example, a group represented by ring CY3 or ring CY5 in Formula 1), and thus, a highest occupied molecular orbital (HOMO) energy level of the organometallic compound may become relatively low. Accordingly, an emission wavelength may shift to a shorter wavelength, thereby enabling the emission of blue light having high color purity.
Accordingly, an electronic device, for example, a light-emitting device, that includes the organometallic compound represented by Formula 1 may have a low driving voltage, high efficiency, and a long lifespan, and may emit deep-blue light, thereby having high color purity.
Synthesis methods of the organometallic compound represented by Formula 1 may be recognizable by one of ordinary skill in the art by referring to Synthesis Examples and/or Examples provided below.
At least one organometallic compound represented by Formula 1 may be used in a light-emitting device (for example, an organic light-emitting device). Accordingly, provided is a light-emitting device which may include a first electrode, a second electrode facing the first electrode, and an interlayer between the first electrode and the second electrode and including an emission layer, and at least one of the organometallic compound represented by Formula 1 as described in the specification.
In an embodiment,
In embodiments, the organometallic compound may be included between a pair of electrodes of the light-emitting device. Accordingly, the organometallic compound may be included in the interlayer of the light-emitting device, for example, in the emission layer of the interlayer. In embodiments, the emission layer may include at least one organometallic compound represented by Formula 1.
In an embodiment, the emission layer may further include at least one Si-based compound.
The term “Si-based compound” may be a compound including a Si atom, for example, a compound including a silyl group.
In an embodiment, the emission layer may include a first host and a second host, and the first host may be different from the second host.
In an embodiment, the first host may be a hole transporting compound including at least one electron withdrawing group, and the second host may be an electron transporting compound including at least one electron donating group.
In an embodiment, the first host may be represented by Formula 1A:
[00155] In Formula 1A,
In an embodiment, the second host may be represented by Formula 301-1 or Formula 301-2:
[00167] In Formulae 301-1 and 301-2,
In an embodiment, the first host may include a Si-based compound.
In an embodiment, the second host may include a Si-based compound.
In an embodiment, the emission layer may further include a fluorescent compound, a thermally activated delayed fluorescence (TADF) compound satisfying Equation 1, or any combination thereof:
In Equation 1, S1 is a lowest excited singlet energy level (eV) of the TADF compound, and T1 is a lowest excited triplet energy level (eV) of the TADF compound.
In an embodiment, the TADF compound may be represented by Formula 3A:
[00180] In Formula 3A,
In an embodiment, the first host may be selected from Compounds ETH1 to ETH84 of Group I, but is not limited thereto.
In an embodiment, the second host may be selected from Compounds HTH1 to HTH52 of Group II, but is not limited thereto.
In an embodiment, the TADF compound may be selected from Compounds DFD1 to DFD12 of Group III, but is not limited thereto.
In an embodiment, an amount of the organometallic compound may be in a range of about 0.01 parts by weight to about 49.99 parts by weight, based on a total of 100 parts by weight of the emission layer.
In an embodiment, the emission layer may emit blue light or blue-green light.
In an embodiment, the emission layer may emit light having a maximum emission wavelength in a range of about 400 nm to about 500 nm.
In an embodiment, the emission layer may emit light having a ClEy equal to or less than about 0.20.
The expression “(an interlayer) includes an organometallic compound” as used herein may include a case in which “(an interlayer) includes identical organometallic compounds represented by Formula 1” and a case in which “(an interlayer) includes two or more different organometallic compounds represented by Formula 1.”
For example, the interlayer may include, as the organometallic compound, only Compound 1. In this regard, Compound 1 may be present in the emission layer of the light-emitting device. In embodiments, 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 a same layer (for example, both 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 layers located between the first electrode and the second electrode of the light-emitting device.
Another aspect of the disclosure provides 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 at least one of the source electrode and the drain electrode. In embodiments, the electronic apparatus may further include a color filter, a color conversion layer, a touch screen layer, a polarizing layer, or any combination thereof. Further details on the electronic apparatus may be found in reference to related descriptions as provided herein.
Hereinafter, the structure of the light-emitting device 10 according to an embodiment and a method of manufacturing the light-emitting device 10 will be described with reference to
In
The first electrode 110 may be formed by, for example, depositing or sputtering a material for forming the first electrode 110 on the substrate. When the first electrode 110 is an anode, a material for forming the first electrode 110 may be a high-work function material that facilitates injection of holes.
The first electrode 110 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. When the first electrode 110 is a transmissive electrode, a material for forming the first electrode 110 may include indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), or any combination thereof. In embodiments, when the first electrode 110 is a semi-transmissive electrode or a reflective electrode, a material for forming the first electrode 110 may include magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), or any combination thereof.
The first electrode 110 may have a structure consisting of a single layer or a structure including multiple layers. For example, the first electrode 110 may have a three-layered structure of ITO/Ag/ITO.
The interlayer 130 is located on the first electrode 110. The interlayer 130 includes an emission layer.
The interlayer 130 may further include a hole transport region located between the first electrode 110 and the emission layer and an electron transport region located between the emission layer and the second electrode 150.
The interlayer 130 may further include, in addition to various organic materials, a metal-containing compound such as an organometallic compound, an inorganic material such as quantum dots, or the like.
In embodiments, the interlayer 130 may include two or more emitting units sequentially stacked between the first electrode 110 and the second electrode 150, and at least one charge generation layer between the two or more emitting units. When the interlayer 130 includes the two or more emitting units and the at least one charge generation layer as described above, the light-emitting device 10 may be a tandem light-emitting device.
The hole transport region may have a structure consisting of a layer consisting of a single material, a structure consisting of a layer consisting of different materials, or a structure including multiple layers including different materials.
The hole transport region may include a hole injection layer, a hole transport layer, an emission auxiliary layer, an electron-blocking layer, or any combination thereof.
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, wherein the layers of each structure may be stacked from the first electrode 110 in its respective stated order, but the structure of the hole transport region is not limited thereto.
The hole transport region may include a compound represented by Formula 201, a compound represented by Formula 202, or any combination thereof:
[00217] In Formulae 201 and 202,
In embodiments, each of Formulae 201 and 202 may include at least one of groups represented by Formulae CY201 to CY217:
In Formulae CY201 to CY217, R10b and R10c are each independently the same as described in connection with R10a, ring CY201 to ring CY204 may each independently be a C3-C20 carbocyclic group or a C1-C20 heterocyclic group, and at least one hydrogen in Formulae CY201 to CY217 may be unsubstituted or substituted with R10a.
In an embodiment, 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 embodiments, each of Formulae 201 and 202 may include at least one of groups represented by Formulae CY201 to CY203.
In embodiments, 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 embodiments, in Formula 201, xa1 may be 1, R201 may be a group represented by one of Formulae CY201 to CY203, xa2 may be 0, and R202 may be a group represented by one of Formulae CY204 to CY207.
In embodiments, each of Formulae 201 and 202 may not include a group represented by one of Formulae CY201 to CY203.
In embodiments, each of Formulae 201 and 202 may not include groups represented by Formulae CY201 to CY203, and may include at least one of groups represented by Formulae CY204 to CY217.
In embodiments, each of Formulae 201 and 202 may not include a group represented by one of Formulae CY201 to CY217.
For example, the hole transport region may include one of Compounds HT1 to HT44, m-MTDATA, TDATA, 2-TNATA, NPB(NPD), β-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (PANI/CSA), polyaniline/poly(4-styrenesulfonate) (PANI/PSS), or any combination thereof:
A thickness of the hole transport region may be in a range of about 50 Å to about 10,000 Å. For example, the thickness of the hole transport region may be in a range of about 100 Å to about 4,000 Å. When the hole transport region includes a hole injection layer, a hole transport layer, or any combination thereof, a thickness of the hole injection layer may be in a range of about 100 Å to about 9,000 Å, and a thickness of the hole transport layer may be in a range of about 50 Å to about 2,000 Å. For example, the thickness of the hole injection layer may be in a range of about 100 Å to about 1,000 Å. For example, the thickness of the hole transport layer may be in a range of about 100 Å to about 1,500 Å. When the thicknesses of the hole transport region, the hole injection layer, and the hole transport layer are within these ranges, satisfactory hole transporting characteristics may be obtained without a substantial increase in driving voltage.
The emission auxiliary layer may increase light-emission efficiency by compensating for an optical resonance distance according to a wavelength of light emitted by an emission layer, and the electron blocking layer may block 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 the materials as described above, a charge-generation material for improving conductive properties. The charge-generation material may be 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, a lowest unoccupied molecular orbital (LUMO) energy level of the p-dopant may be equal to or less than about -3.5 eV.
In an embodiment, the p-dopant may include a quinone derivative, a cyano group-containing compound, a compound containing element EL1 and element EL2, or any combination thereof.
Examples of the quinone derivative may include TCNQ, F4-TCNQ, and the like.
Examples of the cyano group-containing compound may include HAT-CN, a compound represented by Formula 221, and the like:
[00245] In Formula 221,
In the compound containing element EL1 and element EL2, element EL1 may be a metal, a metalloid, or any combination thereof, and element EL2 may be a non-metal, a metalloid, or any combination thereof.
Examples of the metal may include: an alkali metal (for example, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.); an alkaline earth metal (for example, beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.); a transition metal (for example, titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), etc.); a post-transition metal (for example, zinc (Zn), indium (In), tin (Sn), etc.); and a lanthanide metal (for example, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), etc.).
Examples of the metalloid may include silicon (Si), antimony (Sb), and tellurium (Te).
Examples of the non-metal may include oxygen (O) and a halogen (for example, F, Cl, Br, I, etc.).
Examples of the compound containing element EL1 and element EL2 may include a metal oxide, a metal halide (for example, a metal fluoride, a metal chloride, a metal bromide, a metal iodide, etc.), a metalloid halide (for example, a metalloid fluoride, a metalloid chloride, a metalloid bromide, a metalloid iodide, etc.), a metal telluride, or any combination thereof.
Examples of the metal oxide may include tungsten oxide (for example, WO, W2O3, WO2, WO3, W2O5, etc.), vanadium oxide (for example, VO, V2O3, VO2, V2O5, etc.), molybdenum oxide (MoO, Mo2O3, MoO2, MoO3, Mo2O5, etc.), and rhenium oxide (for example, ReO3, etc.).
Examples of the metal halide may include an alkali metal halide, an alkaline earth metal halide, a transition metal halide, a post-transition metal halide, and a lanthanide metal halide.
Examples of the alkali metal halide may include LiF, NaF, KF, RbF, CsF, LiCl, NaCl, KCl, RbCl, CsCl, LiBr, NaBr, KBr, RbBr, CsBr, Lil, Nal, Kl, Rbl, and Csl.
Examples of the alkaline earth metal halide may include BeF2, MgF2, CaF2, SrF2, BaF2, BeCl2, MgCl2, CaCl2, SrCl2, BaCl2, BeBr2, MgBr2, CaBr2, SrBr2, BaBr2, Bel2, Mgl2, Cal2, Srl2, and Bal2.
Examples of the transition metal halide may include a titanium halide (for example, TiF4, TiCl4, TiBr4, Til4, etc.), a zirconium halide (for example, ZrF4, ZrCl4, ZrBr4, Zrl4, etc.), a hafnium halide (for example, HfF4, HfCl4, HfBr4, Hfl4, etc.), a vanadium halide (for example, VF3, VCl3, VBr3, Vl3, etc.), a niobium halide (for example, NbF3, NbCl3, NbBr3, Nbl3, etc.), a tantalum halide (for example, TaF3, TaCl3, TaBr3, Tal3, etc.), a chromium halide (for example, CrF3, CrCl3, CrBr3, Crl3, etc.), a molybdenum halide (for example, MoF3, MoCl3, MoBr3, Mol3, etc.), a tungsten halide (for example, WF3, WCl3, WBr3, Wl3, etc.), a manganese halide (for example, MnF2, MnCl2, MnBr2, Mnl2, etc.), a technetium halide (for example, TcF2, TcCl2, TcBr2, Tcl2, etc.), a rhenium halide (for example, ReF2, ReCl2, ReBr2, Rel2, etc.), an iron halide (for example, FeF2, FeCl2, FeBr2, Fel2, etc.), a ruthenium halide (for example, RuF2, RuCl2, RuBr2, Rul2, etc.), an osmium halide (for example, OsF2, OsCl2, OsBr2, Osl2, etc.), a cobalt halide (for example, CoF2, CoCl2, CoBr2, Col2, etc.), a rhodium halide (for example, RhF2, RhCl2, RhBr2, Rhl2, etc.), an iridium halide (for example, IrF2, IrCl2, IrBr2, Irl2, etc.), a nickel halide (for example, NiF2, NiCl2, NiBr2, Nil2, etc.), a palladium halide (for example, PdF2, PdCl2, PdBr2, Pdl2, etc.), a platinum halide (for example, PtF2, PtCl2, PtBr2, Ptl2, etc.), a copper halide (for example, CuF, CuCl, CuBr, Cul, etc.), a silver halide (for example, AgF, AgCl, AgBr, Agl, etc.), and a gold halide (for example, AuF, AuCl, AuBr, Aul, etc.).
Examples of the post-transition metal halide may include a zinc halide (for example, ZnF2, ZnCl2, ZnBr2, Znl2, etc.), an indium halide (for example, Inl3, etc.), and a tin halide (for example, Snl2, etc.).
Examples of the lanthanide metal halide may include YbF, YbF2, YbF3, SmF3, YbCl, YbCl2, YbCl3 SmCl3, YbBr, YbBr2, YbBr3 SmBr3, Ybl, Ybl2, Ybl3, and Sml3.
Examples of the metalloid halide may include an antimony halide (for example, SbCl5, etc.).
Examples of the metal telluride may include an alkali metal telluride (for example, Li2Te, a na2Te, K2Te, Rb2Te, Cs2Te, etc.), an alkaline earth metal telluride (for example, BeTe, MgTe, CaTe, SrTe, BaTe, etc.), a transition metal telluride (for example, TiTe2, ZrTe2, HfTe2, V2Te3, Nb2Te3, Ta2Te3, Cr2Te3, Mo2Te3, W2Te3, MnTe, TcTe, ReTe, FeTe, RuTe, OsTe, CoTe, RhTe, IrTe, NiTe, PdTe, PtTe, Cu2Te, CuTe, Ag2Te, AgTe, Au2Te, etc.), a post-transition metal telluride (for example, ZnTe, etc.), and a lanthanide metal telluride (for example, LaTe, CeTe, PrTe, NdTe, PmTe, EuTe, GdTe, TbTe, DyTe, HoTe, ErTe, TmTe, YbTe, LuTe, etc.).
When the light-emitting device 10 is a full-color light-emitting device, the emission layer may be patterned into a red emission layer, a green emission layer, and/or a blue emission layer, according to a subpixel. In embodiments, the emission layer may have a stacked structure of two or more layers of a red emission layer, a green emission layer, and a blue emission layer, in which the two or more layers may contact each other or may be separated from each other to emit white light. In embodiments, the emission layer may include two or more materials of a red light-emitting material, a green light-emitting material, and a blue light-emitting material, in which the two or more materials are mixed with each other in a single layer to emit white light.
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 dopant may include the organometallic compound represented by Formula 1.
An amount of the dopant in the emission layer may be in a range of about 0.01 parts by weight to about 15 parts by weight, based on a total of 100 parts by weight of the host.
In embodiments, the emission layer may include a quantum dot.
In embodiments, the emission layer may include a delayed fluorescence material. The delayed fluorescence material may serve as the host or the dopant in the emission layer.
A thickness of the emission layer may be in a range of about 100 Å to about 1,000 Å. For example, the thickness of the emission layer may be in a range of about 200 Å to about 600 Å. When the thickness of the emission layer is within these ranges, excellent light-emission characteristics may be obtained without a substantial increase in driving voltage.
Further details on the host may be found in reference to related descriptions as provided herein.
The host may include a compound represented by Formula 301:
[00273] In Formula 301,
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 embodiments, the host may include a compound represented by Formula 301-1, a compound represented by Formula 301-2, or any combination thereof:
[00282] In Formulae 301-1 and 301-2,
In an 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 any combination thereof.
In embodiments, the host may include one of Compounds H1 to H124, one of Compounds ETH1 to ETH84 (as shown above), one of Compounds HTH1 to HTH52 (as shown above), 9,10-di(2-naphthyl)anthracene (ADN), 2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN), 9,10-di-(2-naphthyl)-2-t-butyl-anthracene (TBADN), 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP), 1,3-di-9-carbazolylbenzene (mCP), 3,3-di(9H-carbazol-9-yl)biphenyl (mCBP), 1,3,5-tri(carbazol-9-yl)benzene (TCP), or any combination thereof:
The emission layer may include a delayed fluorescence material.
In the specification, the delayed fluorescence material may be selected from compounds capable of emitting delayed fluorescence by a delayed fluorescence emission mechanism.
The delayed fluorescence material included in the emission layer may serve as a host or as a dopant, depending on the type of other materials included in the emission layer.
In an embodiment, a difference between a triplet energy level (eV) of the delayed fluorescence material and a singlet energy level (eV) of the delayed fluorescence material may be in a range of about 0 eV to about 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 device 10 may be improved.
For example, the delayed fluorescence material may include a material including at least one electron donor (for example, a TT electron-rich C3-C60 cyclic group, such as a carbazole group) and at least one electron acceptor (for example, a sulfoxide group, a cyano group, or a TTelectron-deficient nitrogen-containing C1-C60 cyclic group), and a material including a C8-C60 polycyclic 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 Compounds DF1 to DF9 or at least one of Compounds DFD1 to DFD12 (as shown above):
The emission layer may include a quantum dot.
The term “quantum dot” as used herein may be a crystal of a semiconductor compound, and may include any material capable of emitting light of various emission wavelengths according to a size of the crystal.
A diameter of the quantum dot may be, for example, in a range of about 1 nm to about 10 nm.
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 thereto.
The wet chemical process is a method including mixing a precursor material with an organic solvent and 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 through a process which has lower costs, and may be more readily performed than vapor deposition methods, such as metal organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE),
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 any combination thereof.
Examples of the Group II-VI semiconductor compound may include: a binary compound, such as CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, or MgS; a ternary compound, such as CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, or MgZnS; a quaternary compound, such as CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, or HgZnSTe; or any combination thereof.
Examples of the Group III-V semiconductor compound may include: a binary compound, such as GaN, GaP, GaAs, GaSb, AIN, AIP, AlAs, AlSb, InN, InP, InAs, or InSb; a ternary compound, such as GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AINP, AINAs, AINSb, AlPAs, AlPSb, InGaP, InNP, InAlP, InNAs, InNSb, InPAs, InPSb, or GaAINP; a quaternary compound, such as GaAlNAs, GaAlNSb, GaAIPAs, GaAIPSb, GalnNP, GalnNAs, GaInNSb, GalnPAs, GalnPSb, InAlNP, InAlNAs, InAlNSb, InAIPAs, or InAIPSb; or any combination thereof. In an embodiment, the Group III-V semiconductor compound may further include a Group II element. Examples of the Group III-V semiconductor compound further including a Group II element may include InZnP, InGaZnP, and InAIZnP.
Examples of the Group III-VI semiconductor compound may include: a binary compound, such as GaS, GaSe, Ga2Se3, GaTe, InS, InSe, In2Se3, or InTe; a ternary compound, such as InGaS3, or InGaSe3; or any combination thereof.
Examples of the Group I-III-VI semiconductor compound may include: a ternary compound, such as AglnS, AgInS2, CulnS, CulnS2, CuGaO2, AgGaO2, or AgAlO2; or any combination thereof.
Examples of the Group IV-VI semiconductor compound may include: 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 any combination thereof.
Examples of the Group IV element or compound may include: a single element material, such as Si or Ge; a binary compound, such as SiC or SiGe; or any combination thereof.
Each element included in a multi-element compound such as a binary compound, a ternary compound, and a quaternary compound may be present in a particle at a uniform concentration or at a non-uniform concentration.
The quantum dot may have a single structure or a core-shell structure. When the quantum dot has a single structure, a concentration of each element included in the corresponding quantum dot may be uniform. When the quantum dot has a core-shell structure a material included in the core and a material included in the shell may be different from each other.
The shell of the quantum dot may serve as a protective layer that prevents chemical degeneration of the core to maintain semiconductor characteristics, and/or may serve as a charging layer that imparts electrophoretic characteristics to the quantum dot. The shell may be a single layer or a multi-layer. An 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 core.
Examples of the shell of the quantum dot may include a metal oxide, a non-metal oxide, a semiconductor compound, or any combination thereof. Examples of the metal oxide or the non-metal oxide 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 any combination thereof. Examples of the semiconductor compound may include, as described herein: 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; or any combination thereof. Examples of the semiconductor compound may include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnSeS, ZnTeS, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InGaP, InSb, AlAs, AIP, AlSb, or any combination thereof.
A full width at half maximum (FWHM) of an emission wavelength spectrum of the quantum dot may be equal to or less than about 45 nm. For example, a FWHM of an emission wavelength spectrum of the quantum dot may be equal to or less than about 40 nm. For example, a FWHM of an emission wavelength spectrum of the quantum dot may be equal to or less than about 30 nm. Within these ranges, color purity or color reproducibility may be increased. Light emitted through the quantum dot may be emitted in all directions, and thus, an optical viewing angle may be improved.
The quantum dot may be in the form of a 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.
Since the energy band gap may be adjusted by controlling the size of the quantum dot, light having various wavelength bands may be obtained from the quantum dot emission layer. Accordingly, by using quantum dots of different sizes, a light-emitting device that emits light of various wavelengths may be implemented. In embodiments, the size of the quantum dot may be selected to emit red, green and/or blue light. The size of the quantum dot may be configured to emit white light by combination of light of various colors.
The electron transport region may have a structure consisting of a layer consisting of a single material, a structure consisting of a layer consisting of different materials, or a structure including multiple layers including different materials.
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 any combination 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, wherein the layers of each structure may be stacked from the emission layer in its respective stated order, but the structure of the electron transport region is not limited thereto.
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-C60 cyclic group.
For example, the electron transport region may include a compound represented by Formula 601:
[00325] In Formula 601,
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 embodiments, Ar601 in Formula 601 may be a substituted or unsubstituted anthracene group.
In embodiments, the electron transport region may include a compound represented by Formula 601-1:
[00336] In Formula 601-1,
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-1,10-1 phenanthroline (Bphen), diphenyl(4-(triphenylsilyl)phenyl)-phosphine oxide (TSPO1), Alq3, BAlq, TAZ, NTAZ, or any combination thereof:
A thickness of the electron transport region may be in a range of about 160 Å to about 5,000 Å. For example, the thickness of the electron transport region may be in a range of about 100 Å to about 4,000 Å. When the electron transport region includes a buffer layer, a hole blocking layer, an electron control layer, an electron transport layer, or any combination thereof, a thickness of the buffer layer, the hole blocking layer, or the electron control layer may each independently be in a range of about 20 Å to about 1,000 Å, and a thickness of the electron transport layer may be in a range of about 100 Å to about 1,000 Å. For example, the thickness of the buffer layer, the hole blocking layer, or the electron control layer may each independently be in a range of about 30 Å to about 300 Å. For example, the thickness of the electron transport layer may be in a range of about 150 Å to about 500 Å. When the thickness of the buffer layer, the hole blocking layer, the electron control layer, the electron transport layer, and/or the electron transport region are within these ranges, satisfactory electron transporting characteristics may be obtained without a substantial increase in driving voltage.
The electron transport region (for example, the electron transport layer in the electron transport region) may further include, in addition to the materials described above, a metal-containing material.
The metal-containing material may include an alkali metal complex, an alkaline earth metal complex, or any combination thereof. The metal ion of an alkali metal complex may be a Li ion, a Na ion, a K ion, a Rb ion, or a Cs ion, and the metal ion of an alkaline earth metal complex may be a Be ion, a Mg ion, a Ca ion, a Sr ion, or a Ba ion. A ligand coordinated with the metal ion of the alkali metal complex or the metal ion of the alkaline earth metal complex may each independently be hydroxyquinoline, hydroxyisoquinoline, hydroxybenzoquinoline, hydroxyacridine, hydroxyphenanthridine, hydroxyphenyloxazole, hydroxyphenylthiazole, hydroxyphenyloxadiazole, hydroxyphenylthiadiazole, hydroxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxyphenylbenzothiazole, bipyridine, phenanthroline, cyclopentadiene, or any combination thereof.
In an embodiment, the metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 (LiQ) or Compound ET-D2:
The electron transport region may include an electron injection layer that facilitates the injection of electrons from the second electrode 150. The electron injection layer may directly contact the second electrode 150.
The electron injection layer may have a structure consisting of a layer consisting of a single material, a structure consisting of a layer consisting of different materials, or a structure including multiple layers including different materials.
The electron injection layer may include 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 any combination thereof.
The alkali metal may include Li, Na, K, Rb, Cs, or any combination thereof. The alkaline earth metal may include Mg, Ca, Sr, Ba, or any combination thereof. The rare earth metal may include Sc, Y, Ce, Tb, Yb, Gd, or any combination thereof.
The alkali metal-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 any combination thereof.
The alkali metal-containing compound may include: alkali metal oxides, such as Li2O, Cs2O, K2O, and the like; alkali metal halides, such as LiF, NaF, CsF, KF, Lil, Nal, Csl, Kl, and the like; or any combination thereof. The alkaline earth metal-containing compound may include an alkaline earth metal compound, such as BaO, SrO, CaO, BaxSr1-xO (wherein x is a real number satisfying the condition of 0<x<1), BaxCa1-xO (wherein x is a real number satisfying the condition of 0<x<1), or the like. The rare earth metal-containing compound may include YbF3, ScF3, Sc2O3, Y2O3, Ce2O3, GdF3, TbF3, Ybl3, Scl3, Tbl3, or any combination thereof. In embodiments, the rare earth metal-containing compound may include a lanthanide metal telluride. Examples of the lanthanide metal telluride may include LaTe, CeTe, PrTe, NdTe, PmTe, SmTe, EuTe, GdTe, TbTe, DyTe, HoTe, ErTe, TmTe, YbTe, LuTe, La2Te3, Ce2Te3, Pr2Te3, Nd2Te3, Pm2Te3, Sm2Te3, Eu2Te3, Gd2Te3, Tb2Te3, Dy2Te3, Ho2Te3, Er2Te3, Tm2Te3, Yb2Te3, Lu2Te3, and the like.
The alkali metal complex, the alkaline earth-metal complex, and the rare earth metal complex may include one of ions of the alkali metal, ions of the alkaline earth metal, or ions of the rare earth metal, and a ligand bonded to the metal ion (for example, hydroxyquinoline, hydroxyisoquinoline, hydroxybenzoquinoline, hydroxyacridine, hydroxyphenanthridine, hydroxyphenyloxazole, hydroxyphenylthiazole, hydroxydiphenyloxadiazole, hydroxydiphenylthiadiazole, hydroxyphenylpyridine, hydroxyphenyl benzimidazole, hydroxyphenylbenzothiazole, bipyridine, phenanthroline, cyclopentadiene, or any combination thereof).
The electron injection layer may consist of an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal-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 any combination thereof, as described above. In embodiments, 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 consist of an alkali metal-containing compound (for example, an alkali metal halide); or the electron injection layer may consist of an alkali metal-containing compound (for example, an alkali metal halide), and an alkali metal, an alkaline earth metal, a rare earth metal, or any combination thereof. For example, the electron injection layer may be a KI:Yb co-deposited layer, an Rbl:Yb co-deposited layer, or the like.
When the electron injection layer further includes an organic material, 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 any combination thereof may be uniformly or non-uniformly dispersed in a matrix including the organic material.
A thickness of the electron injection layer may be in a range of about 1 Å to about 100 Å. For example, the thickness of the electron injection layer may be in a range of about 3 Å to about 90 Å. When the thickness of the electron injection layer is within these ranges, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.
The second electrode 150 may be located on the interlayer 130 having a structure as described above. The second electrode 150 may be a cathode, which is an electron injection electrode. The second electrode 150 may include a material having a low-work function, for example, a metal, an alloy, an electrically conductive compound, or any combination thereof.
The second electrode 150 may include lithium (Li), silver (Ag), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), ytterbium (Yb), silver-ytterbium (Ag—Yb), ITO, IZO, or any combination thereof. The second electrode 150 may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode.
The second electrode 150 may have a single-layered structure or a multilayered structure including two or more layers.
A first capping layer may be located outside the first electrode 110, and/or a second capping layer may be located outside the second electrode 150. For example, the light-emitting device 10 may have a structure in which the first capping layer, the first electrode 110, the interlayer 130, and the second electrode 150 are stacked in the stated order, a structure in which the first electrode 110, the interlayer 130, the second electrode 150, and the second capping layer are stacked in the stated order, or a structure in which the first capping layer, the first electrode 110, the interlayer 130, the second electrode 150, and the second capping layer are stacked in the stated order.
Light generated in the emission layer of the interlayer 130 of the light-emitting device 10 may be extracted toward the outside through the first electrode 110, which may be a semi-transmissive electrode or a transmissive electrode, and through the first capping layer. Light generated in the emission layer of the interlayer 130 of the light-emitting device 10 may be extracted toward the outside through the second electrode 150, which may be a semi-transmissive electrode or a transmissive electrode, and through the second capping layer.
The first capping layer and the second capping layer may each increase external luminescence efficiency according to the principle of constructive interference. Accordingly, the light extraction efficiency of the light-emitting device 10 may be increased, so that the luminescence efficiency of the light-emitting device 10 may be improved.
The first capping layer and the second capping layer may each include a material having a refractive index equal to or greater than about 1.6 (with respect to a wavelength of about 589 nm).
The first capping layer and the second capping layer may each independently be an organic capping layer including an organic material, an inorganic capping layer including an inorganic material, or a composite capping layer including an organic material and an inorganic material.
At least one of the first capping layer and the second capping layer may each independently include a carbocyclic compound, a heterocyclic compound, an amine group-containing compound, a porphyrin derivative, a phthalocyanine derivative, a naphthalocyanine derivative, an alkali metal complex, an alkaline earth metal complex, or any combination thereof. The carbocyclic compound, the heterocyclic compound, and the amine group-containing compound may optionally be substituted with a substituent including O, N, S, Se, Si, F, Cl, Br, I, or any combination thereof.
In an embodiment, at least one of the first capping layer and the second capping layer may each independently include an amine group-containing compound.
For example, at least one of the first capping layer and the second capping layer may each independently include a compound represented by Formula 201, a compound represented by Formula 202, or any combination thereof.
In embodiments, at least one of the first capping layer and the second capping layer may each independently include one of Compounds HT28 to HT33, one of Compounds CP1 to CP6, β-NPB, or any combination thereof:
The light-emitting device may be included in various electronic apparatuses. For example, the electronic apparatus including the light-emitting device may be a light-emitting apparatus, an authentication apparatus, or the like.
The electronic apparatus (for example, a light-emitting apparatus) may further include, in addition to the light-emitting device, a color filter, a color conversion layer, or 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. Further details on the light-emitting device may be found in reference to related descriptions as provided herein. In an embodiment, the color conversion layer may include a quantum dot. 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 subpixels, the color filter may include color filter areas respectively corresponding to the subpixels, and the color conversion layer may include color conversion areas respectively corresponding to the subpixels.
A pixel-defining film may be located between the subpixels to define each subpixel.
The color filter may further include color filter areas and light-shielding patterns located between the color filter areas, and the color conversion layer may further include color conversion areas and light-shielding patterns located between 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. 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 color filter areas (or the color conversion areas) may include quantum dots. For example, the first area may include red quantum dots, the second area may include green quantum dots, and the third area may not include quantum dots. Further details on the quantum dot may be found in reference related descriptions provided herein. 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. The first-first color light, the second-first color light, and the third-first color light may have different maximum emission wavelengths from one another. 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 electronic apparatus may further include a thin-film transistor, in addition to the light-emitting device as described above. The thin-film transistor may include a source electrode, a drain electrode, and an active layer, wherein at least one of the source electrode and the drain electrode may be electrically connected to one of the first electrode or the second electrode of the light-emitting device.
The thin-film transistor may further include a gate electrode, a gate insulating film, and the like.
The active layer may include crystalline silicon, amorphous silicon, an organic semiconductor, an oxide semiconductor, and the like.
The electronic apparatus may further include a sealing portion for sealing the light-emitting device. The sealing portion may be located between the color conversion layer and/or color filter, and the light-emitting device. The sealing portion may allow light from the light-emitting device to be extracted to the outside, and may simultaneously prevent ambient air and moisture from penetrating into the light-emitting device. The sealing portion may be a sealing substrate including a transparent glass substrate or a plastic substrate. The sealing portion may be a thin-film encapsulation layer including an organic layer and/or an inorganic layer. When the sealing portion is a thin film encapsulation layer, the electronic apparatus may be flexible.
Various functional layers may be further included on the sealing portion, in addition to the color filter and/or the color conversion layer, according to the use of the electronic apparatus. Examples of the functional layers may include a touch screen layer, a polarizing layer, an authentication apparatus, and the like. The touch screen layer may be a pressure-sensitive touch screen layer, a capacitive touch screen layer, or an infrared touch screen layer. The authentication apparatus may be, for example, a biometric authentication apparatus that authenticates an individual by using biometric information of a living body (for example, fingertips, pupils, and the like).
The authentication apparatus may further include, in addition to the light-emitting device as described above, a biometric information collector.
The electronic apparatus may be applied to various displays, such as light sources, lighting, personal computers (for example, a mobile personal computer), mobile phones, digital cameras, electronic organizers, electronic dictionaries, electronic game machines, medical instruments (for example, electronic thermometers, sphygmomanometers, blood glucose meters, pulse measurement devices, pulse wave measurement devices, electrocardiogram displays, ultrasonic diagnostic devices, or endoscope displays), fish finders, various measuring instruments, meters (for example, meters for a vehicle, an aircraft, and a vessel), projectors, and the like.
The electronic apparatus of
The substrate 100 may be a flexible substrate, a glass substrate, or a metal substrate. A buffer layer 210 may be located on the substrate 100. The buffer layer 210 may prevent penetration of impurities through the substrate 100 and may provide a flat surface on the substrate 100.
The TFT may be located on the buffer layer 210. The TFT may include an active layer 220, a gate electrode 240, a source electrode 260, and a drain electrode 270.
The active layer 220 may 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 film 230 for insulating the active layer 220 from the gate electrode 240 may be located on the active layer 220, and the gate electrode 240 may be located on the gate insulating film 230.
An interlayer insulating film 250 may be located on the gate electrode 240. The interlayer insulating film 250 may be located between the gate electrode 240 and the source electrode 260 and between the gate electrode 240 and the drain electrode 270, to insulate the gate electrode 240, the source electrode 260, and the drain electrode 270 from one another.
The source electrode 260 and the drain electrode 270 may be located on the interlayer insulating film 250. The interlayer insulating film 250 and the gate insulating film 230 may be formed to expose the source region and the drain region of the active layer 220, and the source electrode 260 and the drain electrode 270 may respectively contact the exposed portions of the source region and the drain region of the active layer 220.
The TFT may be electrically connected to a light-emitting device to drive the light-emitting device, and may be protected by being covered with a passivation layer 280. The passivation layer 280 may include an inorganic insulating film, an organic insulating film, or any combination thereof. The light-emitting device is provided on the passivation layer 280. The light-emitting device may include a first electrode 110, an interlayer 130, and a second electrode 150.
The first electrode 110 may be located on the passivation layer 280. The passivation layer 280 may not completely cover the drain electrode 270 and may expose a portion of the drain electrode 270, and the first electrode 110 may be electrically connected to the exposed portion of the drain electrode 270.
A pixel defining layer 290 including an insulating material may be located on the first electrode 110. The pixel defining layer 290 may expose a region of the first electrode 110, and an interlayer 130 may be formed in the exposed region of the first electrode 110. The pixel defining layer 290 may include a polyimide-based organic film or a polyacrylic-based organic film. Although not shown in
The second electrode 150 may be located on the interlayer 130, and a capping layer 170 may be additionally formed on the second electrode 150. The capping layer 170 may be formed to cover the second electrode 150.
The encapsulation portion 300 may be located on the capping layer 170. The encapsulation portion 300 may be located on the light-emitting device to protect the light-emitting device from moisture and/or oxygen. The encapsulation portion 300 may include: an inorganic film including silicon nitride (SiNx), silicon oxide (SiOx), indium tin oxide, indium zinc oxide, or any combination thereof; an organic film including polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyethylene sulfonate, polyoxymethylene, polyarylate, hexamethyldisiloxane, an acrylic resin (for example, polymethyl methacrylate, polyacrylic acid, etc.), an epoxy-based resin (for example, aliphatic glycidyl ether (AGE), etc.), or any combination thereof; or any combination of the inorganic film and the organic film.
The electronic apparatus of
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 specific region by using one or more suitable methods such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) deposition, ink-jet printing, laser-printing, and laser-induced thermal imaging (LITI).
When respective layers included in the hole transport region, the emission layer, and respective layers included in the electron transport region are formed by vacuum deposition, the deposition conditions may include a deposition temperature in a range of about 100° C. to about 500° C., a vacuum degree of about 10-8 torr to about 10-3 torr, and a deposition speed in a range of about 0.01 Å/sec to about 100 Å/sec, depending on a material to be included in a layer to be formed and the structure of a layer to be formed.
The term “C3-C60 carbocyclic group” as used herein may be a cyclic group consisting of carbon atoms as the only ring-forming atoms and having 3 to 60 carbon atoms, and the term “C1-C60 heterocyclic group” as used herein may be a cyclic group that has 1 to 60 carbon atoms and further has, in addition to carbon, at least one heteroatom as a ring-forming atom. The C3-C60 carbocyclic group and the C1-C60 heterocyclic group may each be a monocyclic group consisting of one ring or a polycyclic group in which two or more rings are condensed with each other. For example, the number of ring-forming atoms of the C1-C60 heterocyclic group may be from 3 to 61.
The term “cyclic group” as used herein may include the C3-C60 carbocyclic group or the C1-C60 heterocyclic group.
The term “Π electron-rich C3-C60 cyclic group” as used herein may be a cyclic group that has 3 to 60 carbon atoms and may not include *—N═*’ as a ring-forming moiety. The term “Π electron-deficient nitrogen-containing C1-C60 cyclic group” as used herein may be a heterocyclic group that has 1 to 60 carbon atoms and may include *—N═*’ as a ring-forming moiety.
In embodiments,
The terms “cyclic group”, “C3-C60 carbocyclic group”, “C1-C60 heterocyclic group”, “Π electron-rich C3-C60 cyclic group”, or “Π electron-deficient nitrogen-containing C1-C60 cyclic group” as used herein may each be a group condensed to any cyclic group, monovalent group, or polyvalent group (for example, a divalent group, a trivalent group, a tetravalent group, and the like) according to the structure of a formula for which the corresponding term is used. For example, a “benzene group” may be a benzo group, a phenyl group, a phenylene group, or the like, which may be readily understood by one of ordinary skill in the art according to the structure of a formula including the “benzene group.”
Examples of a monovalent C3-C60 carbocyclic group and a monovalent C1-C60 heterocyclic group may include a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C1-C60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group. Examples of a divalent C3-C60 carbocyclic group and a divalent C1-C60 heterocyclic group may include a C3-C10 cycloalkylene group, a C1-C10 heterocycloalkylene group, a C3-C10 cycloalkenylene group, a C1-C10 heterocycloalkenylene group, a C6-C60 arylene group, a C1-C60 heteroarylene group, a divalent non-aromatic condensed polycyclic group, and a substituted or unsubstituted divalent non-aromatic condensed heteropolycyclic group.
The term “C1-C60 alkyl group” as used herein may be a linear or a branched aliphatic hydrocarbon monovalent group having 1 to 60 carbon atoms, and examples thereof may include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an iso-nonyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, and the like. The term “C1-C60 alkylene group” as used herein may be a divalent group having a same structure as the C1-C60 alkyl group.
The term “C2-C60 alkenyl group” as used herein may be a monovalent hydrocarbon group having at least one carbon-carbon double bond in the middle or at a terminus of a C2-C60 alkyl group, and examples thereof may include an ethenyl group, a propenyl group, a butenyl group, and the like. The term “C2-C60 alkenylene group” as used herein may be a divalent group having a same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein may be a monovalent hydrocarbon group having at least one carbon-carbon triple bond in the middle or at a terminus of a C2-C60 alkyl group, and examples thereof may include an ethynyl group, a propynyl group, and the like. The term “C2-C60 alkynylene group” as used herein may be a divalent group having a same structure as the C2-C60 alkynyl group.
The term “C1-C60 alkoxy group” as used herein may be a monovalent group represented by -O(A101) (wherein A101 is a C1-C60 alkyl group), and examples thereof may include a methoxy group, an ethoxy group, an isopropyloxy group, and the like.
The term “C3-C10 cycloalkyl group” as used herein may be a monovalent saturated hydrocarbon cyclic group having 3 to 10 carbon atoms, and examples thereof may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group (or a bicyclo[2.2.1]heptyl group), a bicyclo[1.1.1]pentyl group, a bicyclo[2.1.1]hexyl group, a bicyclo[2.2.2]octyl group, and the like. The term “C3-C10 cycloalkylene group” as used herein may be a divalent group having a same structure as the C3-C10 cycloalkyl group.
The term “C1-C10 heterocycloalkyl group” as used herein may be a monovalent cyclic group of 1 to 10 carbon atoms, further including, in addition to carbon atoms, at least one heteroatom as a ring-forming atom, and examples thereof may include a 1,2,3,4-oxatriazolidinyl group, a tetrahydrofuranyl group, a tetrahydrothiophenyl group, and the like. The term “C1-C10 heterocycloalkylene group” as used herein may be a divalent group having a same structure as the C1-C10 heterocycloalkyl group.
The term “C3-C10 cycloalkenyl group” as used herein may be a monovalent cyclic group that has three to ten carbon atoms and at least one carbon-carbon double bond in the cyclic structure thereof and no aromaticity, and examples thereof may include a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and the like. The term “C3-C10 cycloalkenylene group” as used herein may be a divalent group having a same structure as the C3-C10 cycloalkenyl group.
The term “C1-C10 heterocycloalkenyl group” as used herein may be a monovalent cyclic group of 1 to 10 carbon atoms, further including, in addition to carbon atoms, at least one heteroatom as a ring-forming atom, and having at least one carbon-carbon double bond in the cyclic structure thereof. Examples of the C1-C10 heterocycloalkenyl group may include a 4,5-dihydro-1,2,3,4-oxatriazolyl group, a 2,3-dihydrofuranyl group, a 2,3-dihydrothiophenyl group, and the like. The term “C1-C10 heterocycloalkenylene group” as used herein may be a divalent group having a same structure as the C1-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as used herein may be a monovalent group having a carbocyclic aromatic system of 6 to 60 carbon atoms, and the term “C6-C60 arylene group” as used herein may be a divalent group having a carbocyclic aromatic system of 6 to 60 carbon atoms. Examples of the C6-C60 aryl group may include a phenyl group, a pentalenyl group, a naphthyl group, an azulenyl group, an indacenyl group, an acenaphthyl group, a phenalenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a pentaphenyl group, a heptalenyl group, a naphthacenyl group, a picenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group, an ovalenyl group, and the like. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the two or more rings may be condensed with each other.
The term “C1-C60 heteroaryl group” as used herein may be 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 a ring-forming atom. The term “C1-C60 heteroarylene group” as used herein may be 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 a ring-forming atom. Examples of the C1-C60 heteroaryl group may 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, and the like. When the C1-C60 heteroaryl group and the C1-C60 heteroarylene group each include two or more rings, the rings may be condensed with each other.
The term “monovalent non-aromatic condensed polycyclic group” as used herein may be 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 having no aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic condensed polycyclic group may include an indenyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, an indenophenanthrenyl group, an indenoanthracenyl group, and the like. The term “divalent non-aromatic condensed polycyclic group” as used herein may be a divalent group having a same structure as the monovalent non-aromatic condensed polycyclic group.
The term “monovalent non-aromatic condensed heteropolycyclic group” as used herein may be a monovalent group (for example, having 1 to 60 carbon atoms) having two or more rings condensed to each other, further including, in addition to carbon atoms, at least one heteroatom as a ring-forming atom, and having no aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic condensed heteropolycyclic group may include a pyrrolyl group, a thiophenyl group, a furanyl group, an indolyl group, a benzoindolyl group, a naphthoindolyl group, an isoindolyl group, a benzoisoindolyl group, a naphthoisoindolyl group, a benzosilolyl group, a benzothiophenyl group, a benzofuranyl group, a carbazolyl group, a dibenzosilolyl group, a dibenzothiophenyl group, a dibenzofuranyl group, an azacarbazolyl group, an azafluorenyl group, an azadibenzosilolyl group, an azadibenzothiophenyl group, an azadibenzofuranyl group, a pyrazolyl group, an imidazolyl group, a triazolyl group, a tetrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzopyrazolyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a benzoxadiazolyl group, a benzothiadiazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, an imidazotriazinyl group, an imidazopyrazinyl group, an imidazopyridazinyl group, an indenocarbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzosilolocarbazolyl group, a benzoindolocarbazolyl group, a benzocarbazolyl group, a benzonaphthofuranyl group, a benzonaphthothiophenyl group, a benzonaphthosilolyl group, a benzofurodibenzofuranyl group, a benzofurodibenzothiophenyl group, a benzothienodibenzothiophenyl group, and the like. The term “divalent non-aromatic condensed heteropolycyclic group” as used herein may be a divalent group having a same structure as the monovalent non-aromatic condensed heteropolycyclic group.
The term “C6-C60 aryloxy group” as used herein may be represented by -O(A102) (wherein A102 is a C6-C60 aryl group), and the term “C6-C60 arylthio group” as used herein may be represented by -S(A103) (wherein A103 is a C6-C60 aryl group).
The term “R10a” as used herein may be:
In the specification, Q1 to Q3, Q11 to Q13, Q21 to Q23, and Q31 to Q33 may each independently be: hydrogen; deuterium; —F; —Cl; —Br; —I; a hydroxyl group; a cyano group; a nitro group; a C1-C60 alkyl group; a C2-C60 alkenyl group; a C2-C60 alkynyl group; a C1-C60 alkoxy group; or a C3-C60 carbocyclic group or a C1-C60 heterocyclic group, each unsubstituted or substituted with deuterium, —F, a cyano group, a C1-C60 alkyl group, a C1-C60 alkoxy group, a phenyl group, a biphenyl group, or any combination thereof.
The term “heteroatom” as used herein may be any atom other than a carbon atom or a hydrogen atom. Examples of the heteroatom may include O, S, N, P, Si, B, Ge, Se, or any combination thereof.
The term “Ph” as used herein refers to a phenyl group, the term “Me” as used herein refers to a methyl group, the term “Et” as used herein refers to an ethyl group, the terms “ter-Bu” or “But” as used herein each refer to a tert-butyl group, and the term “OMe” as used herein refers to a methoxy group.
The term “biphenyl group” as used herein may be “a phenyl group substituted with a phenyl group.” For example, the “biphenyl group” may be “a substituted phenyl group” having a “C6-C60 aryl group” as a substituent.
The term “terphenyl group” as used herein may be “a phenyl group substituted with a biphenyl group.” For example, the “terphenyl group” may be “a substituted phenyl group” having a “C6-C60 aryl group substituted with a C6-C60 aryl group” as a substituent.
The symbols * and *’ as used 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 detail with reference to the following Synthesis Examples and Examples. The wording “B was used instead of A” when used in describing Synthesis Examples means that an identical molar equivalent of B was used in place of A.
Synthesis Example 1: Synthesis of Compound 13
3.5 g (20 mmol) of 3-bromopyridine-2-amine, 7.5 g (24 mmol) of 1-bromo-2-iodo-4-methoxybenzene, 0.92 g (0.1 mmol) of Pd2(dba)3, 0.11 g (0.2 mmol) of DPPF(1,1′-bis(diphenylphosphino)ferrocene), and 2.7 g (28 mmol) of NaOtBu were placed in a reaction vessel and suspended in 100 ml of toluene. The reaction mixture was heated to a temperature of 120° C. and stirred for 20 hours. After completion of the reaction, the reaction result was cooled at room temperature, 300 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 6.4 g (18 mmol) of Intermediate 13-1.
6.4 g (18 mmol) of Intermediate 13-1, 10.8 g (72 mmol) of Nal, 0.034 g (0.18 mmol) of Cul, and 0.032 g (0.36 mmol) of N,N′-dimethylenediamine were placed in a reaction vessel and suspended in dioxane. The reaction mixture was heated to a temperature of 110° C. and stirred for 24 hours. After completion of the reaction, the reaction result was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution, and dried using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 7.7 g (17 mmol) of Intermediate 13-2.
7.7 g (17 mmol) of Intermediate 13-2, 2.7 g (34 mmol) of selenium powder, and 3.8 g (68 mmol) of potassium hydroxide were suspended in a dimethyl sulfoxide solution. The reaction mixture was heated to a temperature of 110° C. and stirred for 24 hours. After completion of the reaction, the reaction product was cooled at room temperature, and an appropriate amount of sodium hydrogen carbonate was added thereto to perform neutralization. 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An extracted organic layer was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 4.0 g (14.5 mmol) of Intermediate 13-3.
4.0 g (14.5 mmol) of Intermediate 13-3, 4.7 g (22 mmol) of 2-bromo-4(tert-butyl)pyridine, 6.7 g (29 mmol) of potassium phosphate tribasic, 0.53 g (2.9 mmol) of Cul, and 0.32 g (2.9 mmol) of picolinic acid were placed in a reaction vessel and suspended in 60 ml of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C. and stirred for 24 hours. After completion of the reaction, the reaction result was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 5.3 g (13 mmol) of Intermediate 13-4.
5.3 g (13 mmol) of Intermediate 13-4 was suspended in an excess of bromic acid solution. The reaction mixture was heated to a temperature of 110° C. and stirred for 24 hours. After completion of the reaction, the reaction product was cooled at room temperature, and an appropriate amount of sodium hydrogen carbonate was added thereto to perform neutralization. 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An extracted organic layer was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 4.8 g (12 mmol) of Intermediate 13-5.
4.7 g (12 mmol) of Intermediate 13-5, 4.9 g (18 mmol) of 1-(3-bromophenyl)-1H-benzo[d]imidazole, 5.5 g (24 mmol) of potassium phosphate tribasic, 0.43 g (0.24 mmol) of Cul, and 0.027 g (0.24 mmol) of picolinic acid were placed in a reaction vessel and suspended in 50 ml of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C. and stirred for 24 hours. After completion of the reaction, the reaction result was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 5.9 g (10 mmol) of Intermediate 13-6.
5.9 g (10 mmol) of Intermediate 13-6 and 15 mmol of diphenyliodanium were suspended in toluene. The reaction mixture was heated to a temperature of 110° C. and stirred for 24 hours. After completion of the reaction, the reaction result was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 6.6 g (8.3 mmol) of Intermediate 13-7.
6.6 g (8.3 mmol) of Intermediate 13-7 and 4.1 g (25 mmol) of ammonium hexafluorophosphate were placed in a reaction vessel and suspended in a mixed solution including 160 ml of methyl alcohol and 40 ml of water. The reaction mixture was stirred at room temperature for 24 hours. After completion of the reaction, the resulting solid was filtered and washed with ether. The washed solid was dried to obtain 6.3 g (7.8 mmol) of Intermediate 13-8.
6.3 g (7.8 mmol) of Intermediate 13-8, 3.0 g (8.1 mmol) of dichloro(1,5-cyclooctadiene)platinum, and 1.3 g (16 mmol) of sodium acetate were suspended in 80 ml of dioxane. The reaction mixture was heated to a temperature of 110° C. and stirred for 72 hours. After completion of the reaction, the reaction result was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 1.8 g (2.1 mmol) of Compound 13.
Synthesis Example 2: Synthesis of Compound 24
Intermediate 24-1 was obtained in the same manner as used to prepare Intermediate 13-5 of Synthesis Example 1, except that 4-bromopyridin-3-amine was used instead of 3-bromopyridin-2-amine.
5.5 g (14 mmol) of Intermediate 24-1, 3.7 g (21 mmol) of 1-bromo-3-fluorobenzene, and 6.5 g (28 mmol) of potassium phosphate tribasic were placed in a reaction vessel and suspended in 50 ml of dimethyl sulfoxide. The reaction mixture was heated to a temperature of 160° C. and stirred for 12 hours. After completion of the reaction, the reaction result was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 6.6 g (12 mmol) of Intermediate 24-2.
6.6 g (12 mmol) of Intermediate 24-2, 4.5 g (13 mmol) of N1-([1,1′:3′,1″-terphenyl]-2′-nyl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)benzene-1,2-diamine, SPhos (0.98 mmol), Pd2(dba)3 (0.65 mmol), and sodium t-butoxide (26 mmol) were suspended in 100 ml of a toluene solvent, heated to a temperature of 100° C., and stirred for 5 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 9.0 g (11 mmol) of Intermediate 24-3.
9.0 g (11 mmol) of Intermediate 24-3 was dissolved in 550 mmol of triethylorthoformate, and 13 mmol of HCl was added dropwise thereto. The temperature was raised to 80° C. and the mixture was stirred for 20 hours. After completion of the reaction, the solvent was removed therefrom under reduced pressure, and an extraction process was performed thereon by using methylene chloride and distilled water. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 8.6 g (10 mmol) of Intermediate 24-4.
8.6 g (10 mmol) of Intermediate 24-4 and 4.9 g (30 mmol) of ammonium hexafluorophosphate were placed in a reaction vessel and suspended in a mixed solution including 200 ml of methyl alcohol and 50 ml of water. The reaction mixture was stirred at room temperature for 12 hours. After completion of the reaction, the resulting solid was filtered and washed with ether. The washed solid was dried to obtain 9.0 g (9.3 mmol) of Intermediate 24-5.
9.0 g (9.3 mmol) of Intermediate 24-5, 3.4 g (10.2 mmol) of dichloro(1,5-cyclooctadiene)platinum, and 1.5 g (18.6 mmol) of sodium acetate were suspended in 100 ml of dioxane. The reaction mixture was heated to a temperature of 110° C. and stirred for 72 hours. After completion of the reaction, the reaction result was cooled at room temperature, 200 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 2.4 g (2.4 mmol) of Compound 24.
Synthesis Example 3: Synthesis of Compound 33
Intermediate 33-1 was obtained in the same manner as used to prepare Intermediate 13-5 of Synthesis Example 1, except that 2-bromopyridin-3-amine was used instead of 3-bromopyridin-2-amine, and 2-bromopyridine was used instead of 2-bromo-4(tert-butyl)pyridine.
Intermediate 33-2 was obtained in the same manner as used to prepare Intermediate 13-6 of Synthesis Example 1, except that Intermediate 33-1 was used instead of Intermediate 13-5, and Intermediate A-1 was used instead of 1-(3-bromophenyl)-1H-benzo[d]imidazole.
6.4 g (10 mmol) of Intermediate 33-2, 8.8 g (15 mmol) of Intermediate A-2, and 0.18 g (1.0 mmol) of Cu(OAc)2 were added to dimethyl sulfoxide, and the reaction mixture was heated to a temperature of 150° C. and stirred for 12 hours. After completion of the reaction, the reaction result was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 5.7 g (6.2 mmol) of Intermediate 33-3.
2.1 g (2.2 mmol) of Compound 33 was obtained in the same manner as used to prepare Compound 13 of Synthesis Example 1, except that Intermediate 33-3 was used instead of Intermediate 13-8.
Synthesis Example 4: Synthesis of Compound 52
Intermediate 52-1 was obtained in the same manner as used to prepare Intermediate 13-4 of Synthesis Example 1, except that 3-bromo-5-chloropyridin-2-amine was used instead of 3-bromopyridin-2-amine.
4.4 g (10 mmol) of Intermediate 52-1, 1.6 g (13 mmol) of phenylboronic acid, 0.23 g (1.0 mmol) of palladium acetate, 0.95 g (2.0 mmol) of Xphos, and 6.5 g (20 mmol) of cesium carbonate were suspended in 90 ml/30 ml of dioxane/water. The reaction mixture was heated to a temperature of 100° C. and stirred for 12 hours. After completion of the reaction, the reaction result was cooled at room temperature, 100 ml of distilled water was added thereto, and an extraction process was performed thereon by using ethyl acetate. An organic layer extracted therefrom was washed with a saturated aqueous sodium chloride solution and dried by using sodium sulfate. A residue obtained by removing the solvent therefrom was separated by column chromatography to obtain 4.6 g (9.5 mmol) of Intermediate 52-2.
Intermediate 52-3 was obtained in the same manner as used to prepare Intermediate 13-5 of Synthesis Example 1, except that Intermediate 52-2 was used instead of Intermediate 13-4.
Intermediate 52-4 was obtained in the same manner as used to prepare Intermediate 24-2 of Synthesis Example 2, except that Intermediate 52-3 was used instead of Intermediate 24-1.
Intermediate 52-5 was obtained in the same manner as used to prepare Intermediate 24-3 of Synthesis Example 2, except that Intermediate 52-4 was used instead of Intermediate 24-2, and Intermediate A-3 was used instead of N1-([1,1′:3′,1″-terphenyl]-2′-nyl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)benzene-1,2-diamine.
Intermediate 52-6 was obtained in the same manner as used to prepare Intermediate 24-4 of Synthesis Example 2, except that Intermediate 52-5 was used instead of Intermediate 24-3.
Intermediate 52-7 was obtained in the same manner as used to prepare Intermediate 24-5 of Synthesis Example 2, except that Intermediate 52-6 was used instead of Intermediate 24-4.
2.1 g (1.8 mmol) of Compound 52 was obtained in the same manner as used to prepare Compound 24 of Synthesis Example 2, except that Intermediate 52-7 was used instead of Intermediate 24-5.
Synthesis Example 5: Synthesis of Compound 60
Intermediate 60-1 was obtained in the same manner as used to prepare Intermediate 13-5 of Synthesis Example 1, except that 3-bromopyridin-4-amine was used instead of 3-bromopyridin-2-amine, and 2-bromo-1-phenyl-1 H-benzo[d]imidazole was used instead of 2-bromo-4(tert-butyl)pyridine.
Intermediate 60-2 was obtained in the same manner as used to prepare Intermediate 24-2 of Synthesis Example 2, except that Intermediate 60-1 was used instead of Intermediate 24-1.
Intermediate 60-3 was obtained in the same manner as used to prepare Intermediate 24-3 of Synthesis Example 2, except that Intermediate 60-2 was used instead of Intermediate 24-2, and Intermediate A-4 was used instead of N1-([1,1′:3′,1″-terphenyl]-2′-nyl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)benzene-1,2-diamine.
Intermediate 60-4 was obtained in the same manner as used to prepare Intermediate 24-4 of Synthesis Example 2, except that Intermediate 60-3 was used instead of Intermediate 24-3.
Intermediate 60-5 was obtained in the same manner as used to prepare Intermediate 24-5 of Synthesis Example 2, except that Intermediate 60-4 was used instead of Intermediate 24-4.
1.7 g (1.6 mmol) of Compound 60 was obtained in the same manner as used to prepare Compound 24 of Synthesis Example 2, except that Intermediate 60-5 was used instead of Intermediate 24-5.
Synthesis Example 6: Synthesis of Compound 85
Intermediate 85-1 was obtained in the same manner as used to prepare Intermediate 13-2 of Synthesis Example 1, except that 2-bromoaniline was used instead of 3-bromopyridin-2-amine.
Intermediate 85-2 was obtained in the same manner as used to prepare Intermediate 13-3 of Synthesis Example 1, except that Intermediate 85-1 was used instead of Intermediate 13-2, and tellurium powder was used instead of selenium powder.
Intermediate 85-3 was obtained in the same manner as used to prepare Intermediate 13-4 of Synthesis Example 1, except that Intermediate 85-2 was used instead of Intermediate 13-3.
Intermediate 85-4 was obtained in the same manner as used to prepare Intermediate 13-5 of Synthesis Example 1, except that Intermediate 85-3 was used instead of Intermediate 13-4.
Intermediate 85-5 was obtained in the same manner as used to prepare Intermediate 24-2 of Synthesis Example 2, except that Intermediate 85-4 was used instead of Intermediate 24-1.
Intermediate 85-6 was obtained in the same manner as used to prepare Intermediate 24-3 of Synthesis Example 2, except that Intermediate 85-5 was used instead of Intermediate 24-2, and Intermediate A-5 was used instead of N1-([1,1′:3′,1″-terphenyl]-2′-nyl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)benzene-1,2-diamine.
Intermediate 85-7 was obtained in the same manner as used to prepare Intermediate 24-4 of Synthesis Example 2, except that Intermediate 85-6 was used instead of Intermediate 24-3.
Intermediate 85-8 was obtained in the same manner as used to prepare Intermediate 24-5 of Synthesis Example 2, except that Intermediate 85-7 was used instead of Intermediate 24-4.
2.1 g (1.9 mmol) of Compound 85 was obtained in the same manner as used to prepare Compound 24 of Synthesis Example 2, except that Intermediate 85-8 was used instead of Intermediate 24-5.
Synthesis Example 7: Synthesis of Compound 100
Intermediate 100-1 was obtained in the same manner as used to prepare Intermediate 52-4 of Synthesis Example 4, except that 2-bromo-4-chloroaniline was used instead of 3-bromo-5-chloropyridin-2-amine, and tellurium powder was used instead of selenium powder.
Intermediate 100-2 was obtained in the same manner as used to prepare Intermediate 24-3 of Synthesis Example 2, except that Intermediate 100-1 was used instead of Intermediate 24-2, and Intermediate A-6 was used instead of N1-([1,1′:3′,1″-terphenyl]-2′-nyl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)benzene-1,2-diamine.
Intermediate 100-3 was obtained in the same manner as used to prepare Intermediate 24-4 of Synthesis Example 2, except that Intermediate 100-2 was used instead of Intermediate 24-3.
Intermediate 100-4 was obtained in the same manner as used to prepare Intermediate 24-5 of Synthesis Example 2, except that Intermediate 100-3 was used instead of Intermediate 24-4.
2.0 g (1.6 mmol) of Compound 100 was obtained in the same manner as used to prepare Compound 24 of Synthesis Example 2, except that Intermediate 100-4 was used instead of Intermediate 24-5.
Synthesis Example 8: Synthesis of Compound 128
Intermediate 128-1 was obtained in the same manner as used to prepare Intermediate 85-3 of Synthesis Example 6, except that 2-bromobenzo[d]thiazole was used instead of 2-bromo-4(tert-butyl)pyridine.
Intermediate 128-2 was obtained in the same manner as used to prepare Intermediate 85-4 of Synthesis Example 6, except that Intermediate 128-1 was used instead of Intermediate 85-3.
Intermediate 128-3 was obtained in the same manner as used to prepare Intermediate 13-6 of Synthesis Example 1, except that Intermediate 128-2 was used instead of Intermediate 13-5.
Intermediate 128-4 was obtained in the same manner as used to prepare Intermediate 13-7 of Synthesis Example 1, except that Intermediate 128-3 was used instead of Intermediate 13-6.
Intermediate 128-5 was obtained in the same manner as used to prepare Intermediate 13-8 of Synthesis Example 1, except that Intermediate 128-4 was used instead of Intermediate 13-7.
1.7 g (1.9 mmol) of Compound 128 was obtained in the same manner as used to prepare Compound 13 of Synthesis Example 1, except that Intermediate 128-5 was used instead of Intermediate 13-8.
Synthesis Example 9: Synthesis of Compound 140
Intermediate 140-1 was obtained in the same manner as used to prepare Intermediate 24-2 of Synthesis Example 2, except that 2-bromoaniline was used instead of 4-bromopyridin-3-amine, 5-bromo-4-iodo-2methoxypyridine was used instead of 1-bromo-2-iodo-4-methoxybenzene, and tellurium powder was used instead of selenium powder.
Intermediate 140-2 was obtained in the same manner as used to prepare Intermediate 24-3 of Synthesis Example 2, except that Intermediate 140-1 was used instead of Intermediate 24-2.
Intermediate 140-3 was obtained in the same manner as used to prepare Intermediate 24-4 of Synthesis Example 2, except that Intermediate 140-2 was used instead of Intermediate 24-3.
Intermediate 140-4 was obtained in the same manner as used to prepare Intermediate 24-5 of Synthesis Example 2, except that Intermediate 140-3 was used instead of Intermediate 24-4.
2.3 g (2.2 mmol) of Compound 140 was obtained in the same manner as used to prepare Compound 24 of Synthesis Example 2, except that Intermediate 140-4 was used instead of Intermediate 24-5.
1H NMR and MS/FAB of the compounds synthesized according to Synthesis Examples 1 to 9 are shown in Table 1. Synthesis methods for other compounds than the compounds shown in Table 1 may be readily recognized by those skilled in the technical field by referring to the synthesis paths and source material materials described above.
1H NMR (δ)
As an anode, a glass substrate with 15 Ωcm2 (1,200 Å) ITO thereon, which was manufactured by Corning Inc., was cut to a size of 50 mm×50 mm×0.7 mm, and the glass substrate was sonicated by using isopropyl alcohol and pure water for 5 minutes each, and ultraviolet light was irradiated for 30 minutes thereto, and ozone was exposed thereto for cleaning. The resultant glass substrate was loaded onto a vacuum deposition apparatus.
2-TNATA was vacuum-deposited on an ITO anode formed on the glass substrate to form a hole injection layer having a thickness of 600 Å, and NPB was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 300 Å.
Compound 13 (10 wt%) as a dopant and Compounds ETH2 and HTH29 (weight ratio 3:7) as a host were co-deposited on the hole transport layer to form an emission layer having a thickness of 300 Å.
ETH2 was vacuum-deposited on the emission layer to form a hole blocking layer having a thickness of 50 Å. Alq3 was 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 an Al electrode having a thickness of 3,000 Å(cathode) to form an LiF/Al electrode, thereby completing the manufacture of a light-emitting device.
Light-emitting devices were manufactured in the same manner as in Example 1, except that, in forming an emission layer, for use as a dopant and a host, compounds shown in Table 2 were used at corresponding weight ratios.
A light-emitting device was manufactured in the same manner as in Example 1, except that, in forming an emission layer, Compound 100 (10 wt%) and Compound DFD2 (0.5 wt%) were used as a dopant, and Compounds ETH66 and HTH29 (weight ratio 3:7) as a host were co-deposited to form an emission layer having a thickness of 400 Å.
A light-emitting device was manufactured in the same manner as in Example 1, except that, in forming an emission layer, Compound CE1 (10 wt%) as a dopant and Compound ETH2 as a host were co-deposited to form an emission layer having a thickness of 300 Å.
A light-emitting device was manufactured in the same manner as in Example 1, except that, in forming an emission layer, Compound CE2 (10 wt%) as a dopant and Compound ETH2 as a host were co-deposited to form an emission layer having a thickness of 300 Å.
A light-emitting device was manufactured in the same manner as in Example 1, except that, in forming an emission layer, Compound CE3 (10 wt%) as a dopant and Compounds ETH2 and HTH29 (weight ratio 3:7) as a host were co-deposited to form an emission layer having a thickness of 300 Å.
To evaluate characteristics of the light-emitting devices manufactured according to Examples 1 to 11 and Comparative Examples 1 to 3, the driving voltage at the current density of 50 mA/cm2, luminance, CIE, luminescence efficiency, color conversion efficiency, and lifespan thereof were measured. The driving voltage of the light-emitting devices was measured using a source meter (Keithley Instrument Inc., 2400 series). The lifespan is a measure of the time (T95) taken for the luminance to reach 95 % of the maximum luminance. Table 2 shows the evaluation results of the characteristics of the light-emitting devices.
Referring to Table 2, it can be seen that the light-emitting devices of Examples 1 to 11 have excellent driving voltage, color purity, luminescence efficiency, color conversion efficiency, and lifespan, as compared to the light-emitting devices of Comparative Examples 1 to 3.
The organometallic compound may be used in manufacturing a light-emitting device having high efficiency and a long lifespan, and the light-emitting device may be used in manufacturing a high-quality electronic apparatus high efficiency and a long lifespan.
Embodiments have been disclosed herein, and although terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purpose of limitation. In some instances, as would be apparent by one of ordinary skill in the art, features, characteristics, and/or elements described in connection with an embodiment may be used singly or in combination with features, characteristics, and/or elements described in connection with other embodiments unless otherwise specifically indicated. Accordingly, it will be understood by those of ordinary skill in the art that various changes in form and details may be made without departing from the spirit and scope of the disclosure as set forth in the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0156046 | Nov 2021 | KR | national |
